CHAPTER THe 18 VALeNce ELecTRON RULE 2.1 IntRopuCTION ‘The elementary basis for discussing structure and bonding in organometallic compounds is based on the 18 valence electron rule. This rule, in combination with the concept of backbonding or extent of r-acceptor capabilities of ligands, helps one to arrive at the relative stahility of arganometallic compounds. Hapticity and sandwich compounds A number of unsaturated organic anions and molecules such as allyl, cyclopentadienyl and benzene can bind to a metal in more than one way. The different modes are distinguished by the number of carbon atoms participating in linkage with the metal (to be more precise, one has to see how many carbon atoms are present within bonding distance from the metal atom). The hapto symbol, n, with a numerical superscript, provides topological description by indicating the connectivity between the ligand and the central atom. For example, if all the five carbon atoms of a cyclopentadienyl moiety are equidistant from a metal atom, we term it as n°-cyclopentadienyl. 2.2 Tue 18 Evectron Rute This rule was first formulated by Irwing Langmuir in 1921 with a view to extend the octet theory of G N Lewis ~ based on the static-atom model ~ beyond argon in the periodic table.! He derived the following equation where v, = the number of shared electrons ofa given atom in a compound or metal complex, = the number of electrons required for the completion of its valence shell and e = the number of valence electrons in the isolated atom. For example, NH, 3=8-5 Ni(CO), 8 =18~ 10 Cr(CO), 12= 18-6The 18 valence electron rule 19 For common organic compounds where the octet rule was followed, the value of s was 8 and for organometallic complexes ~ such as metal carbonyls, on which this rule was first effectively employed ~ the value of s was 18. An alternative electron counting procedure, now well known as the effective atomic number rule (EAN), based on Bohr’s atom model and electronic configuration, was proposed by Nevil Sidgwick in 1923 The Tocus of this, fale was not just on the valence shell electrons but also on the total atom electron count of a compound and the stability of the compound was cquated to the electronic configuration of the nearest noble gas. The EAN rule was popular till the 1960s and was applied to all types. of metal complexes. However, by the late 1960s, the chemical community reverted to the 18 electron rule basically due to the ease of usage. It is evident that the EAN rule invokes the use of the chemically inactive core electrons that results in separate numerical stability standards for each row of the transition metals [36 (Kr, first row), 54 (Xe, second row) or 86 (Ra, third row)] while for the 18 electron rule, a single numerical standard is applicable to the entire block of transition metals. The rule has since then been very popular among organometallic chemists? ‘To apply this rule, the assumptions made were that the ligands were Lewis bases and the metal ions were Lewis acids. The rule states that thermodynamically stable transition metal organometallic compounds are formed when the sum of the metal d electrons and the electrons conventionally considered as being supplied by the surrounding ligands equals 18. An alternate and general statement is that when the metal in question achieves an outer shell configuration of ns? (n ~ 1)d” np’, there will be 18 electrons in the valence orbitals and a closed, stable configuration is attained. This rule of thumb is obeyed with a rather high frequency by organometallic compounds. In general, the conditions favouring adherence to the 18 electron rule are, an electron rich central metal (one that is in alow oxidation state) and ligands that are good n-acceptors.** By counting the number of outer shell electrons surrounding each metal atom in a complex, it is possible to predict whether the complex will be stable and in some cases, whether there will be metal-metal bonds present or not. There are two methods of electron counting—the neutral atom counting method and the oxidation state counting method. ‘The neutral atom method is more foolproof as it does not require the correct assignment of metal oxidation states (which is sometimes difficult in organometallic compounds). However, the oxidation count method is more realistic as it reflects the precise number of electrons available for donation on a ligand. Table 2.1 gives the electron contributions for avariety of ligands according to the neutral atom and oxidation state counting methods.”* 2.3 COUNTING OF ELECTRONS AND FiNoING MeTAL—MeTAL Bonps, Since metal carbonyl compounds contain the metal in the low oxidation state, there are many compounds that possess M-M bonds and fall into the category of metal carbonyl clusters. Indeed, the largest and structurally most complex cluster compounds belong to this class. To determine the total number of M-M bonds and to find out the number of bonds each metal makes with the other metal atoms in a cluster, the following procedure is followed. ‘This procedure applies only to those complexes having a nuclearity < 4. The electronic structures are easily understandable in terms of an electron pair bond between each adjacent pair of metal atoms, with each metal atom attaining the 18 electron configuration.20 Basic organometallic chemistry I ¥ € [A-(HO)-W] aPROTy-T - ¥ € GN-(Caa)-W) oprydsoya-r I y € — DA-CaN)-W] opty r z 1 ony vaSoreH =x iS ¥ € (a-x-w) xt 0 ¥ ¥ audyty-t r z 1 Hal 0 z z tw-(09)-W] 09-4 t z 1 (as-1) areIOrEL, b z 1 (HO-W) aPROATY Se 9 € (a= yy) eudqrea, e y z Cx =14) au9qieD rd 9 t Huayrerdayopo-t + z € avout sont 0 9 9 susauag-, r z 1 quag 1Ason1N tr 9 s jAuarperuadopdd- wonngryu0> afrey wonngru0> unog = wore Poured YOM toe powaur ares uoRePALO porpaur wore fesINAN, pussy] pouaur ayes uonepAXO wow jenMaN, puvsry SuO}NgHIUD UO!DE/s JJeu) PUB spUBB|| UOWWOD Lz e1GeLThe 18 valence electron rule 21 neutral atom oxidation state method method Ru 8 6 (Rus2) nP-allyl a 4 2PPhy 4 4 co 2 2 charge __-1 not required 16 16 nT Me << Fe 8 6 (Fe +2) a Me 2a8.cp 10 12 @ 3 Calculating the M—M bond (i) Determine the total valence electrons (T'VE) in the entire molecule (that is, the number of valence electrons of the metal plus the number of electrons from each ligand and the charge); Say it is A. (ii) Subtract this number from n x 18 where n is the number of metals in the complex, that is, (mx 18) - Aj say, it is B. (iii) (a) B divided by 2 gives the total number of M-M bonds in the complex. (b) A divided by n gives the number of electrons per metal. If the number of electrons is 18, it indicates that there is no M-M bond; if it is 17 electrons, it indicates that there is 1 M-M bond; if it is 16 electrons, it indicates that there are 2 M-M bonds and so on. Table 2.2 TVE calculation of some mononuclear complexes using the oxidation state electron counting method Compound Formal oxidation state of metal | TVE Cx(CO), 0 6+ (2x6) =18 Fe(CO), 0 84+ (2x5)=18 nf-CpFe(CO),Cl 2 6+6+442=18 CH.Mn (CO), 4 2464 (2x5)=18 (Fe(CO),.* 2 8+ (2x4) +2=18 {n'-Cp,Co}* 8 (6x 2)+7-1=18 (Mn(Co), + 7+ (2x6)-1218 n-Cp n?-Cp Fe(CO) 2 446464221822 Basic organometallic chemistry Table 2.3 M-M bond calculations for some multinuclear complexes Molecule ‘IVE (18xn)-A TotalM-M Bonds per _Basic geometry of a) ®) bonds (B/2) metal metal atoms Fe,(CO),, 48 54-48=6 — 6/2=3 48/3 =16;2 Fe— Fe W Co{CO),, 60 72-60=12 12/2=6 /\\, NZ Co. {n’-CpMo(CO),], 30 -36-30=6 = 6/2=3 30/2=15;3 Mo=Mo @CH),Fe(CO), 30 36-30=6 = 6I2=3, 30/2= 15:3 Feske Fe(CO), 34 36-34=22D=1 34/2 = 1751 eRe In drawing the most probable structure of the given compound, the metal core is written firct. The carbonyl groupe and the other ligands are arranged on the metal in ouch a way that each metal atom follows the i8e rule. The CO group can occupy eithera terminal or a bridged position. To illustrate this concept, consider the example of (t1~CO),-[n°-Cp Rh], (CO). TVE=4+ (6 +8) x 3] +2=48 0rd + [5 +9) x3] +2=48 (otal number of M-M bonds = (3 x 18) - 48 = 6/2 =3 Number of bonds per metal atom = 2 (since 48/3 = 16; each metal makes two M-M bonds) ‘he two plausible structures are given below. Among them, structure A is the right one. The vay structure B is drawn (it satisfies the given formula with 2 bridged CO and one terminal 30), the electron count on the three Rh atoms is 17e, 18e and 19e. Hence the structure is not cceptable? RAN ByASN I~ INS oc— Ah » &> 2 ey € 18 electron rule forms the fundamental basis on which many physical and chemical aperties of organo-transition metal compounds can be explained. It can be used predict the number of ligands a particular metal can coordinate with as well as the bility/reactivity of the complex thus formed. The rule works best for low-valent metals with the It elec Le Wh fiek earl Rh, orb ont tot par dor she rep. th th re ekThe 18 valence electron rule 23 with small ligands that are strong o-donors and/or m-acceptors. Such small ligands allow the metal to be coordinately saturated and give a large value of ligand field splitting. It may be noted that as in the case of the octet rule, there are many exceptions to the 18 electron rule. arene | EC 2.4 COMPLIANCE AND VIOLATION OF THE 18 ELECTRON RULE While a large number of organometallic complexes, especially those possessing strong field ligands such as CO obey the 18 electron rule, there are many complexes like those of early transition metals (such as Ti, Zr, V) and square planar late transition metals (such as Rh, Pd, Pt) which do not obey the rule. To find an explanation, the basics of the molecular orbital interactions in a typical organometallic complex have to be understood first. Based on thenature of the metal-ligand orbital interactions, organometallic ligands are observed to behave as 6-donors, 2-donors or m-acceptors. While the type of interaction in the first ‘two cases is similar ~ where an electron pair is donated from the ligand to an empty or partly empty orbital of the metal — in the case of the t-acceptor type interaction, the donation of electrons takes place from the metal to the antibonding orbital of the ligand which has a comparable symmetry and energy to the metal orbital involved. Figure 2.1 shows the difference between these two types of interactions (see Fig. 3.3 for a pictorial representation). ° a Metal Ligand Metal Ligand Molecular orbital formed by 2 Molecular orbital formed by a «5 donor ligand (Example NH) 1 acceptor ligand (Example CO) Fig. 21 MO diagrams of o-donor and r-acceptor ligands. Information on the compliance of the 18 electron rule can be obtained by considering the molecular orbital picture of the complexes. The 6 only MO diagram of an octahedral complex (Fig. 2.2) indicates that there are six bonding orbitals, which are closer in energy to the original ligand group orbitals. These can accommodate a totat of 12 borrdiyrg electrons ‘fom the ligands. Now most of the organometallic octahedral complexes which obey the 18 electron rule have m-acceptor ligands. The electrons from the metal can be accomodated24 Basic organometallic chemistry in the #,, orbitals, which in a purely o only consideration are nonbondirig, but become bonding’ when 1 back bonding is considered. For example, in the case of, Mo(CO), the strong O-donor ability of carbon monoxide raises the energy of the ¢," orbitals making them more antibonding while its strong x-acceptor ability helps to stabilise the t, orbitals further as bonding orbitals. These t, bonding orbitals can now accommodate another 6 electrons, thereby giving a total of 18 electrons. Antibonding Nonbonding Bonding Lag Metal Complex 6 Ligands Fig. 2.2 6 only MO diagram of an octahedral complex A similar situation can be seen in the MO diagram of sandwich compounds such as ferrocene (Fig. 18.3) where electrons are filled in the bonding and nonbonding orbitals, and the HOMO is a nonbonding a, (d,2) orbital. ‘The energy level diagram of bis(benzene) chromium, another 18e sandwich complex is quite similar to that of ferrocene, For complexes having only o- or x-donor ligands, the possibility of violation of the 18 electron rule is therefore more frequent. Fig. level elect base isar elec int} ado sinc spli cor the hav tetr fror elecThe 18 valence electron rule 25 +06, + 0178A, 10228 Ao 4 Octahedral Tetrahedral Square planar “Trigonal bipyramidal ing diagrams of various geometries showing approximate energy levels Fora five-coordinate trigonal bipyramidal complex such as Fe(CO), which obeys the 18 electron rule, the crystal field splitting diagram (Fig, 2.3) indicates that four of the metal based orbitals have negative crystal field splittings and are low in energy and only one orbital is antibonding. These four bonding/nonbonding metal based orbitals can accommodate 8 electrons and the 10 electrons donated by the five ligand group orbitals are accommodated in the ligand based bonding molecular orbitals of lower energy—the total of 18 electrons is accounted for. For a tetrahedral complex such as Ni(CO), which obeys the 18 electron rule, the practice adopted so far in explaining compliance with the 18 electron rule does not appear to work since four ligands will supply 8 electrons and only two orbitals have negative crystal field splittings. However, in tetrahedral complexes the magnitude of splitting between the f, and corbitals is very small and therefore both the t, and the e sets of d orbitals donate electrons to the m acceptor orbitals of the CO ligands leading to a bonding interaction. MO calculations have shown that these x bonding interactions dominate over the o bonding interactions in tetrahedral complexes, which account for the splitting of the d orbitals. Thus contributions from all the five metal d orbitals are to be taken together to account for the required 10 electrons along with the 8 electrons supplied by the four ligands."26 Basic organometallic chemistry Pitfalls encountered while counting electrons While counting of the valence electrons of organometallic complexes having only terminal ligands is rather straightforward, there are many pitfalls that one should be concerned about while undertaking the counting of electrons of multimetallic complexes possessing bridging ligands with or without metal-metal bonds. Bridging ligands are often of the jt, type and rarely bt, Selected examples of organometallic complexes having bridging ligands and their electron counting based on the neutral atom counting method are shown below. For neutral ligands such as carbonyls, irrespective of whether they are terminal, 41,0 ty or whether following the neutral atom/oxidation state counting method, the electron count remains the same (2). For bridging mono-anionic ligands such as Cl’, using the neutral atom counting method, itis a 3e donor when itis p, anda Se donor when tis u.,. This can be envisaged from the assumption that the ligand binds to one metal through the anionic charge and to others using the available lone pair(s). In the case of bridging H’ and CH, since no lone pairs are available, they remain one-electron donors. For multi-anionic ligands, bridging of the metal sites takes place using the anionic charges and therefore CH,” and O* remain 2e donors, while RCandN™ are 3e donors as per the neutral atom counting method. Note that these will be 4e and 6e donors eaThe 18 valence electron rule 27 respectively in the oxidation state counting method. Similar to bridging halides, y, bridging amido ligands are 3e donors as are phosphides and alkoxides. Each metal-metal single bond involves 2 electrons and the contribution to electron counting per metal will be one electron which is essentially an electron shared from the other metal. Understanding such a metal-metal bond becomes easier ifit is compared to the covalent bond between the two chlorineatoms in Cl,. A dear violation of the 18 electron rule is the case of square planar organometallic complexes of the late transition metals. As shown in the erystal field splitting diagram, four of the d orbitals either have a negative or a small positive crystal field splitting (Fig. 2.3). One of the orbitals, the 422, has a large positive crystal field splitting. of +1.228A,, In MO terms, this orbital is clearly antibonding and normally remains unoccupied. ‘The total valance electron count in this case therefore includes 8 electrons donated by the fou ligands and 8 electrons from the four low energy d orbitals totalling only 16. In addition, many organometallic complexes of the early transition metals violate the 18 electron rule (for example Cp,TiCl,, WMe, Me,NbCI,, CpWOCL,). A possible reason is that some of the orbitals of these complexes are too high in energy for effective utilisation in bonding, or the ligands are mostly o-donors, Many high valent d® complexes have a lower electron count than 18, Also, sterically demanding bulky ligands force complexes to have less than 18 electrons. The 18 electron rule fails when bonding in moderate to big organometallic clusters are considered. The bonding of clusters and their stabilities are therefore considered under other electron counting rules (see Chapter 10, Metal Clusters). Also, the rule is not applicable to organometallic compounds of main group metals and to those of lanthanide and actinide metals, Problems and Exercises 2,16 Suggest and draw possible 18 electron structures which can be formed from the following combinations of metals and ligands. Use at least one unit of each ligand listed for the particular metal. Propose only neutral complexes. Do not use more than two metal centres and show your electron counting. If there is more than one possibility, indicate which complex will be the most stable (note that ligands are indicated without charges). (@) Ru, CO, CH, PMe, (b) Mo, allyl, Cp, NO © Rh, dppe (chelating), 1-CO,HC2CH ——(d) Ix, Cp, H, PMe, 2.2, Consider the 18 electron rule as a guide and determine the value of m in the following complexes. (@) Na,Fe(CO). ate (b) MnBr(Co), = S (oWay-CH ICO), 428 @RhGy-C,H (C0), EEL (©) Cr(r?-C,H,)(CO),(CH) yr (6) InBr,(CO),(PPh,),(CH,) +=" 2.3. For the following molecules, give the formal oxidation state of the metal, d electron count, total valence electrons (TVE) and the number of M-M bonds if any.28 Basic organometallic chemistry Complex Oxidation State delectron count TVE M-Mbonds [CpCo(CO)), (1-CO) +1 B 2 4 (cyclo C,H, PACI, ah @ 16 SI (np-ally).Ni ane g 44 e CpMo(CO}; ° 6 {& co Ru(PPh,),C(NO) (linear NO) & & \¢ 6 Cpin'-C,H)Mn a é (8 Ci Cp,21Hi(CH,CH,CH,) th UY 6 O CpMn(CO), *\ & 1 6 CpZrCl, 44 g WW a 2.4. Predict M if it is a first row transition element and [M(?-C,H,)(CO),] is a stable compound. \/ 2.5, ‘The complex [M(n°-C,H,)(CO),], obeys the 18 electron rule and has one metal-metal double bond. Predict Mand sketch the probable structure of the complex. 2.6. A metal complex having the empirical formula FeC,H,O,Cl, has one ligand as a substituted cyclopentadienyl group. Itisan ionic compound and has poor solubility in hydrocarbon solvents. The compound gives a white precipitate on treatment with AgNO, solution. Assuming that it obeys the 18 electron rule, suggest its structure. 2.7. Determine the number of metal-metal bonds in the following complexes which obey the 18 electron rule. (@) (CO),Rh(u-Cl),Rh(CO), (b) (q°-C,H,)(CO)Fe(t-CO), Fe(CO}(n-C,H,) 2.8. Determine the unknown quantity Moni (@) [CpW(CO),], (has W-W single bond) 4-2, (b) [(CO),Ni-Co(CO),}* (© [CpMn(CO),], (has Mn=Mn double bond) (4) (Cp), Ni,(4, CO), (has 3 Ni-Ni bonds) © [CpM(CO),), (has a single M-M bond; M = F* row transition metal) 2.9. The given complexes are thermodynamically stable. Comment on the nature of NO in these complexes. Which among them is expected to have a shorter metal-nitrogen bond? Give reasons. (@) (7-allyl)Ru(CO),(NO) (b) (n°-Cp)Ru(CO), (NO) 2.10, The given dimeric rhodium complexes have two symmetrically bridging groups (H and Ch. The geometry around the rhodium in both cases is square planar. Draw the possible structures and determine the expected bond order of the rhodium-rhodium bond in both cases. “ @)[(y?-ethylene), Rh(w-H)], (b) [ir?-ethylene),Rh(u-Cl), 211. oc. oc— oc’ 2.12. 2.13. 2.14,‘The 18 valence electron rule 29 2.11, The metal duster {Ru,(CO),(PPh,),] is very stable. Which among the following will be the actual structure of the molecule? Justify your answer. / co og co. ye AY oc, FOPMT | co. oc. SL co. Qn" Q # - ee 4 Se co OC hu—Fu-—-RO—CO co INI /\_ YS S| | \ oN 7 \Z “co oc—Fu ‘Ri RU—co oc Ri CO Phy Go CO NN oe VA INS \ oc“/ \ o' ¢ § co o¢ Pern PhP A 8 c 2.12. The following reactions of first row transition metal containing metallocenes having n®-Cp ligands lead to stable products. Identify the transition metals A, Band C present in these compounds. " b ~~ i avai oe VY 2.13.. Chromium is known to form complexes with carbonyl and nitrosyl ligands. For complexes of the type Cr(CO),(NO),,, determine the values of mand 1, so that one can realise compounds which obey the 18 electron ruleand which have only linear nitrosyl ligands. Note that there can be more than one answer. The value of m and m can be zero or higher. 2.14, Following the 18e rule as a guide, determine x in the following complexes. (a) {n?-CpOs(CO},}, (has an Os-Os single bond) _(b) [Co(CO),* (©) {(Ni(CO), NO} (consider NO as linear) (€) In'-Cp Fe(CO),|* (©) [n°-(C,H)Mn(CO) (CH, {n'-Cp(CO),Fe(PhC = CH)]* 2.15. For the given compounds, calculate (a) the total number of M-M bonds in each molecule and (b) the number of M-M bonds each metal makes with the other metal. Also draw the most appropriate structure in each case. (a) (u-H), [r#-Cp(NO)WH], (NO is linear) (b) (u-Br), [Mn(CO),], (© u-CO--CH,-[n°-CpRh], (4) {p-X--CH,0s,(CO),.)”30 Basic organometallic chemistry (e) (CO),V(w-PR,),V(CO), (£) [’-CpMn(CO),], (g) {n°-CpCr(CO),}, (b) [n-CpFe(CO),], t (i) [n*-CpMo(CO),],- @)Ir(CO),, (k) (u-CO)-In¢ -CpRe(CO),], (D (w-CO}- [nt (C,H)Fe(CO)), (m) (¥,-CO)-(Pe (CO), > 2.16. Draw the structure of [HRu(PPh,),]* which obeys the 18 electron rule, 2.17. Trimetallic complexes of phosphido bridges are well known. Assuming that the 18e rule is followed, postulate the structure of [Mn(}1-PH,)(CO),],, (Organometallics, 1989, Vol. 8, 857) 2.18. Predict the formal charge and the oxidation state electron count of the starred ligand in the given complexes, all of which obey the 18 electron rule, The oxidation state of Fe = +2and Co= +1 in these compounds. g | Qa Fe | Co ZZ. G 8 : ie es Ph S| Xi NY Z (al and B with one H) (CeMes)FeCp {(7, 8-CoBeH1.)FeCp)_ [(CeHs)«Ca]CoCp Supplementary reading 1. Langmuir I, Types of valence, Science, 1921, Vol. 54, 59, 2. Sidgwick N V, The electronic theory of valency, Clarendon Press, Oxford, 1927, Chapter 10. 3. Jenson W B, The origin of the 18-electron rule, J. Chem. Educ., 2005, Vol. 82, 28. 4 Mitchell P R, Parish J, The eighteen-electron rule, J. Chem. Educ., 1969, Vol. 46, 81. 5. Pyykko P, Understanding the eighteen-electron rule, J. Organomet. Chem., 2006, Vol. 691, 4336, 6. Tolman C A, The 16 and 18 electron rule in organometallic chemistry and homogeneous catalysis, Chem. Sac. Rev., 1972, Vol. 1, 337. 7. Huheey J E, Keiter E A, Keiter RL, Inorganic Chemistry. Principles of structure and reactivity, 4th ed., Harper Collins College Publishers, New York, 1993, 624 8, Douglas BE, McDaniel DH, Alexander] J, Concepts and models in inorganic chemistry, 3rd ed., Wiley, NY, 1994, 9. Paulus E F, Fischer £ O, Fritz H A, Schuster-Wolden H, Die struktur eines isomeren von tris, (x-cyclopentadienyl-Rhodium-carbony!), J. Organometal. Chem., 1967, Vol. 1 3. 10, Wulfsburg G, Inorganic Chemistry, University Science Books, CA, USA, 2002, 479,a CHAPTER METAL CARBONYLS S Carbon monoxide is one of the most important ligands in organometallic chemistry. Homoleptic carbonyls (complexes containing only carbonyls as ligands) can be prepared for many of the d-block metals and these are useful as precursors for other organometallic complexes. The bonding of the carbonyl tothe metal is highly sensitive to electronic effects on the metal centre, ‘This is usually monitored by infrared (IR) spectroscopy. Figure 3.1 shows representative examples of some well known metal carbonyls. Most of the metal carbonyls have the metal in very low oxidation states, sometimes even zero and negative oxidation states.-6 ic r P st Cin, 1 gytCO Nica oc—Fex" Cr oo Wee [co oot | co co co ©00¢ co & co 0c, \f \/ LN ar ne oc 96, ‘Co—CO of bo oc ~=—6O oc’ Nf Noo co or. co oe on / 60 OR Osteo oc IZ INL 007 NYG co i oN, me co oc® | co | Nco oc \ co co ee Fig. 3.1 Some examples of homoleptic metal carbonyls32 Basic organometallic chemistry 3.1 STRUCTURE, 7-BONDING AND INFRARED SPECTROSCOPY The properties of CO as a x acid ligand are well explained by the molecular orbital (MO) diagram of CO (Fig. 3.2). The HOMO of CO is a o orbital having a higher amplitude on the carbon atom than the oxygen atom and is therefore considered as a carbon based orbital which is also slightly antibonding in nature with respect to the oxygen atomic orbitals. The it antibonding orbitals which are the LUMOs are closer in energy to the carbon atomic orbitals than the oxygen atomic orbitals and thus have a greater amplitude on carbon. This explains why CO binds through the carbon atom and also why it is good G-donor and a good m-acceptor. There exists strong back bonding or x overlap of metal electrons to the 1* antibonding orbitals of CO. Ht 2 15.9 ev c Fig. 3.2 Molecular orbital picture of carbon monoxide (not to scale) Most of the metal carbonyls obey the 18 electron rule andin cases where tis not obeyed, the carbonyl will be comparatively more reactive and will undergo reactions such as dimerisation or electron abstraction to gain eighteen electrons, Dimerisation is also dependent upon the size of the metal and the number of ligands it cai accommodate WiowSTEHETEPUISION, ‘This is @ reason why the 17 electron species, V(CO), does not undergo dimerisation while anotl ofan jn at Arete elect coun term the x For « with streti simi] freq T comy throt make dens tore] ore 1 (ro thatMetal carbonyls 33 another 17 electron species Mn(CO), dimerises readily to gain 18 electrons by the formation ofa metal-metal bond [V,(CO),,, prepared by direct condensation of V and CO is table only in. a CO matrix at extremely low temperatures). dL It has been’ found that CO. mainly shows two types of bonding—terminal and bridging. As the C-O stretching frequency is quite sensitive to small changes in the electronic environment, one can identify these by IR spectral studies. (In electron counting methods to find out if the complex obeys the 18 electron rule, both bridging and terminal CO are considered as 2 electron neutral donors) It is rather difficult to arrive at the number of bridging and terminal ligands by using just the electron counting method, For example, Co,(CO), has two isomers - one with no bridging carbonyls and another with two bridging carbonyl groups - both of which are 18 electron species. the C-O stretching frequencies of terminal carbonyls are observed in the range of 2120-1850 cm similar to the free carbon monoxide molecule (2143 cm”) while bridging carbonyl stretching, frequencies are observed in the range of 1850-1750 cm (saturated ketones ~ 1715 cnr"), ‘The bonding of CO to a metal can be described as consisting of two components. The first component is a two electron donation of the lone pair on carbon (coordination exclusively through the oxygen is extremely rare) into a vacant metal d orbital. ‘This electron donation makes the metal niore electron rich, and in order to compensate for this increased electron density, a filled metal d orbital can interact with the empty 1* orbital on the carbonyl ligand tordlieve itself of the added electron density. This second components called m-backbonding ormbackdonation?-? ‘The two components of this bonding re synergistic, More the ¢ donation by thecarbonyl (or other donors on the metal centro), stronger is the n-backbonding interaction, Notice that although this involves the occupation of a m* orbital on the CO, it is still a bonding Carbon monoxide in medicine Carbon monoxide (CO) is known as a toxic gas. Paradoxically, the human body itself produces 3-6 cm’ of CO every day. Certain diseases cause this quantity to increase, which can be detected on the patients breath. British researchers Mannand Motterlini have developed afamily of CO-releasing complexes that could turn out to be a new class of medicines. CO has been demonstrated to play a crucial role as a signal carrier in certain physiological processes, particularly in the cardiovascular system, and is important in various areas of medicine. It thus helps to suppress rejections aftr organ transplants, and reduces the damage caused by disruption of the blood supply to an organ or tissue Gschemia). ‘he use of CU as a drug thus seems obvious. Mann and Motterlini did not want to use CO as a gas; however they were searching for a ‘solid’ form, a compound that would release CO inside the body. They chose to use metal carbonyl complexes. A number of ruthenium and iron complexes proved to be particularly promising. The ruthenium complexes very quickly release CO in the presence of myoglobin, a protein involved in oxygen transport in muscles. In trials, they demonstrated a vasodilatory effect and a significant increase in life expectancy in animalsafter heart transplants. Also noteworthy are some iron complexes that do not transfer CO to myoglobin, yt still acts as vasodilators. In this case, the CO seems to be released directly into cells, which may make it possible to bring CO directly into tissues. CO-releasing molecules such as carbonyl complexes could lead to the development of new drugs for the treatment of cardiovascular diseases as well as neurodegenerative and inflammatory diseases. (Mann B et al, Angew Chem. Int. Ed. Engl, 2008, Vol 42,3722; Otterebin LE et al, Nature Medicine, 2003, Vol. 9,183)34 Basic organometallic chemistry interaction as far as the metal centre is concerned. There is a fundamental similarity between the nature of carbonyl-metal bonding and that of alkenes, acetyJenes, phosphines and dihydrogen. This occupation of the 1* on CO does lead to a decreaséd_hond order in the carbon monoxide molecule itself. The consequences that we might expect if. the CO bond order was reduced would be a lengthening of the C-O bond, shortening of the M-C bond and a decrease in the carbonyl stretching frequency in the IR spectra. As the electron density on a metal centre increases, more m-backbonding to the CO ligand(s) takes place. ‘This weakens the C-O bond further by pumping more electron density into the formally empty carbonyl n* orbital. This increases the M~CO bond strength making it more double- bond-like, that is, the resonance structure M=C=O becomes more important (Fig. 3.3). bond backbond a 2 om JTS anety files filed ¢ 7 empty 1 Peis eorbital orbital orbital Fig. 3.3 Orbital overlap for o and 1 bonding in metal carbonyls Table 3.1. Variation in v,. (em) of the first row transition metal carbonyls!® ‘CO free CO BH;CO 2184 2143 2164 Cu(co)," 2202 Ni(CO), 2057 Co(CO)," Co(CO), 1890 2044(av, ter) Be(CO),} {ke(CO)* Fe(CO), 1815 204 2030 (Mn(Co),- Mn(CO),* Mn,(CO},, 1600, 1790 2098 2013 (av) {ex(Co), J cx(CO), 1462, 1657 2000 VCO), ICO}, 1860 1976 THCO) 1747Metal carbonyls 35 Src Yq Values given in Table 3.1 clearly illustrate the effect of charge, and*thereby electron density on the extent of metal to CO m-backbonding, Although some additional factors such as electronegativity and size of the metal are being projected as influencing the electronic effects, they are minimal and contribute less to the observed CO stretching frequencies. ‘The donorfacceptor ability of the ligands on a metal has considerable effect on the absolute amount of electron density on that metal. This naturally affects the Vz, infrared seething frequencies of metal cxtonys when other ligands are present on the same metal ton the ability of the ligand trans to a CO isa o-donor ligand, it will increase the M-CO bond strength by allowing unrestricted metal-to-CO backbonding. Table 3.2 shows the effect of a series of transligands on the v,,, infrared stretching frequencies of fac isomers of Mo(CO),L,, Pyridine and other amines are not very strong o-donors, and they are even worse n-backbonding ligands, So the CO has virtually no competition for w-backbonding, which results in lower Veg Values. ‘Two interesting trends are observed in the infrared spectra of carbonyl complexes that are both consistent with the concept of m-backbonding. Table 3.2 Effect of different co-ligands on v,, (em) of Mo(CO},L,"* Complex (fac isomers) Mo(CO)(PF,), 2090, 2055, Mo(CO),(PC1,), 2040, 1991 Mo(CO),(P(OMe),], 1977, 1888 Mo(CO),(PPh,), 1934, 1835 Mo(CO),(NCCH,), 1915, 1783, Mo(CO) (dien)* 1898, 1758 Mo(CO),(Py), 1888, 1746 * dien = diethylenetriamine (tridentate) + With each negative charge added to the metal centre, the CO stretching frequency decreases by approximately 100 cm + ‘The better the o donating capability (or poorer the = acceptor ability) of the other ligands on the metal, the lower the CO stretching frequency. The following ligands can be ranked in order of their n-acceptor abilities based on infrared spectral data available on metal carbonyls substituted by ther [NO > CO > PF,> PCI, > POR), > BR; ROEN> NR, | cbonding ligands36 Basic organometallic chemistry In addition to these two significant factors, the effect of electronegativity and size of the metal arealso considered. The former has a marginal effect (Table'3.3) and the latter has no_ effect on the Vig stretching frequencies. [Cr(CO),: 2000cm"; Mo(CO),: 2004.6 Wem W(CO),: 1998 cm" Table 3.3 Relationship between electronegativities of the metal and carbonyl stretching frequencies Metal carbonyl ViCO), _CH(CO), MnO), Fe(CO), _Co,(CO), _Ni(CO), Veg (Eur) 1976 2000 2013 (av) 2023 (av) 2044 (av) 2057 Electronegativity of 1.6 16 16 19 19 the metal (Pauling) Js Bonpinc Moves oF CO CO typically bonds in an end-on fashion through carbon (Fig. 3.4). However, bridging + carbonyls are not uncommon and often undergo exchange with terminal carbonyls. M | c i ° terminal Yoo 2120-1850 cm? ° Yeo(br)1832, 1871 om” ° 1 . v2 bridging He 1850-1700 om 1645 om! J\\ w—\-™ y= bridging 11s 4730-1620 om isocarbonyl coordination 06.00 ee Po. ow *CpeTi, gi os. “cc” “c6. oc’ CO 1895 om" Fig. 3.4 Various bonding modes of CO a bite bridg noter acute centi ofm carb: rathe and four viny met: typi 3.3 and ban: cou: sub: com app. Tab Oo oc less 3. In reeMetal carbonyls 37 Abifferent types of symmetrical and unsymmetrical bridging are observed. within the bridging carbonyls. Among bridging carbonyls, ,-CO is most often encountered and it is noteworthy that j,-CO is not a dimetallaketone. ‘The bond angle in M,CO is much more acute (77-90°) than in R,CO (126*) and is also highly delocalised. Bridging of three metal centres (or capping ofthe triangular Tice ofa polyhedron) is also observed with many dusters, of metal carbonyls [for example, Rh,(CO),, = Rh,(CO),(j-CO),). A variant ofa bridging carbonyl is the ‘semi-bridging’ carbonyl, in which the M-CO-M bond is, asymmetric rather than symmetric. These cai be considered as being, intetmediate between terminal and bridging carbonyls. In another unsymmetrical form called the af bridge, CO acts as a four or six electron donor, and shows a side-on coordination similar to the coordination of vinyl complexes. Isocarbonyl coordination through the oxygen atom ofa coordinated CO to metals such as titanium, aluminum and the lanthanides is also observed, but very rarely. The typical v,, stretching frequency ranges of neutral metal carbonyls are as given in Fig. 34. 3.3 SvMMETRY OF METAL CARBONYLS The local symmetry around the central metal atom of metal carbonyls decides the number and intensity of the carbonyl stretching bands in their IR spectra. The number of IR active bands possible for a specific isomer can be arrived at by using group theory. By simply counting the number of IR bands present, one can deduce the symmetry of most of the substituted metal carbonyls, Table 34 shows the symmetry and number of IR bands for common isomers of substituted octahedral metal carbonyl complexes. The same analysis is applicable to tetrahedral and trigonal bipyramid metal carbonyls. Table 3.4 Relationship between symmetry and number of carbonyl stretching bands®* co L L L L 06», \, CO OC I gos0 Cinq st©9 OCrnngh wt OC 1 sCO Cn, oc” | “co 00% | “co oc% | co ocr | co uo | Loc co co L co co L Mono Trans Cis Fac Mer On(T,,) C.QA+E) Dy) C,QA,+B,+B) C,(A,+B) C,0A,+B) One Thre One Four* Two Three* “The number of bands expected is based on formal selection rules. In some cases, fewer bands are observed. In ML(CO), ifthe four-fold array of CO ligands lies in the same plane, only two bands will be observed. In the cases of cis ML, (CO), and mer ML (CO), if the trans CO ligands are collinear, one band less will be observed 3.4 SYNTHESES OF METAL CARBONYLS In 1868, Schutzenberger prepared the first metal carbonyl compound, [PtCl,(CO)], by the reaction of PtCl, with carbon monoxide. PICh+ CO ———» [PICL(CO)p_ + Cis PICI,(CO}, on38 Basic organometallic chemistry ‘The first metal carbonyls'”** Although Schutzenberger was the first to make a metal carbonyl, the chemistry community considers Ludwig Mond as the father of metal carbonyl chemistry. The serendipitous discovery of Ni(CO), (1890) by Mond and coworkers was followed by discoveries of afew more metal carbonyls such as. Fe(CO), (1891), Co,(CO), and Mo(CO), (1910) by the same group. Mond, who was also the founder of the famous Imperial Chemical Industry (England) was smart enough to notice the industria! potential of his nickel carbonyl and obtained a British patent for making pure nickel by the Mond process in 1890. His ‘Mond nickel company’ was making over 3000 tons of nickel in 1910 with a purity level of 99.99%. It isto be noted that Ni(CO),,a clear liquid which boils at 42°C and decomposes around 180°C to pure nickel is extremely toxic and Mond’s ingenuity has to be complimented as he was able to handle this compound in large quantities successfully at that time. The BASF company in Germany, by using a similar procedure, nowadays manufactures ‘more than 10,000 tons of Fe(CO), per year for making iron oxide pigments used in magnetic tape manufacture. It may be of interest to note that it was during this period of discovery of metal carbonyls that Alfred Werner's theory of bonding in metal complexes was being proposed (1893) and chemists had no idea about the actual shape of metal carbonyls. Indeed the original formulae of Ni(CO), and Fe(CO), given in common chemistry textbooks (see below) published around 1925 reflect the perception at that time. Ni Fe, c&c-c-c ¢-0-o5C if fo Hudew 60009 00000 Ni(CO}, Fe(CO)s Simple homoleptic or binary metal carbonyls are made by two basic methods—direct reaction of the metal with CO and reductive carbonylation in which a metal salt reacts with CO in the presence of a reducing agent. 3.4.1 Direct Carbonylation ‘This method is applicable to the synthesis of only a few metal carbonyls; Ni(CO), is the classic example which was discovered by Ludwig Mond in 1890 and has since then been utilised in the refining of nickel as well.” ——> nico, 17" (3.2 N+ 400) Tae HCO}, colourless mp ~17°C, bp 42°C (32) Fe + 5CO ———__ Fe(CO)s_paleyellow mp -20°C, bp 103°C (3.3) 400 bar, 150°C 3.4.2 Reductive Carbonylation Reductive carbonylation is the most commonly utilised method for the preparation of binary metal carbonyls. Reducing agents such as aluminium, sodium, zinc, tr he Re a uw 2l al In ca reY Metal carbonyls 39 trialkylaluminium and Grignard reagents are used in the reaction with a metal halide or acetate along with carbon monoxide at high pressures and temperatures. Representative reactions are given below, Cat tty 1h + Ale 800 EM. crcoy, + acy CiCip + Ale 600 oper woe CMCOMs + AIC diglyme MoCls + 5Na+ 6CO —————_» oie» ON Shan Oe MOCO}e + § NaCl Vol + 4Na+ 609 SBME INaraiatymeyal ico} POS Vico), 30 bar 240,670 Stain 2-eboxyoharot 0, 200 aim RuCls. 3420 +CO+H, ————"", Rus(Co) = Ru(CO) stable b Se Pus(CO}2 > Ru(COp (unstable) KOH, 75° WCls + 3Zn+ 6CO W(CO)g +3 ZnCk, {ico-P1),0 2Mn(OAc)z +10CO+AIEty ————~_» Mn{CO)io +AlOAc)s + Cabo 207 bar, 80-100°C 2Mn(OAc)p +4Na + 1000 ———DME____Ming(CO)ip +NaO Ac 185°0, 240 bar MeOH 3 Ru(acac)s + 12CO +4.5 Hy; —————» Ru,(CO)jp + 9 MeC(O)CH2C(O)Me i(acac)s He 6, tbo aim Wus(CO)r2 'eC(O)CH,C(O)Me (3.4) (3.5) (6) @n (3.8) 69) (a.t0) (3.11) In the case of metal oxides, carbon monoxide itself acts as a reducing agent and gets converted to CO, in the process. The reaction conditions are relatively more drastic for such reactions. OsO4 +CO MeOH Osa(CO)12 + 4002 CTS aim 1 Re,O, + 1700 eee Rep(CO)i9 + 7CO. uO. x HzO +o toluene Ritg(CO)2 +00 20atm, 160°C C00 + co {9002 Cos(CO)p +00, are 2(CO)s, 2 Fes03 + CO — 200. Fe(CO)s + CO, 225°0 MoO3 + CO — a, Mo(CO)g + C02 300°C 100-150" 2C0COs + 2+ CO BEE Conc}, + 2002 + 2H2O 3.12) (3.13) (2.14) (3.15) (3.16) (17) (218) ‘There are alsoa variety of other methods, however, they are specific to a few metal carbonyls, clusters and industrially useful carbonyls.40 Basic organometallic chemistry MeOH fi NagltCl +CO. ——— > Nte(COpr2 . (3.19) reflux, faim Fe heptane AhCh. 3H0 +co —MH_, tAncoyzci, —TEM — Ahs(COhe (8.20) 100°C, faim 60, 140, NaHCO, MeOH Rhy. BHO +CO ————>_he(CO)re (2%) 60°C, 40-80 atm WMes + excessCO —————» W(CO)z + 3MezCO. (3.22) RhCK(PPhs)3 +ACHO ————» RhCI(CO)(PPhs)z + RH (3.23) (Geinsertion) [Ru(NHg)sH2OP* 22 > [RU(ntH)s(Coy] (3.24) 0k, hy 2 Fe(CO)s — Fex(CO)o +CO (3.25) ‘sunlight : - MnO, ; 3 Fe(CO)s+ 6 OH” a= SINFe(CO\l ——“» Fes(CO}e +3 0 +3MnO (3.26) 2 Co2(CO)e wor COW(COhe + 4CO (3.27) 3.5 Reactions oF METAL CARBONYLS Depending upon whether the metal carbonyl is an 18 electron species or not, dissociative and associative pathways are observed in substitution réactions. For example, a 16 or 17 electron containing metal carbonyl can react by an associative mechanism and it will be much faster than the reactions on an 18 electron metal carbonyl which proceeds by a dissociative mechanism. Substitution of carbonyl groups under thermal and photochemical conditions constitutes the most common reaction of metal carbonyls, In addition, reactions such as disproportionation, oxidative decarbonylation, reduction and addition of nucleophiles on the carbon monoxide also can be carried out on metal carbonyls 3.5.1 Activation of Metal Carbonyls Lewis bases, olefinsand arenes are some of the ligands which can b rbonyls. A complete substitution of all carbonyl groups is “wiiethod that is usually adopted is the activation of a metal hexacarbonyl by the intermediate introduction of relatively more labile ligand that is replaced later by other ligands under mild conditions.” Some of the M(CO), transfer reagents are (THE)Mo(CO), (CH,C1,)Cr(CO),, 20),(norboradiene) (where M = Mo, W) and Fe(CO),(cyclooctadiene). These are prepared by direct reaction of the homoleptic metal carbonyl with the solvent or reagent, under thermal or photochemical conditions, oe aby once caer cc: 3.5 Som liga 3M 3.5 Nuc grot Hiei tor cata oc ocMetal carbonyls 41 Cr(CO}g, a0, 100 min “oO (8.28) THF teow, — OC | cro, + 4] A ligeoin, rete 9 ae HCN ca Cr(CO)p —— 7 — Oh — re oom | noch; 25° G30) NCCHg 3.5.2 Disproportionation : Some multi-metal carbonyls can undergo disproportionation in the presence of suitable ligands often leading to carbonyl anions. 0 BMn{CO)jg + 12Py ZS. 2IMnipy)eP* + 4 {Mn(CO}s) ~ (3.31) 3.5.3 Nucleophilic Addition to CO Nucleophilic addition to the electron deficient carbon atom ofa metal coordinated carbonyl group has become a powerful tool in organometallic chemistry; it is commonly called the Hieber base reaction, Fischer carbenes can be prepared by the addition of alkyllithium ‘to metal carbonyls followed by methylation. Carbenes are important reagents as well as catalysts for a host of organometallic transformations. i CH [Me,O)BF, — CCén, i ait ce | Seco (3.32) co Fischer carbene 3.5.4 Electrophilic Addition to the Carbonyl Oxygen Lewis acids such as AIEt, can attach to the oxygen-end of a coordinated carbonyl group. Only bridging carbonyl groups are nucleophilic enough to undergo this reaction as far as42 Basic organometallic chemistry neutral metal carbonyls are considered. Addition of electrophiles becomes more facile with anionic carbonyl metallates."* er o “Et Q co 2AIEty c, fat \, oN aa pe SS ef, (3.33) s iN oo SY fe D 7 e-Ar er Et 3.5.5 Carbonyl Anions, Cations and Hydrides Carbonyl anions are also formed by reduction or by reactions with strong nucleophiles.*** Mng{CO}jg + 2Na ———» 2 Na[Mn(CO)s} (3.34) CoxCO}s + 2Na ———» 2Na[Co(CO),] (3.35) NaH Fe(CO}s + MeOH rseal Na[HFe(CO),] ——> NaFe(CO), (3.36) While reduction with common reducing agents such as Na amalgam results in mono- or dianionic species, with strong reducing agents such 2s Na/lig. NH, or Na/HMPA, they can be further reduced with the formal oxidation states of the metal reaching even ~4. NajMn(C0}s) +3Na HMPA sya. in(Coyg + 1p NaxCzO2 37 ig Ny K[Co(CO};] + 3K Ta Ni Kg [Co(CO}g] + t/p KCx02 (3.38) Carbonyl cations are prepared mostly by oxidative carbonylation. Lewis acids in anhydrous HE or superacids such as HF-SbE, along with an external oxidant are found to be ideal for realising carbonyl cations. CO (1 atm) Fe(CO)s + XeF2 + 4SbF5 (Fe(CO}el(Sb2F ile (3.39) HP-SbFs, 50°C, 2d CO (0.6 bar) Mng(CO}19 + 2HF + 2BF3+2CO = ———=—— 2 [Mn(CO)eJBFs + H, (3.40) ina(CO}i0 3 arto [Mn(CO)e]BFs + He Carbonyl hydrides are prepared from carbonyl anions, carbonyl halides and dimeric carbonyls. The term hydride is assigned based on the formal oxidation state; however, the pr Based signifi 3.5.¢ Na,Fe Ongar Coll 3.5. ‘The : inser meta mole‘Metal carbonyls 43 the properties of the organometallic hydrides vary from hydridic to protic in character. Based on the nature of the metal and the ligands, the acidity of these complexes varies significantly. Table 3.5 Synthesis of carbonyl hydrido complexes” Methods of synth pKa Comparable acidity [Co(CO) +H = ———» Hco(Co), «1H Lfe(Co),+'NaBti, OHS inpe(cO), 47 CH,COOH Mn,(CO), +H, > 2HMn(CO), 7 HS Fe(CO), + OH” ——> [HFC Mm HO : 3.5.6 Collman’s Reagent ' Na,Fe(CO),, called Collman's reagent, has found many applications in organic synthesis. Organic halogen compounds can be functionalised in many ways via reaction with the Collman’s reagent (Fig, 3.5)2°>° Ry 20 RX NalRFe(CO)47 —_CO ¢ Jat ee Yo mo aon =e” co co Xe — > RCOX RCOOH Fig. 3.5 Uses of Coilman's reagent 3.5.7 Migratory Insertion of Carbonyls The ability of metal carbonyls, especially metal carbonyl anions, to undergo migratory insertion has been utilised in organic synthesis for the preparation of acyl substituted metal carbonyls. These are good precursors for a host of carbonyl containing organic molecules.44 Basic organometallic chemistry ir Cm, | CO Min ae 3.41 oc™ | co high pressure Co oo 3.5.8 Oxidative Decarbonylation Carbonyl metal halides are prepared by oxidative decarbonylation and are good reagents for reactions with metallated reagents. In addition, substituted metal carbonyls can be converted to metal oxides by oxidative decarbonylation, Mng(CO)jp + lp 9 2 Mn(CO)s ee Cp Mn(CO}s (3.42) Fe(CO)s +l —— Fe(CO)ap (3.43) 3.5.9 Photochemical Substitution Photochemical substitutions are the most common photoreactions in organometallic chemistry. Kinetic studies have shown that the rate constant for the dissociation of one. CO unit which precedes the entrance of a new ligand is increased upon photochemical excitation by a factor of (0's. e W(CO)g+ PPhs TY __. w(CO}s(PPhs) + CO (3.44) y 4 Fe(co)s + f\ —™ _» f--Fe(co}y +200 (2.45) Photochemical substitution of CO by monodentate ligands often results only in the displacement of one carbonyl unit. ‘This is because, photochemical excitation of a metal carbonyl with a coordination sphere of mixed substituerits causes the dissociation of the ligand which is the most weakly bonded in the ground state. Therefore, attempts to substitute a second carbonyl from an M(CO),L species results in the displacement of L itself. If ligands of comparable ligand strength are used, one can displace all the carbonyl groups. tw M(CO}s ————> M(CO)sTHF_'”_, coy, + THE (3.46) THF bw Mo(CO) ———* Mo[P(OMe) + 10 (3.47) Ce SO jO[P(OMe)ale + 6 6 (247) Ifafter the dissociation ofa ligand, no suitable free ligands are present, the free coordination site generated through photochemical dissociation of CO may get closed by dimerisation. ‘The gap may also be filled internally by rearrangement of a ligand such as allyl or cyclopentadienyl from 1 to 1 or nto nf. memati 3.5. Carbs accels canb oven quite yields the re [cpm this ¢ NaC) prepa by cra Cm, ‘Then subst: Cn, 3.6 NO elects one « bent nitro electMetal carbonyls 45 Win(CO)g 48) —MuCO's + ny A aq -co 3.5.10 Microwave Assisted Carbonyl Substitution Carbonyl substitution reactions under thermal conditions can often be improved, accelerated and simplified by carrying out the reaction in a microwave oven. The reactions can be carried out in a dedicated microwave oven using teflon reactors or a conventional oven fitted with a facility for inserting a water circulated reflux condenser. Reactions quite often proceed without the need for an inert atmosphere, are clean and give high yields. Usually a solvent such as diglyme or diglyme/THF mixture is used, For example, the reaction of Mo(CO), with dicyclopentadiene affords a simple one step synthesis of [CpMo(CO),], in 94% yield in one hour. In contrast, the conventional methods to synthesise this compound involve (i) the preparation of NaCp and its reaction with Mo(CO), giving Na[CpMo(CO),], followed by oxidation with iron (II) ammonium sulphate or (ii) the preparation of Mo(CO),(CH,CN), and its reaction with freshly prepared ‘C,H,’ obtained by cracking of dicyclopentadiene.” gt go 60.06 26m, 00 . 750W (ricrowave) tho M- aia ohm, th \ oc | “co Smo. ‘0c bo co co a, 94% The microwave assisted method is also useful for high yield synthesis of a variety of cis substituted M(CO),L, complexes from M(CO), within an hour. 750W (microwave) excess | iglymel Orbe THE, 15-40 min (3.50) Lepiperidine (63%) pyridine (50%) Le= phenanthroline (81 %) bipyridine (94%) dppe (98%) 3.6 MeTAL Nitrosyis NO contains one more electron than CO in a N-O 1* orbital and thus can act as a three electron donor. In electron counting terms, 3CO = 2NO. However, NO can also act as a one electron donor when the lone pair resides on the nitrogen and the geometry is in the bent form. In the oxidation state counting method, the ligand is viewed as a coordinated nitrosyl ion, NO*, when in the linear form and as a coordinated NO" when bent. Itis a two electron donor in both the forms. Although either atom in NO is a potential donor, the46 Basic organometallic chemistry nitrogen atom coordinates preferentially avoiding a large formal positive charge on the more electronegative oxygen atom. Nitrosyl complexes are readily formed by the replacement of carbon monoxide with nitric oxide. Only a few organometallic compounds containing nitrosyl ligands alone are known but many mixed carbonyl-nitrosyl complexes obeying the 18 electron rule are known. One problem in the synthesis of nitrosyl complexes by direct reaction with NO is that excess nitric oxide at high temperatures and pressures can cause unfavourable oxidation and decomposition. So, many current synthetic routes use reagents such as nitrosyl chloride (NOC), nitrites and nitrosonium salts. Likecarbonyl complexes,nitrosyl complexesare also characterised using IR spectroscopy. ‘The unpaired electron in NO resides in a n* antibonding orbital and is easily removed to give NO! (as in NO*PR,,). NO* is isoelectronic with CO. Infrared stretching frequencies of free NO is observed at 1896 cm", free NO* at 2250 cm and M-NO in the range of 1600- 1900 can". Bridging nitrosyls are also known, for example, CpCr(NO),Clon treatment with [NaBE, gives [CpCr(NO)(j:NO)], The terminal nitrosyl in this compound are observed at 1675 cm while the bridging NO is observed at 1505'cm" (Fig. 38). — ° ° 0 BA? Vv NZS ones \ | i 0 ‘ oO oO ll 4 NO linear 1672 Nobiidge 1505 om" _ eee Fig. 3.6 Examples of metal nitrosyl complexes NO bent 1687 om Problems and Exercises 3.1. The V-C bond distances in V(CO); and V(CO), are 1.93 and 2.00A respectively. Justify. the difference in bond distances in these compounds. 3.2. In a carbonyl complex having a linear (OC)-M-(CO) group, indicate how v,,, will change when (a) one CO is replaced by E1,N, (b) a positive charge is placed on the complex and (c) a negative charge is placed on the complex. 3.3. Considering NO as a 3e donor, give the formula of the corresponding neutral metal carbonyls which are isoelectronic with Cr(NO),, Mn(CO)(NO),, Co(NO), anc Fe(CO),(NO),, 3.4, V(CO), readily reacts with Na to give Na[V(CO),]. Why? 3.5. N, and CO are isoelectronic molecules but M-N, complexes are much weaker compared to M-CO complexes. Offer a reasonable explanation. 3.6. What happens to vg, when CO gets coordinated to BH, or Ni(CO),? pene ee Cx OmMetal carbonyls 47 3.7. “In LnM-CO complexes, ifCO gets coordinated to aLewisacid A andbecomesLnMCO-A, what will happen to its v,, value? Justify your answer. (Ln = non 7 acid ligand) 3.8. The infrared spectrum of (n’-CpFe(CO),], when measured at room temperature indicated three bands at 2005, 1961 and 1795 cnr? and when measured at high temperature gave a different spectrum with three bands at 2015, 1973 and 1938 cm, In contrast, the infrared spectrum of [n?-CpOs(CO).,], gave bands at 2040, 1986 and 1948 cm when measured both at room temperature and high temperature, Both the compounds obey the 18 electron rule. Draw possible structures of the compounds explaining this phenomenon. Photolysis of [°-CpBe(CO),}, at -78°C results in the loss of a colourless gas and {7 formation of an iron containing product having a single carbonyl band at 1785 cmt \-" and containing 14.7% oxygen by mass. Suggest a structure for the product. 3.10. Arrange the following in the decreasing order of back donation. pCO), [Ti(CO),}*s [Mn(CO),}*s [Ir(CO),]**s [V(CO), J . { 3.147” “The complex (Cx(CO),(PPh,),] has one very strong IR absorption at 1889 cmt and & (CF two other very weak bands in the CO stretching region. What is the probable structure |.” of this compound? = e 12. Suggest a sequence of reactions for the selective preparation of cis-Fe(PPh,),(CO),. Ze You are given Fe metal, CO, Ph,P. Use any reagent of your choice. 3.13. Suppose you are given a series of metal tricarbonyl compounds having the respective symmetries C,, D,, and C, Which of these should display the greatest number of CO stretching bands? op 3.14, Refluxing W(CO), in butryonitrile (C,H,CN) gives three products—W(CO), (NCC\H)), W(CO),(NCC,H,), and W(CO),(NCCH,),, The following v,, (em) values are observed. W(CO)(NCC\H,) 2077, 1975, 1938 W(CO),(NCC,H,), 2017, 1898, 1842 W(CO)(NCC,H,), 1910, 1792 On the basisofthe number ofbands, determine thelikely isomers of W(CO),(NCC,H,), and W(CO),(NCC,H,), and justify the changes in v,, as the number of butyronitrile groups increases. 3.15. On the basis of the given information on the v,, band, which ligand among the following pairs of complexes, (CO or CSe and NS or NO) is the better 1 acceptor ligand. Explain briefly. (a) n-CpRe(CO), 2024, 1937 cm! and n>-CpRe(CO), CSe 2035, 1946 cm™* (b) nP-CpCr(CO), (NS) 2033, 1962 cm" and n°-CpCr(CO), (NO) 2028, 1955 cm? 3.16. Among the given two complexes (a) and (b), which will show a lower carbonyl stretching frequency? Give reasons for your answer.48 Basic organometallic chemistry 3.17. 3.18. 3.19, 3.20, 3.21, 3.22. 3.23, 3.24. Cp oA acl 10 2086 P00 op cp (a) (o) Which one of the given complexes (a) and (b) will undergo ligand substitution faster oat Why? x (b) [V(CO),- A first row transition element M forms a homoleptic carbonyl complex A with the empirical formula M(CO),. A reacts with Na/Hg in tetrahydrofuran solvent to give a compound B whose empirical formula is C,O,MNa. Treatment of B with Mel followed by excess of CO at high pressure resulted in a compound C with the empirical formula CH,O,M. Unlike A and B, compound C had in its infrared spectrum, an extra band in the range 1600-1700 cm. Define the metal Mand write the structures of A, B and C. Compound A on reaction with I, followed by reaction with NaCp loses a colourless gas and gives a stable organometallic compound D with the empirical formula C,H,O,M (a derivative of compound D has applications in the petroleum industry). Suggest the structure of D. Select the best choice in each of the following and briefly justify the reason for your choice. (a) Complex with the shortest C-O bond Ni(CO), {Co(CO),}> [Fe(CO),}* (b) Complex with the lowest C-O stretching frequency Cr(CO),, V(CO);, Fe(CO)2* ‘The compound (n-C,H,)Co(CO), (A) upon UV irradiation, resulted in the evolution ofa gasand formation of new compound, B. While the infrared spectrum of A showed absorptions around 1988 cm, the spectrum of B showed absorptions only at 1798 cm" Compounds A and B obey the 18 electron rule and both have the cyclopentadienyl group in the nf mode, Draw the structure of compound B. An organometallic compound A with the empirical formula MC,O, reacts with nitric oxide to give a new compound B with the empirical formula MC,NO,. B on further reaction with excess of NO under drastic conditions gave a new compound C with the molecular formula MN,O,, Compounds A, B and C are stable and neutral and one among them contains more than one metal atom. Draw the structures of A, B and C The compound Re(CO),Br upon UV irradiation resulted in the evolution of an equimolar amount of a colourless gas and the formation of a new stable complex, X. ‘The infrared spectrum of compound X indicated the absence of any metal-metal bond and showed bands in the range of 2040-1965 cm", ‘The starting material Re(CO),Br also showed bands in the same spectral range. Draw the structure of compound X. in°-CpFe(CO)], isa dark green stable compound. Its infrared spectrum shows a single CO stretching band at 1640 cm. The 'H NMR spectrum shows a single line even at low temperature. Propose a structure for this compound based on the given data, in the given pair of complexes pick out the complex having lower energy CO stretching frequency in its infrared spectrum, Rationalise your choice. meee3.25. 3.26. Metal carbonyls 49 (a) Mo(CO), or Mo(CO),PPh, (b) Fe(CO), or Fe(CO),Br, Provide a plausible explanation for the differences in infrared wave numbers between each of the pairs (a) Mo(PF,)(CO),, 2043 and 1991 cm" vs Mo(PMe,(CO), 1945, 1851 cm (b) MnCp(CO), 2023, 1939 cm? vs MnCp*(CO), 2017, 1928 cm”. When compound A is heated, CO gas is driven off. The product B so formed, readily reacts with CO and reverses the reaction. infrared spectral studies indicate the vg value of A at 1960 cm and B at 1850 cm”', Draw the structures of A and B. -200 Inf-CpMo(CO)se <== n*-opMo(Co)} A +200 8 Supplementary reading L 2. Werner H, Complexes of carbon monoxide and its relatives. An organometallic family celebrates its birthday, Angew. Chem. Int. Ed, 1990, Vol. 29, 1077, . Cotton F A, Metal carbonyls: Some new observations in an old field, Prog. Inorg. Chem, 1976, Vol. 21, 1. Ellis] E, Beck W, New surprises in metal carbonyl chemistry, Angew. Chem. Int. Ed., 1995, Vol. 34,2489 Herrmann W A, 100 years of metal carbonyls: A serendipitus chemical discovery of major scientific and industrial impact, J. Organomet. Chem., 1990, Vol. 383, 21 ‘Trout W E, The metal carbonyls: VIE. Industrial significance, . Chem. Educ., 1938, Vol. 15,113. Hieber W, Forty years of metal carbonyl chemistry, Adv. Organomet. Chem., 1970, Vol. 7,1 Wulfsburg G, Inorganic Chemistry, University Science Books, CA, USA, 2002, 479. Gardner L, Samson} A R, J. Chem. Phys, 1975, Vol. 62, 1447. Jorgensen W L, Salem L, The organic chemists book of orbitals, Acad. Press, San Diego, 197378 Ameen J G, Durfee H F, The structure of metal carbonyls, J. Chem. Educ., 1971, Vol. 48, 372 Atwood J D, Ligand and metal effects on the reactivity of metal carbonyls, . Organomet. Chem, 1990, Vol. 383, 59. . Kettle SF A, The bonding in M(CO), groups (wheren = 1,2,3 &4), J. Chem. Soc. A, 1966, Vol. 4, 420. Blanchard A A, Valence relations among the metal carbonyls, Chem. Rev., 1940, Vol. 26, 409. Abel EW, Bennett MA, Wilkinson G, Substituted carbonyl complexes of chromium, molybdenum, tungsten and manganese, [. Chem. Soc., 1959, 2323. Darensbourg M Y, Darensbourg D J, Infrared determination of stereochemistry in metal complexes. An application of group theory, . Chem. Educ., 1970, Vol. 47, 33. Cotton F A, Chemical applications of group theory, 2nd ed, Wiley NY, 1971 Mond L., HiritzH, Cowap MD, Some new metallic carbonyls, . Chem. Soc. Trans, 1910, Vol.97, 798. Fischer EO, Hafner W, Oefele K, Aromaticcomplexes of metals XXXI, A synthesis of chromium hexacarbonyl, Chem. Ber, 1959, Vol. 92, 3050. Podall H B, Prestridge H B, Shapiro H, Reductive carbonylation synthesis of metal carbonyls 1V, Synthesis of group VIB metal carbonyls using sodium as the reducing agent, J. Am. Chea Soc., 1961, Vol. 83, 2057. {@) Podall H E, Reductive carbonylation synthesis of metal carbonyls 1, A novel synthesis of metal carbonyls by use of Bt,Al as the reducing agent, J. Am. Chem. Soc., 1958, Vol. 80, 5573,50 Basic organometallic chemistry 22, 23. 24, 25. 26. 21. 28. 29. 30. 31 32. 33, 34. (b) Hagen A P, Miller T S, Terrell D L, Hutchinson B, Hance R L, Daniels L, High pressure synthesis of transition metal carbonyls, J. Chem. Educ., 1979, Vol. 56, 479. Liu X, Ellis } E, Miller T D, Ghalasi P, Miller J S, Transition metal carbonyl complexes. Hexacarbonyl vanadate (I-) and hexacarbonylvanadium(0), Inorg. Syuth., 2004, Vol. 34, 96 Samanska-Buzat, T, Photochemical reactions of group 6 metal carbonyls with alkenes, Coord. Chem. Rey., 2006, Vol. 250, 976. Hill A F, Simple carbonyle of ruthenium. New avenues for the Hieber base reaction, Angew. Chem. Int, Edit, 2000, Vol. 39, 130. Alich A, Nelson, N J, Strope D, Shriver D F, Interaction of bridging carbonyl ligands with aluminum alkyl, Inorg. Chem., 1972, Vol. 11, 2976. Ellis] E, Faltynek R A, Highly reduced organometallic anions I. Synthesis and properties of tetracarbonylmetallate(3-) anions of manganese and rhenium, J. Am. Chem. Soc., 1977, Vol. 98, 1801, Geier J, Willner H, Lehmann C W, Aubke B, Formation of hexacarbonylmanganese (I) salts, [Mn(CO),}'X- in anhydrous HE, Inorg. Chent., 2007, Vol. 46, 7210. Walker H W, Kresge CT, Ford P C, Pearson R G, Rates of deprotonation and pX, values of transition metal carbonyl hydrides, J. Am. Chem. Soc, 1979, Vol. 101, 7428. Colman J P, Winter $ R, Clark D R, Selective synthesis of aliphatic ketones using sodium tetracarbonylferrate(-I1), J. Amt. Chem. Soc. 1972, Vol. 94, 1788, Siegel W, Colman J P, Acyl and alkyl tetracarbonylferrate(0) complexes and intermediates in the synthesis of aldehydes and ketones, J. Am. Chem, Soc., 1972, Vol. 4, 2516. Collman J P, Winter § R, Komoto R G, Selective synthesis of aliphatic carboxylic acids, esters and amides using sodium tetracarbonylferrate (-II), J. Am. Chem. Soc., 1973, Vol. 95, 249. Wrighter M, Photochemistry of metal carbonyls, Chen. Rev., 1974, Vol. 74, 401. Strohmeier W, Photochemical reactions of transition metal carbonyls, Angew. Chem., 1963, Vol. 75, 453. Ardon M, Hogarth G, Oscroft D T W, Organometallic chemistry in a conventional microwave ‘oven: The facile synthesis of group 6 carbonyl complexes, J. Organomet. Chem., 2004, Vol. 689, 2429, Abel £, Ludwig Mond - father of metal carbonyls - and so much more, J. Organomet. Chem. 1990, Vol. 383, 1. PH Ca Speci ina then react wide! 41 Phos comy a spr pota: as ni orga phos ster: ther pola Vari In parsCHAPTER EUTRAL SPECTATOR LIGANDS: | PHOSPHINES AND N-HETEROCYCLIC CarBENES Spectator ligands are ligands which are present on the metal centre but do not take part in a reaction although their properties (mainly steric and electronic) alter the reactivity of the metal centre, They often play a role in the formation of the intermediate complex in a reaction and may also influence the rate of a reaction. Phosphines are some of the most widely used spectator ligands. 4.1 PiospHines: STERIC AND ELECTRONIC PARAMETERS Phosphine (PH,), the parent compound of the enormous range of trivalent phosphorus compounds known in chemical literature, was first reported in 1783 by Genembre as a spontaneously inflammable gas obtained by the reaction of phosphorus with caustic potash. Like amines, the phosphines have a pyramidal structure and can function both as nucleophiles and as bases. Depending on the number of hydrogen atoms replaced by organic groups in PH,, phosphines are classified as primary, secondary or tertiary. Tertiary phosphines are one of the most important ligands used in organometallic chemistry as their steric and electronic properties can be easily modified to fine-tune the catalytic activity of the metal theyare bound to. Phosphines are excellent soft donor ligands (which are large and polarisable) with a variety of substituents which differ in steric and electronic properties. Variation of the three R groups can effect: inges in the steric size of the phosphine (from small to enormous), + changes in the basicity and nucleophilicity of the phosphine which in turn results in lange changes in its donor/acceptor properties (from excellent donor/poor n-acceptor and vice versa), and + preparation of a variety of multidentate polyphosphines (bi, tri, tetra, penta, hexa or cyclo) that can assume different coordination geometries and stereochemistry (chelating, bridging, chiral, cis-enforcing or facial). in 197%, Chadwick ‘Tolman (Dupont Chemicals) developed the steric and electronic parameters for phosphines to explain the ligand effects of L.Ni-catalysed hydrocyanation52 Basic organometallic chemistry of butadiene. ‘This study forms the cornerstone for analysing the steric and electronic effects of phosphines. He published a classic review article covering the methods that he developed for arranging a wide variety of phosphine ligands in order of their clectron-donating ability and steric bulk. It was shown that ligand dissociation from the tetrakisphosphine complex NiL, was the crucial step in understanding the activity of the metal complex as a catalyst in the hydrocyanation reaction (Eq. 4.1). Tolman compared his steric and electronic parameters with the equilibrium dissociation constant (K,) of the dissociation. ‘The size or steric bulk of a phosphine ligand was determined from simple 3-D space-filling models of, the phosphine ligands." NiLy + HCN ——» NCL NN ™ af aT ra Niky Nilg +L The steric parameter 6 for a symmetrical phosphine was taken as the apex angle of a cylindrical cone, centered 2.28 A from the centre of the phosphorus atom which just touches the van der Waals radii of the outermost atoms of the model. Real M-P bond lengths vary from 2.12-2.55 A. Tolman coined the name cone angle for the steric parameter to indicate the approximate amount of ‘space’ that the ligand occupied about the metal centre, Cone angles of some of the well known phosphines are given in Table 4.1."? ‘The electron donating ability of a phosphine ligand was determined by reacting one equivalent of the phosphine (monodentate) with Ni(CO), to make a Ni(CO),(phosphine) complex. ‘The veo stretching frequency (the very sharp a, high energy mode in the infrared spectrum) of the Ni(CO),(phosphine) complex was then measured. The more the electron Table 4.1 Cone angles of selected phosphines PR, Cone angle (°) PR, Cone angle (°) PH, 7 PEPh, 140 PE, 104 PPh, 145 P(OMe), 107 PU-PD), 160 PMe, 18 PCy, 170 Pcl, 124 P(O--Bu), 175 PCOPh), 128 P(t-Bu), 182 BBr, BI PCE), 184 PEt, PPr, 132 P(o-Tol), 194 PICE, 137 P(mesity!), 212 woe ee we lelNeutral spectator ligands: Phosphines and N-heterocyclic carbenes 53 density donated by the phosphine ligand to the metal centre, the more was the w-backbonding to the carbonyl ligands, weakening the CO triple bond, thus lowering the vg, stretching frequency. ‘Tolman defined the electronic parameter x (Table 4.2) simply as the difference in the vc, carbonyl stretching freqiienciesof he Ni(CO), (phosphine) complex andtheNi(CO),P(-Bu), complex. Later on, Crabtree also computed the electronic parameters using quantum calculations and compared the same with Tolman’s experimentally determined electronic parameters. A good correlation was obtained (except for PCI,), which helped to theoretically predict the relative donor capabilities of phosphines as well as non-phosphorus based ligands such as HO and halides which do not form stable complexes with Ni(CO),* Table 4.2 The v,, infrared stretching frequencies of Ni(CO), (phosphine) and Tolman’s electronic parameters (1) of selected phosphines aeapean be PR, Yeo) Xa PR veg tem) xlear) “PO-Bu), 2056.1 0.0 PPh (CF) 2074.8 187 PCy, 2056.4 03 P(O+-PD, 20759 pe | PUPr), 2059.2 3A P(OED), 2076.3 20.2 PEt, 2061.7 56 PEP-CH, 2076.6 20.5 P(NMe,), 2061.9 58 PPhH, 207.0 209 PMe, 2064.1 8.0 P(OMe), 2079.5, 234 PBs, 2066.4 103 PPh(OP), 2079.8 237 P(o-Tol), 2066.6 105 PPh, Cl 2080.7 246 PMePh, 2067.0 109 PH, 2083.2 mA P(m-Tol), 2067.2 Md P(OPh), 2085.3 29.2 PPh, 2068.9 128 PCE, 2090.9 348 P(P-CH,F), 2071.3 152 Pcl, 2097.0 409 PPh.H 2073.3 172 PE, 2110.8 547 PPh{OPh) 2074.6 185 PCE), 2115.0 589 PR3 Lowest CO stretching frequency Highest CO stretching frequency Most donating phosphine 4, Least donating phosphine best conor 4,” Nie best m acceptor 4.2 Basiciry of PHosPHINEs While Tolman’s electronic parameter helps one to classify phosphines as good ¢ donors and good m acceptors, it should be remembered that what one observes experimentally is54 Basic organometallic chemistry the combined outcome of these two effects. A relatively lower o donor capability of a ligand can get masked by its high n acceptor capability. To get an idea about the o donor capebility ofa phosphine exclusively, one can compare the pK values of phosphines. The pK, value is typically used as a measure of the o donor ability of phosphines coordinated to metals. Generally, phosphines are less basic compared to amines (pKa of NEt, = 10.87 while that of PRt, = 8.69). Table 4.3 lists the pK. values (in water) of a variety of phosphines.“¢ Table 4.3 Basicities of selected phosphines RP’ pK, RP PK, (Bu),P 1140 P(-MeOC,H), 457 oe 970 P(-MeC,H,), 3.94 BLP 8.69 PG-MeC,H), 3.30 , Me 8.65 PQ2-MeC,H,), 3.08 e)P 8.64 PPh, 273 (Bu"),P 8.43 Ph,POMe 2.69 PhPMe, 6.49 PU-RC,H,), 197 PhPEt, 6.25 P-CICH), 1.03 ‘There are many examples of reactions where a phosphine or amine bound to a metal is displaced by another phosphine. For example, in the synthesis of Grubbs first generation catalyst, the two PPh, units (0 = 145°, x = 12.8 cm" and pK, = 2.73) bound to the precursor complex are easily displaced by two PCy, units (@ = 170°, x = 0.3 cm” and pK, = 9.70) (Fig. 4.2). It may be noted that PR, ligands that are less electron donating than PPh, cannot be used for substitution in such a reaction.” PPh Poys Cn] ph _2PCv, ly, | aS owt PPhg Poys (4.2) Dissociation ofa phosphine ligand from a metal complexis often a very important step in the formation of the active species of many homogeneous catalysts. Both steric and electronic perturbations affect the dissociation of a phosphine from a complex. A representative example involves the studies carried out by Grubbs on the rate of dissociation of various phosphines from the Grubbs second generation catalyst. The rate of dissociation of P(n-Bu), (0 = 132°) from the ruthenium complex is less (0.006 times) compared to the rate of dissociation of Cy,P (8 = 170°) although both have comparable electronic parameters. Here, the steric factors seem to play an important role, However, the rate of disssociation of PPh,(OMe) (0 = 132°) is 13 times faster than that of PCy,. In this case, the lower donor enna AcE strer of at Pa whic wher Nes: ‘The inth com acce high Bu), acce colo are rear bon pho liga bul! rea can byt bis tot meNeutrat spectator ligands: Phosphines and N-heterocyclic carbenes 55 strength of PPh,(OMe) (pk, = 2.69) compensates for its smaller size. The dissociation of aryl phosphines in general is faster in these reactions [PPh, is 58 times faster and P(4-CIC,H,), is 138 times faster than PCy,]. One can conclude that from a metal complex which is not electron rich and in which the metal is in a relatively high oxidation state, a weak donor phosphine dissociates faster than a strong donor phosphine. Aryl phosphines when compared to alkyl phosphines dissociate faster.* m™ rm Mes-NN—Mes Mes—NN-Mes ow.) Ph aS on.) Ph 43) Ru=< Ru . av | oH aw PRo ‘The situation can be different for a metal complex which is electron rich and has the metal in the zero or negative oxidation state. For example, in the case of Ni(PR)), the inost stable complexes are those where the PR, corresponds to phosphites. Phosphites being good acceptors are more effective in bonding with electron rich metal centres. 4.3. MONODENTATE PHOsPHINES Triphenylphosphine is the most widely used monodentate phosphine as itis air and moisture stable and isan easily accessible solid phosphine. Almost all alkyl phosphines are fairly to highly ait-sensitive, get oxidised to phosphine oxide on exposure to air and someare also pyrophoric. ‘They are strong o donors, usually colourless liquids and foul smelling (unless they have very high molecular weight and are nonvolatile). The o donor ability increases from PMePh, to P(t- Bu), which is in concordance with the x values as shown by Tolman (see Table 4.2). “The phosphites on the other hand are relatively poor o donors, but can be fairly good 7 acceptor ligands (about half as good as CO). Low molecular weight compounds are usually colourless liquids and higher molecular weight compounds are white solids. Phosphites are usually air-stable but moisture sensitive. Phosphites can also undergo the Arbusov rearrangement forming the pentavalent tetracoordinate phosphorus compound with a P=O bond. The formation of the P=O bond is the driving force for many reactions involving phosphorns (IIT) compounds and oxygen containing reagents. PF, isa very strong macceptor ligand and is almost as good as CO in its acceptor propertis Recent years have witnessed an added interest in the design, synthesis and use of bulky as well as electron rich phosphines, especially in palladium catalysed cross coupling reactions. Aryl chlorides which generally have poor reactivity in cross coupling reactions can be made to react under mild conditions to give good yields of cross coupled products by using such phosphines along with palladium. The basic difference that these phosphines bring about is in the nature of the palladium complex which becomes tricoordinate due to the steric bulkiness. Some of the bulky phosphines used in such reactions are shown in Fig. 4.1, Water soluble phosphines find use in cases where catalyst recovery is important by means of biphasic catalysis.56 Basic organometallic chemistry cs tun Oho. : = aX Xx ray Meo om Pa eee P P P(tBU)s cataGxtum A ‘S-Phos Q-Phos Fig. 4.1 Sterically hindered and electron rich tertiary phosphines 4.4 MULTIDENTATE PHOSPHINES Among multidentate phosphines, bidentate phosphines are the most important as they find applications in many catalytic reactions. Some of the most widely used bidentate phosphines are described below. Being bulky ligands, two monodentate phosphine units ona metal centre generally prefer an orientation trans to each other. The important characteristic of bidentate ligands is that they are cis enforcing and thereby, one can fine tune the catalytic activity of , a metal centre. Chiral biphosphines are very important as they can induce chirality on the metal bound by them. A very important feature of the biphosphines, chiral and non-chiral, which helps one to select the best phosphine for a specific application, is their natural P-M-P bite angles. Natural bite angles along with electronic and steric properties are varied on biphosphines bound to metal catalysts to get better selectivity of products. For example, one of the problems associated with hydroformylation of alkenes using a rhodium catalyst, HRh(CO)(PPh,),, is that one gets a mixture of linear and branched aldehydes as products (see Chapter 13). In 1987, the Texas Eastman company patented the rhodium catalyst having BISBI, a biphenyl derived biphosphine which gave excellent selectivity to the linear aldehyde compared to other phosphine ligands. The high selectivity observed with BISBI was attributed to the active catalyst species RhH(BISBI)(CO), with the BISBI having a natural bite angle of 120° (Fig. 4.2). Later, detailed studies on a series of xanthphos biphosphines having a natural bite angle varying from 102~123° further confirmed the PhaP Pehp PhP PPh PhP PPh (a depen cope ppp 72° 85° ot " @ C0 Ph2P PP hg PPh, Phy alse! Benzoxantphos 120° 1206" Fig. 4.2 Bite angles of selected biphosphines Ani bu ani use ace!Neutral spectator ligands: Phosphines and N-heterocyclic carbenes 57 high selectivity for linear aldehydes, when biphosphines having a natural bite angle very close to 120° were used? Some of the other important chiral and achiral biphosphines and their specific applications are given below. “ (AP De a chiral biphosphine with a bite angle of 92° and has been used ina variety of asymmetric catalysis reactions, Introduced by Noyori in © © 1980 (Nobel prize 2001) both the R and $ isomers have been separated and used. Along with rhodium, it is used in the industrial synthesis of © menthol, a chiral aromatic substance. Later Noyori used it along with ruthenium for the asymmetric hydrogenation of ketones. One of the well known processes in which BINAP is used is in the production PhP Pha of (R)-1,2-propanediol for the industrial synthesis of the antibiotic (8) BINAP levofloxacin.” DIPAMP ‘This was the first chiral biphosphine to have found wse in an industrial process, William Knowles (Nobel prize 2001) used it in the asymmetric hydrogenation of methyl-(Z)-a- oi) "xO acetamidocinnamate which was then used for the synthesis Maal Vga of L-dihydroxy phenylalanine. L-DOPA (Levodopa) is used as a prodrug to increase the dopamine levels in the treatment of Parkinson's disease, since it is able to cross the blood-brain barrier where dopamine cannot. Once levodopa has entered the central nervous system, it is metabolised to dopamine" DIPAMP DPPF ‘This biphosphine has a bite angle close to that of BINAP (96°) and has been used in many reactions as a cheaper substitute for the costly ¢E57—PPhe chiral BENAP. It has been extensively used in palladium catalysed cross“) coupling reactions. PdCl,dppf when used in the Kumuda-Hayashi coupling (coupling of aryl bromides with Grignard reagents) gives syne excellent selectivity of products. DPPF has been used to achieve good yields and selectivity in palladium catalysed reactions such as the Suzuki oo and Buchwald-Hartwig C-N coupling reactions."* JOSIPHOS This is one of the examples of ferrocene-derived chiral biphosphine Hs having both normal and planar chirality that is industrially useful. The fj CH N Mes-NNeMes ' ay al y Cm | ‘hue ‘ oh _ . i off bu cif] Ph on D | 4 stable low activity stable, high activity stable, high activity recyclable Grubbs second __Grubbs-Hoveyda catalyst generation catalyst F Fig. 4.3 N-Heterocyclic carbenes and olefin metathesis catalysts 4.5.1 Synthesis of NHCs NHC with saturated carbene rings have been prepared with five, six or seven membered rings. Initially, these were prepared by the reaction of acyclic diamines (or diimines) with a formyl unit to close the ring (Fig. 4.4). However, this method was found to be low yielding and had problems while preparing functionalised NHCs. A recent method uses the reverse methodology ‘wherein a formamidine fragmentis first prepared and the rng is closed witha dibromo or diiodo hydrocarbyl unit using a base. This potentially useful method is high yielding as well? As the deprotonation of the halide can sometimes lead to partial decomposition, the halide ions were exchanged for tetrafluoroborate ions, and the resulting salts were easily purified by crystallisation and readily converted to the free carbene. x Nae SY ane N-Ar MeN retty 7 HOE, «HX NS aes ao 4 oo Ay? From diamines Fromtonnamidnes & ore , / _NaBFe [\ kysieds | \ WN O NAD RECN THO ATTN @ NAR ye AN Nar wy SZ HE Ve H H os Fig. 4.4 Synthesis of NHCs with saturated carbene rings62 Basic organometallic chertistry Synthesis of NHCs with unsaturated carbene ringssuch as 1,3-bis(2,6-diisopropylphenyl) imidazoliumchloride (IPrHCi) has been carried out as follows. Glyoxal on addition to 2, 6-diisopropylinilite in absolute ethanol with 4 catalytic amount of fotmic acid results in the formation of a diazabitadiene in the form of a yellow solid. This cothpound teacts with paraformaldehyde and HCI in toluene to forth 1,3-bis(2,6-diisopropylpheny!) imidazoliumchloride (IPtHC) in moderate yields. The free carbene IPr is generated when IPFHC is reacted with potassiom tert-buitoxide in THE 4 AN ok > HoH ry KoBut rF HoooH NN “Hor” Ar-NQ Near Wh Near o>, WON Tou “OY Are Fig. 4.5 Synthesis of NHCs with unsaturated carbene rings I Problems and Exercises ai 4.1. Artange ithe following ligands in the order of iticteasing o donot capability. | PCy, SIMes, PMe,, P(O#),, PPh, PE, f 4.2. Consider the followitig reaction. Show in which case the ligand sibstitution reaction” occurs faster: when L = CO or when L = PMe,? } PMeg / Ni +60 aco 4.3, If a highly substituted complex, Mo(CO),L, is desired, which of the ligands PMe, or P(‘Bu), would be piefetied and why? Namie the isomer fornied from that reaction. 4.4, Among Cr(CO),(PF,) and Cr(CO),(PMe,), which one do you think will have ' . = (a) the stronger C-O bonds (b) the stronger Cr-C bonds? 4.5. Whichamong the following pairs of metal complexes will have the higher CO stretching 7 frequenicy? Give reasons. (a) TiO,(PEt,),(CO), and Cp,Ti(CO), (b) {Rh(CO), [P(OPh),},}* and Rh(CH,),(CO) dmpe (0) (yf-allyl)Co[P(OMe),](CO), and (ij-1,3-dimethyl-allyl)Co(PMe,)(CO), (d) Os(CF,),(CO), [P(OMe),), and Fe(CH,),(CO), (PMe,), 4.6. _ Arrange the following in the decreasing order of Rh-C bond lengths. (a) Rh(CO)CI(PPh,), (b) Rh(CO)CIPEL), —_—_(c) RH(CO)CIIP(C,F_),], 4.7. The thenium coniplex Re(Cl)(N,)(PMe,Ph), on heating loses a colourless gas and forms a new complex.The new complex obeys the 18 electron rule, does not possessNeutral spectator ligands: Phosphines and N-heterocyclic carbenes 63 metal-metal bonds and its **P NMR chemial shift values are comparable to that of the parent compound. Suggest a possible strucutre for this complex. 4.8. The Vc, stretching frequency (a, high energy mode) values obtained for a series of cis- L,Mo(CO), complexes where L = PR, are given below in the increasing order. Given that the trends of the electronic parameters of cis-1,Mo(CO), are similar to that of LNi(CO),. match the phosphines with the streching frequency values, 2013, 2015, 2022, 2037, 2046, 2092 [PR, = PE, PMe,, PPh,, P(OPh),, PEt,, P(OMe),} 4.9. From the given list of phosphines choose the most suitable one to use along with the metal catalyst for the reactions provided [dppe, dppf, BISBI, P(‘Bu),, P(OPh), PMe,] (for reactions, see chapters 12, 13 and 16). (a) Hydrocyanation of butadiene —_(b) Hydrogenation of propylene (©) Kumada-Hayashi coupling (@) Suzuki coupling of aryl chlorides (e) Hydroformylation of propene 4.10. Which among the given phosphines is most likely to give a positive reaction in the given scheme? PR, R= (a) 4-FC,H, (b) Bu’ (c) Bt (d) 4-MeOC,H, PPhs prs ct en 2PPS. oy, | pn Ru av] oH ov | oH PPh PR 411. If Tolman’ electronic parameters were to be applied to N-heterocyclic carbenes, indicate the range in which the x values of the NHCs will appear. 4.12. Place the following dinitrogen complexes in order of their increasing N-N bond length, N N F awn] L2 try, NFB, oF tins — Fi Rh ™~; ™~ oF Phy om ‘Ph, Gi PPM PPh N Li =PhsP L2=MegP LS = FP LA = (MeO),P 4.13. Consider the following data and explain the observed trend in reaction rates. Mo(COllz + CO— a Mo(CO)s. + L L=PhPMe, <1x 10% PhPMe 13x 105s? =PhP 32x10"