Coordination number of the central metal atom/ion given complex compound is equal ion number of the central metal atom/ion in a gi ‘th the central metallic atom; Coordination rot doer atoms which are actually attached wi | metallic atom is equal cy eal bes SA er ie eorraraaeayraa Soe ee RATE atom, Bivens a1 which the ligand) tached with the ex igands, the coordination In case of complex compounds which contain only monodentate Tigan Tights Soondien number of the central metallic atom is equal to the number of mo: nee) EORUAIDICE Gerrans he metallic atom. This rule does not hold good for the comp Ge, bidentate, tridentate, tetradentate etc.) ligands. ompound, Coordination number of the metallic atom predicts the geometry ef tha comic Thus for coordination number equal to 2,3,45 and 6, the Eeametyg ring ee is linear trigonal planar, tetrahedral (or square planar), trigonal en at idea about fe pabectively. This discussion shows that the coordination number gives Way in which the ligands are arranged round the central metallic atom. Coordination sphere and ionisation sphere While writting the Structural formula of a &iven complex compound the central metal atom and the ligands attached with it are always written in a Square bracket, (1. This square bracket is called coordination (or inner) sphere. The portion outside the coordination sphere is called tonisation (or Outer) sphere. Thus in (Co(NH),CICI,, the square bracket which contains the central metal ion (Co™* ion) and the ligands (five NH, molecules and one CY ion) is coordination sphere and the portion that Contains two CI ions is ionisation sphere. The species written in ionisation sphere are ionisable and h means of a suitable Prec: ‘ence can be precipitated by ‘pitating agent while those given in the coordination sphere (i.e, metallic atom and ligands) are n ‘on-ionisable and hence cannot be precipitated, This is shown below for [CotNH;),CIICI, (Co(NH),CICL, === (Co(NH,);Cl)* + 2¢7 Two Cl ions present in ionisation sphere can b i AgNO; solution, T multidentate ligands. These ligne ed oe adentate, if the number tetradentate, a 4 ‘nt in one Molecule of the Of these ligands ig Coordinated at mea SS , respectively. Thy: Me the . y- 'S One molecule other words, we can say that one molecule then igo at 2 3 vel f 5 14, 5 and 6 sites Tespectively. coordinate bon ds respective % ligands Makes 2, 3,4,5 spectively. + and 6 metal— ligandExamples of monodentate ligands Examples of monodentate ligands are given in Table 1.1. Table 1.1. Examples of monodentate ligands. (a) Neutral ligands which are named as such, Their abbreviations, if any, are also given. (GH)sN Tricthy! amine (Cells),P .» Triphenyl phosphine NHNH; of Nt. Hydrazine CH,CN Acetonitrile CHNH, =. Methyl amine O2 oF ‘Ome v= Dioxygen NH,OH w= Hydroxyk Naor :Ne=N: ... Dinitrogen (CHy:NH Dimethylamine Pr; v= Phosphorus trifluoride CsHSN or py Pyridine (GqHs)sP .» Triethyl phosphine (b) Neutral ligands which are given: special names, e.g. co Carbonyl NO Nitrosyt cs Thiocarbonyt NS Thionitrosyt H,O Aquo or aqua NH Ammine According to latest system of nomenclature, the word ‘taqua’’ is used for H,O molecule. (©) Anionic (negative) ligands. The names of negative ligands end in 0, Examples are given below: Fr . Fluoro GR Chloro Todo Acetato Br ~- Bromo r ~- Hydro or hydride CHyCOO™ or cH; =c—C NH; v» Amido NHP » Imido Ne w=» Nitrido INH(OR)- Hydroxo amido [(CH,):NT- -- Dimethyl amido on Hydroxo or hydroxyl oF «Oxo HO; Perhydroxo. 20 = OF or Peroxo 0; or ‘Superoxo HS w=» Mercapto s Sulphido or thio soj- .. Sulphito so} . Sulphato coe vn Carbonate cy" + —- Cyno(coordination 3 through C-atom) NC. s« Iso-cyano_ $,03° ‘Thiosulphato (coordination through N-atom) CHO" v= Methoxo GH,O- 22), Ethoxo Ny w Azido NO; r Nitro (coordination thorough N-atom) ONO; «» Nitrito (coordination = SCN Thiocyanato through O-atom) Iso-thiocyanato NO; . Nitratoligands ions. Examples of bidentate ecules OF anions. . . ' tral molecu ive a number of diamj Bidentate ligends may be roan gc, buatyiene and isobutylene Bern in Table 1.2, ine 1. Alkenes, like ethy!ehe Prope as bidentale tigands a8 1 nd to act 8 . es. derivatives whieh Lec : z a en en a Bidentare ligands ‘Alkenes act ‘amine (en) CH CHa " i Fihylene diamine ( { ‘ Th NH, ‘™2 Ethylene C=C ’ i —c i t Ethylene diphosphine ae ie (diphos) PH, PH, al re Propylene oe Propylene diamine (p) HC TG HH NB, NH, This compound is also called 1, 2-diamino propane (pn) 1 2 3 CH,—CH—CH, , since the structure of propane is NH, NH, CH,—CH, — CH, i 2 3 1,3-diamino propane or CH, —CH— trimethylene diamine (tn) | aH To? NE, NH, au ‘ig CH, CH, Butylene Fo Butylene diamine (bn) HC —CH HOH Is | =a NH, NH, 3 Isobitylene ed i ; = Isob iin 1 Igebutylene disinine —c—c—H CH, H | cH, os Tetr fetramethyl ethylene C—=C ‘Tetramethyl ethylene CH, CH, diamine (zetrameen)asie Concopts of Coordination Chomiatry 7 Ethylene diphosphine (diphos) have one lone pair of electrons ene tw Espns which oct as donor atoms, since they P The coordination of this ligand to the ce tral metal om takes place through these two P-atoms, leading to the formation of one ee ring Each of the diamines gets atached wit r i h the central donor ators), forming ong S-membeted sing inc Eee fave bile? oy ihe structures of [Co"(er),C1]? and [PL*(bn),P* ions given in Fi a s is eviden ‘and unsymmetrical bidentate ligands). given in Fig. 1.20 (see symmetrical 2. 2, 2-bipyridine (bipy) (also called bij » 2 also ca ridyl), It i wc ea Sa al en a se ed eel with a metal atom M, 5-membered ring is obtained [See (6) of Fig. 1.1] igand gets Jini SS 4 ak Ne eer sdisai tes ) “bipyridine (bipy) or bipyridyl (6) Attachment of bipy with the central metal Fig. 1.1. (a) Structure of 2, atom, M 3. Hydrazine, NH,—NH,. Its attachment to a metal atom occurs through its two N-atoms, aN ' 4 1™ This ring is very strained 2 forming one 3-membered ring which can be represented as and hence is unstable. 4, o-phenanthroline or 1, 10-phenanthroline (o-phen or phen o™ phenan). It is a neutral symmetrical bidentate ligand, since its two donor atoms viz, Natoms are similar atoms. Its SMeture is given at (a) of Fig. 1.2. It is abbreviated as phen or phenan. When it gets attached with a metal atom, it is denoted as 5 phen and its attachment to a metal atom, M is indicated N as mx Phen For example this ligand gets attached with Fe ion and gives [Fe(phen) 3) complex ion whose structure is given at () of Fig. 1.2. Fea a SUN Cy SS @) Fig. 12. (a) Structure of tp-phenonthroline (phen or phenon) (2) structure of [Fe(phen)a]™ ion @) ‘The structure and the mode of its arsine (diars:or D). Here two As‘atoms 5. 0+ bis dimethyl s oth cent mmplexes are shown in Fig. 1 attachment with the central ‘metal atom in Co} are donor atoms:“Vay 6 jG CHs Hyg Hs “S74 a Ol Cx x ~ AN tH, HC ‘his dimethyl arsine (diars or D) (6) Mode of attachment of diay shenylene Fig. 1.3. (a) Structure of o-phen: St il ‘metal atom, M in complex ’ 6 sceslsocanato jon (acac). This ion is obtained when one molecule of the eno ee ee - ». 1.4). of aceijl asctone (Hacac) loses a proton, H” (see Fi. it =c— c—c—ci=c—cH, > HE cH=¢—cn, ll ° OH Fig. 14. To get acac” ion from Hacac molecule. hed with the central metal atom through its two O-atoms - ai E This ligand Be aoe having one 6-membered ring as shown in Fig. 1.5, forms a chelated complex hi and Fig. 1.5. Mode of attachment of acetylacetonato ion to the metal atom, M. 7. Benzoyl acetonato ion. The structure of this ligand and the mode of its att with the cental metal atom can be shown as depicted in Fig. 1.6. me H 4 Ay E— che — ca H,c—c~ “6 — CH Neve a Fig. 1.6. (a) Structure Pe ) | @s ML, Pn209 acetonato ion (6) Mode of attachment of benzoyl acetonato ion to the 8. Oxalato ion, C,02 (0: (A:C,0, or H,02) loses two Sion can be obtained when one molecule of oxalic acid Protons (see Fig. 1.7), o=>C—oH : O=C—on ¢ ; Hox moleculeoats through its both we vely Shree O-atoms (acidic donor atoms), forming S-membered complex as is evident from the structur 0} i 2 vi come po it ide a, re of dioxalato platinate (M1) ion, [Pt*(C,04)a 2- 2- . jo=c—o o Fig. L& Structure of dioxalato platinate (11) ion, [P2%(C20u)2\ or {Pi2*(ox)2]~ (square planar complex ion). 9. &-hydroxyl quinolinato ion (oxine™ or oxinat 10"). This ion is obtai attached with the ring of 8-hydroxyl quinoline molec sas seas ae ee tule, Hoxine loses a proton (H*) as shown in Fig. 1.9. Se Ss a2 N NZ OH R 8-hydroxy 8-hydroxy quit onlin etovate salve Fig. 1.9. To get oxine” ion from H oxine molecule. The attachment of oxine~ ion with a metal atom (M) in complex compounds takes place as shown in Fig. 1.10. By this type of attachment a 5-membered ring is formed. -10. Attachment of oxine” ion to a metal atom (M) in complex compounds. 10. Dimethyl glyoximato ion (dmg” or DMG°). This ion is obtained when one OH group attached with N-atom in Hdmg molecule loses a proton (Fig. 1.11). cs Gs CH;—C=N: CH; —C=nN: | + H cH,—c = CH, ea OH o Dimethyl glyoxime (Hdmg, dmg” or DMG” ‘or HDMG) Fig. L11. To get dmg” ion from Hdmg molecule. ‘Two dmg” ions react with Ni2* or Pd®* ion in ammoniacal solution and form an insoluble neutral red chelated complex, [M(dmg),|° (M = Ni%*, Pd?*) which has two 5-membered and two 6-membered rings. The formation of [Ni(dmg),]° has been shown in Fig. 1.12.ova 10 H,C —C=N: + , + Ni + Hyc—C=Ni * I ° O—H dmg ion dtmgr ion HC — — H,C—C=N' oO oO He Bis.(dimethylglyoximato) r chelated complex, {Ni (dmg)2} nickel I cheated compl Fig. 1.12. Formation of [Ni(dmg)2}° (chelated complex). 11. o-nitroso B-naphthol anion. This anion is obtained when c-nitroso B-naphtho] molecule loses a proton (H*) from OH group (see Fig. 1.13). , o= e-nitroso B-naphthot Fig. 1.13. To get o-introso B-n: This ion gets linked with metal at charged O-atom. A S-membered ring i naphthol ion aphthol ion from a-nitroso B-naphthol molecule, fom, M through its N-atom of NO is fomed at M atom Fig. 1.14). O=N —+mM group and negatively H.N—CH,—c—oyq —-H+ N Ean il H.N—CH, ° Giyeine molecule Higly)le asia Concepts oF Luvramauens caranny Glycinato ion cal a bidentate monobasic ligand and its co-ordination to the metal ion occurs through neusra Deaiban (oeiinaliicr atom) and negatively-charged O-atom (acidic donor forming a 5-m ing as is cvident from the strucuture of cis-and trans-isomers atom), a ' fof octahedral iriglycinato chromium (IID, [Cr(NH,—CH,—C—O),)° or [Cr(gly)s]” shown in | . ° vig. 121 (6ee syminetical and wnsymmetrical bidentate ligands). 13. Biguanido fon (big"). This ion is obtained when bigua NH group in C=NH unit (sce Fig. 1.16), \ W,N—C—NH— C—NH, l NH NH :NT NH Biguanide molecule (big H) Biguanido ion (big) ig Fig, 1.16. To get big” ion from Hbig molecule. This ion gets attached with the central metal atom through its negatively-charged N-atom and N-atom of NH froup and forms a chelated complex containing 6-membered fing as shown in Fig. 1.17. 14. Carbonate (CO2), nitrato (NO;) and sulphato (02). The structure of these ions and the way in which they are coordinated to' the metal atom are shown below i tig. 1.18. Fig. 1.17. Attachment of biguanido ion with metallic atom: ‘Sulphato, SOy Fig. 1.18. Structure of CO3”, NO; and SO?" ions and their attachment with metal atom, M. Note. Carbonato, nitrato:and sulphato ligands also act as monodentate ligands as is evident from the following. complex: ions Pentammine carbonato cobalt (IIT) ion (octahedral) Pentammine sulphato cobalt (IID) ion (octahedral) Tetranitrato titanium (IV) (square planar) [Co* (NH;),(CO3)]* [Co* (NH;),(SO,)I* Imi*@NO,),)°“yy, ato cobalt (III) ion a 96 ” pis-cotnylon? diamine) dinite ba - icomtemsnonn ve ligand 2” be 5 sed co have en obtained by clin 15, Pero OF te (FB 1.19). ing N ‘é protons from 1202 es ¢ y-0- H Boe % iydroget™ yeroxide Peroxo group (02 ) molecule, 1302 . é i ig. 119 T° get perore jenltOn OCR hydrogen perorié ¢ molecule (H20.) On coordinated ( the central metal atom as yim following two ways: following three types of bidentate 4, tral atoms. Examples of s Bands, iene bis, dimethyl arsine (, ee ligang » As) te, jaentate ligands have been clasified into the Classification L. This classification gives the 1. Bidentate ligands whose both donor atoms are nel are ethylene diamine (Ns N), dipyridy! (Ns N), o-phenyl ‘The symbols give racket are the donor atoms: 2. Bidentate ligands which have one neutral and one ic ani such gands are acetylacetonate jon (O, 8-hydroxy quinalin donor atom. Exam, : B-naphiol ion (N, 0”) ete ate ion (N, OF neo | r pidentate ligand which have both anionic donor atoms, e.g. oxalate i yeni fy es ion (07, O°, +O), carbone ion (07 0°), sulphate ion (O", OF ete Classification I. fi i ‘cation I. According to this classification, bidentate ligands may be sym metrical bidentate ligands or unsymmetrical bi in which the two donor er ene ligands. Symmetrical bid ya i the two donor atoms are fifferent. while unsymmetrical tea ligands are thos 2 in which two A’s different. Thus a symmetri videntate ligand: a is denoted as (AB) it ; are two similar donor at nmetrical bidentate li Is are those bid in which A an ‘atoms while an te ligand is jidentate ligands are given he aed B are two different donor unsymmetrical ee denoted Donor atoms have been sh atoms, Examples of s; ite Ligne own in bracket. symmetrical brac Classifi Bidentate lig: fi cH— i fe oe CH, : Bee ai Bee die i yen iia, Lo | an NH, NH, Butylene diamine, bn (N,N)For example the attachment of (wo molecules of ethylene diamine, NH;—CH;—CH;—NHz 0 oo ico to a the GakEDACHI” ion (octahedral jon) can be shown as t (a) Of . arly, the attachment of two motecul butylene diami: depicted at (CTs) (bn) to Pe" 4 molecules of butylene diamine, CH(CH))—CH(CHy 2 (bn) to PP* ion to form Pi NHC) of Fig. 1.20. square planar (Pt(en))/* ion can be —t t > e 20.5 f trans-isom: £ bis (etylent Fig. 1.20. Smucture of trans-isomer of bis (ethylene diamine) dichloro cobalt (IMD) ion, (Co(NH2—CH: ! (CHz—NH2)2Cho]” or [Co(en}2 Clz]* (octahedral ion) [shown, at (a)} and bjs (batylene Giamine) ! platinum (11) ion, [Pt{NH2—CH(CH3)—CH(CHs)—NH2}2]"* or {Pt(bn)2}"* (square planar ion) . [shown at (6)]. d Examples of unsymmetrical bidentate ligands are given below. Donor atoms are given in al | bracket. Glycinato ion, gly 8-hydroxy quinolinato ion ‘a-nitroso -naphthol ion (Wo7) WO Wo) ‘The attachment of an unsymmetrical bidentate ligand to the central metal atom is shown A by a curve ae where L is the abbreviation of the ligand and A and B are two (different) B | donor atoms. For example, the attachment of three glycinate ions, NH,—CH,—C — O- (ely) by ll yo | © Cr* ion to form cis-and trans-isomers of octahedral [Cr(gly)s]° can be shown as depicted in TeeAdvanced Inorganic Chemisty 4 OR cle-isomer trans-isomer Fig. 121, Structure of cis-and srans-isomers of [Cr(NH2 — CH, — f _ i Obs}? oF {Cx(glyysp ° Examples of tridentate ligands ‘These ligands may be neutral molecules or anionic species. Important examples are give, below: Fariaminopropane, The structure of this ligand is given at (a) 0 that it has three Na f Fig. 1.22 which show The coordination of this li igand to the central met Freese Conor atoms), leading (o the formation of two S-memberei {(CH,(NH) —CH(NH,) —CHNH,)),}** ion (a chelated ue a —cH—cu, NH, NH, NH, Fig. 1.22, « 2 () "8-122. (a) Structure of triaminop id i 3 — CHRNH,)}2}* jon (ected eee ceapt) Stucure Seaman ctasic Concepts vs vw ee ). Hs structure is given in Fig. 1.23 (a). This ligand gets 2. Diethylene triamine (di 1 fom thi mm through its three N-atoms (donor atoms) and forms a 4 with the cent al attached afelate which contains (wo S-membered rings, [See 1.23 (by). 1 th . fai, HN —CH)—CH, Nit + the, mM fe HN —CH,—CH, 11,c —-N— CH H t (a) of diethylene triam (H) ure of diethylene triamine (dien) (b) chelated complex (es by dien with a metallic ig. 1.23. (a) St bs atom, M. 43, 2, 2, 2’-terpyridine or terpyridyl (terpy), , oe the central metal atom are shown below in I peter See OSE) | ~ Nh eN Z OD os ® Fig. 1.24. (a) Structure of 2, 2’, 2”-terpyridine (terpy) (b) Mode of attachment of terpy with the central metal atom, M 4, Imido di-acetato ion (imda”), This ion is obtained when imido di-acetic acid loses two protons (See Fig. 1.25). ont HO —C— CH,— NH — CH, fi OH > C—CH;—NH— CH, Cc. \ ° Imido di-acetato ion (imda”) oO Imido di-acetic acid (H2imda) Fig, 1.25. To get imda”” ion from Haimda moelcule. This ligand links to the central metal, atom, M through its Natom and two negatively-charged O-atoms, forming a chelated complex which contains two S-membered rings as . shown in Fig. 1.26. 5. Anion of diamino propionic acid. This ligand is obtained by removing one proton from diaminopropionic acid HN——M. as shown in Fig. 1.27. \ \ as Obviously it is a tridentate monobasic ligand and its HC wpe ——— place through its two coordination to the metal ion takes atively-charged i N-atoms (natural donor atoms) and one neg: CH,—CH—C=O + CH,—CH—C=0 Oo | > | to 1s Fig. 126. Structure of the NH, NH, OH NH, NH, ‘0: chelated complex formed by wo @ ® jmido diacetato with metallic Diamino propionic acid ‘Anion of diamino pro- ‘atom, M. pionic acid Fig, 127. To get an anion from diamino propionic acid molecule ‘hu removing one proton from it.¢ of UIE m the siuctur * ion (chelated complex ion : H(NH2}—COO)2]" i 1.28. Structure of [C0 {(CH2(NH2)—C eof ligands ; eof iven below: / Examples of ae of these ligands are eae a dade 163 _ ‘ole ir ie e st h t Import thylene tetramine oar ‘N-atoms as its donor tons (etal one 12 This sau shows that oe be metal ion takes slece nro ee Se ms a ination of this ligan takes pla ne corrg complex containing three S-membered ring: a ca atom) NH, —CH,—CH,—NH—CH, NH, — CH; — CH;—NH— CH, - H, H, @) Fig. 1.29. (a) Structure Ae apie tetramine (rien) molecule (b) Chelated complex formed by triethylene {etramine molecule with the metallic atom, M. 2, Triaminotriethylamine (tren), N(CH,—CH,—NH))3, Ils structure is given at (a) of Fig 1.30. This structure shows that it has four N-atoms as its donor atoms. The attachment of this Ii to the central metal atom, M in its complexes takes place through its four N-atoms, Tesulting in the formation of chelated complex having three S-membered rings as shown at (b) of Fig. 1.30. HC = H. e aa os Nr NH,—cH, — C—N—Cu, — cH, —iin, oN VA va CH, CH, CH, CH, ‘ M of om H a ™y : H, (a) Fig. 1.30. (@) Structure Of triami Ne complex fe powiethylamine (ty nme by the atachnen <2), N(CH; 12—NH2)3 (b) Structure of the chelated Swethylamine molecule with metallic atom, M.3. Nitrilotriacetato jon inte? or NTA™). The structure of this ion is given at (a) of Fig. This sructure shows thet tus ligand is a tibasic tetradentate ligand. The coordination of this “nd 10 the metal ion takes place throu; ‘atom (neutral donor atom) and three negatively-charged zoms (acidic donor atoms) of COO” groups. This type of coordination gives rise to the formation acpeiae having tee S-membered rings as shown at (b) of Fie, 13 N (@) (6) 131. (a) Structure of nitrilotiacetato ion (nta"* or NTA™ (6) Structure of the chelated complex formed by nta™ ion. Examples of pentadentate ligands Important examples are given below: 1, Tetraethylene pentamine (tetraen). The structure of this molecule is shown at (a) of Fig. 1.32. This structure shows that it has five N-atoms as its donor atoms (neutral donor atoms). Thus this ligand coordinates to the metal atom through these five N-atoms and forms four 5-membered rings as shown at (b) of Fig. 1.32. Ee ma Ib HN —(CH)y—NH— (CH).\_ HN — (CH,)2—NH— (CH), (@) ¢ Fig. 132, (a) Structure of tetraethylene pentamine (tetraen) (b) Structure of the chelated complex formed by tetraethylene pentamine with metallic atom, M. 2. Ethylene diamine triacetate ion. It is an anionic ligand and its structure is shown at (@) of Fig. 1.33. This structure shows that it has three negative charges and five donor atoms viz two N-atoms (numbered as 1 and 2) and three negatively-charged O-atoms (numbered as 3, 4 and 5). Its coordination to the metal atom occurs through two N-atoms (neutral donor atoms) and three negatively-charged O-atoms (acidic donor atoms) of COO- groups, forming four S-membered rings as shown at (b) of Fig. 1.33. Example of hexadentate ligand Ethylene diamine tetracctate ion (edta* or EDTA™ or Y~) is an important example of hexadentate ligand. It structure is given in Fig. 1.34.™~, 1 ° . 1 Sa, : We woe A ° cH, — - il as N, M. % Pe a SHC Q oy HON. Co brH) oO. No | 29 CEN CH, CHO, oa (5) . » CH, ‘CH,’ 1” ) NE Hu H, ° 5 a of the chel; we (a) . iacetate ion (6) Structure of the chelated complex f, vine triace! 7 ‘Ormey ture of ethylene diam eee vith metallic atom, M. Fig, 133. (0) Simeryylene diamine tricetate fon . oO MW 2) CH)— @ mG—CHEN eg OH , 2" NcH,—c— OF w —c—H,c “fl ° Fig, 14, Structure of ethylene diamine tetracetate ion (edtat or EDTA‘) ‘The structure shows that it has two neutral N-atoms (numbered negatively-charged O-atoms (numbered as 3, 4, 5 and hhexadentate ligand. ‘The co-ordination of this Neatoms and four O-atoms, form d and I-forms of [Co*(EDTA)|- ee optical isomerism exhibited as 1 and 2) 6) as its donor atoms. Thus it 2 24 fou is tetrabasie ligand to the metal atom takes place thorugh two g five 6-membered rings as is evident from the structure of jon given in Figures 4.33 and 4.34 on Page S1of chapter 4 by octahedral complexes containing polyd i mi uaanas. When lentate ligand having ined PeO™ through either of its two eae fate dite - plex compounds are. obtained, These compounds are different mpounds are called linkage isomers and the ue to the tendency of tt atoms, it because they phenomenon is ferent 5 the ambidentate inkage isomers aon OUBN its two different do ~~ ay wsBasie weno as ne, ON ea aes ‘and contains one unshared pair of electrons while in , me enpe charged and this Q-atom contains three unshared pairs Ef alecoons. Thus when NO, jon sets as a monodentate Higand, it may be linked to the contal metal atom pe through os Jone pair of electrons on negatively-charged N atom of structure (1) Be through the Jone pair of electrons on negatively-charged on O-atom of structure (). Thus: (@) When NO; ion Ths: coordinated to the metal atora through a lone pair of electrons on «|S or OON — M or O,N— MI, it is called nitro ligand and is written as 0 ° , NO;, The complexes containing nitro ligand are called nitro complexes. me (NOYICh (el ys ce esto low brown) is called pentammine nit tro c ide, si inati ODE ee oy cca teeagh Nom, ‘obalt (II1) chloride, since the coordination (© When NO; ion gets coordinated to the metal atom through a lone a pair of electrons on O He NO: or MCONO}, it is called nitrito ligand which is written as ONO. ‘The complexes containing nitrito ligand are called nitrito [Co'*(NH,),(ONOJCI, (red) is called pentammine nit nitrito complexes. For example a Cl trito. cobalt ide, coordination of NO; ion to Co™ ion takes place through O-atom. Oe Sometimes ambidentate ligands are distinguished by putting the symbol of th which the coordination of the ligand to the central metal atom tes plece, For se GONE), {NO,)ICk; (yellow-brown) is called pentammine nitrito (N) cobalt (It) chloride and [Co™(NHs)s (ONO)ICh (red) is called pentaramine nitrito (O) cobalt (Ul) chloride. Both nitro and nitrito complex compounds mentioned above are called linkage isomers and the isomerism shown by them is called linkage isomerism. - ‘Another example of a pair of linkage isomers is furnished by diammine bis (pyridine) dinitro cobalt (III) nitrate, (Co (NH3),(Py)ANO2)2INOs and diammine bis (pyridine) dinitrito cobalt (ID) nitrate, (Co (NHs):(Py){ONO):INOs, Tt has been found that nitro (NO;) is a stronger ligand than the nitrite (ONO”). Linkage isomers can bé identified by infra-red spectroscopy: 2. SCN” ion. We know that this ion can be represented by any of the following two structures: J—C=N: :S=C ‘Structure (1) Structure ay (Thio cyanato group) (iso-thiocyanato group) Structures given above show that when SCN ion acts as a monodentate ligand rit may be coordinated to the central metal atom either through the lone pair of electrons on $ atom [Structure (1)] or through the lone pair of electrons on Ne atom (Structure (I)]. Thus: (a) When SCN™ ion gets coordinated to the metal atom through the lone pair on negatively-charged S-atom [Mc | —Ce=N: or McSCNI, it is called thiocyanato ligand and is written as SCN. The complexes containing thiocyanato ligand are called thiocyanato complexes. For example [Pd**(dipy) (SCN),]° (orange yellow) is called dipyridyl dithiocyanato palladium (1), - . .. watt tan takes place through S-atom. This compound~OnIy Ny (6) When Ou, 2 =, is ion is called Isothiocyanato ligand ang jw, N: or Me-NCS), this ion 1 r * Written & oy ing NCS ion as a monodentate ligand are Calleq Ney s hav’ ; i Igo 4% The complex compounds having 'S),]° (light yellow) is called pyridy th, complexes. For example: [Pd”(dipy) (NCS).I 2" a egy, Hadium (I), since Pa is linked with SCN ligand through N-atom. It is algo um (U1), i ot cyanato (N) palladium (I). ellow and light yellow) show, “ Inge . n al Both the complex compounds (orange y POV a tiny te he coordination of SCN ion to the metal atom taxes plac, the ce (Me Calley yy ty isomers e soles, pairs of linkage isomers containing SCN/NC3 ions arg. Other examples q 0 (a) [Pd?*(PhyP)(SCN)2I° and [Pd?*(Ph3P),(NCS)2I (b) [Mn(CO),(SCN)] and [Mn(CO)s(NCS)] / has been observed that first row transition metals form N-bonded thiocyanate (ison compienel while second and third row transition elements form S-bonded thiocyanays (thiogy/% aorta acid ions (e.g., Pa, PU etc.) prefer to form thiocyanato complexes with soy. while hard acid ions (e.g., Co™, Cr* etc.) prefer to give isothiocyanato complexes wig i ion: N i . 7 marr spectroctemical series of ligands SCN (thiocyanate ion) lies close to C1 jg va NCS™ (isothiocyanate ion) is close to H,O. 3. Cyanide ion, CN”. This ion can be represented by any of the following two structures, Gon ‘Structure (1) * Structure (ID (Cyano group) (Iso-cyano group) Structures given above show that-when CN” ion acts as a monodentate ligand, it may be linked to the central metal atom either through the Ione Pair of electrons on C-atom [Structure @) or through the lone pair of electrons on N atom [Structure dD}. Thus: @) When this ion gets linked to the metal atom as a monodentate ligand through C-aton (MeG=n: or Mech), ion is called cyano ligand which is written as CN-. (©) When this ion is linked to the metal atom as a monodentate ligand through N-atom (MeN=C: or MCNC), this ion is called isocyano ligand, Actual isomeric compounds containin; yet been fully established, 4. Thiosulphate ion, $,02- B cyano (CN) and isocyano (NC) ligands have not + This ion can have any of the following two structures: (Thiosulphato ~ O ion, OS028?) Uhiosulphato—S ion, SSOs7]—- Structures given above show that when S,02 jon acts ‘as a monodentate ligand, it ms!