Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Table 2.1 Selected bond lengths and angles in {[(Ph PCH2SiMe )2N]Cr} (u-Cl)2 (1).
2 2 2

Atom Atom Distance ( A ) Atom Atom Distance (A)

Cr(l) P(D 2.529(4) Cr(l) Cr(l)* 3.64

Cr(l) P(2) 2.514(4) Cr(l) N 2.078(8)

Cr(l) Cl(l) 2.397(3) N Si(l) 1.745(9)

Cr(l) Cl(l)* 2.546(3) N Si(2) 1.629(9)

Atom Atom Atom Angle (°) Atom Atom Atom Angle (°)

P(l) Cr(l) P(2) 136.8(1) Cl(l) Cr(l) N(l) 179.2(3)

Cl(l)* Cr(l) P(l) 107.4(1) Cr(l) Cl(l) Cr(l)* 94.6(1)

Cl(l)* Cr(l) P(2) 115.4(1) Si(l) N Si(2) 123.0(5)

Figure 2.1 Molecular structure (ORTEP) and numbering scheme for

{[(Ph2PCH2SiMe2)2N]Cr>2(p-Cl)2 (1). Phenyl substituents on phosphorus have
been removed for clarity.

36 References begin on page 100

 Chapter 2: Cr(H) and Co(II) Halide and Alkyl Complexes

bridging chloride ligands in the axial sites, and the two phosphine donors and the remaining

bridging chloride in the equatorial positions.

There is little axial distortion as is evident from the Cl(l)-Cr(l)-N(l) angle of 179.2(3)°.

In the equatorial plane, however, the P(l)-Cr(l)-P(2), Cl(l)*-Cr(l)-P(l) and Cl(l)*-Cr(l)-P(2)

angles of 136.8(1)°, 107.4(1)° and 115.4(1)°, respectively, do show substantial distortion from

ideal trigonal planar geometry due to the large steric repulsion between PPh donors. The Cr-Cr
2

distance of 3.64 A is too large to invoke the existence of a metal-metal bond. 19

The Cr-Cl bond lengths of 2.397(3) and 2.546(3) A indicate that the Cr (u.-Cl)2 bridging 2

core is highly unsymmetrical, similar to that found for [(dippe)CrCl]2(|i-Cl)2 (dippe = 1,2-

bis(diisopropylphosphino)ethane); 20
the Cr-Cl-Cr angle in 1 is 94.6(1)°. Hence, the structure is

best described as two loosely associated monomers. As a result it is not surprising to note that in

the mass spectrum of 1 only a monomer peak at 615 mle is observed (as opposed to a dimer

peak). Room temperature magnetic susceptibility measurements indicate a magnetic moment of

4.6 B.M. per chromium, consistent with an uncoupled high-spin d system. As will be shown
4

later, the two chromium centres are weakly antiferromagnetically coupled via chloride-mediated

superexchange.

The Cr-P bond lengths in 1 of 2.529(4) and 2.514(4) A are longer than the Cr-P bond

lengths of 2.488(2) and 2.507(2) A reported for [(dippe)CrCl] (u-Cl)2. The Cr-N bond length
2
20

of 2.078(8) A is similar to that found in rraAW-Cr[N(SiMe3) ]2(THF) (2.089(12) A ) . The N-Si

2 2
2 1

bond lengths of 1.745(9) and 1.629(9) A indicate the degree of ligand distortion; the shorter of

the two Si-N bond distances is the shortest reported, considerably shorter than in free disilazane

(1.735(12) A ) 2 2
but comparable to that found in rrans-Cr[N(SiMe3)2]2(THF)2 (1.674(17) A ) . 2 1

37 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

(ii) Reactivity of {[(Ph PCH SiMe2)2N]Cr} (ji-Cl)2 (1) with donor ligands
2 2 2

The extreme asymmetry of the metal-halide core in chromium chloride 1 suggested that

the bridge could be easily cleaved by coordinating solvents or ligands. Consistent with this idea,

1 is only slightly soluble in non-coordinating solvents such as benzene or toluene, but is

extremely soluble in THF, acetonitrile or pyridine. Addition of CO to a blue solution of 1 in

toluene results in the rapid formation of a bright yellow adduct, which quickly reverts to its

original blue upon removal of CO. A solution IR measurement of the yellow solution shows one

assignable CO stretch at v c o = 1971 cnr , a value consistent with a simple, five coordinate CO
1

adduct. Similarly, removal of THF or acetonitrile results in the recovery of blue, dimeric 1.

[2.2]

38 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

In the case of pyridine, the resulting adduct is stable even with no excess pyridine

present. Although crystals suitable for X-ray analysis could not be prepared, elemental analysis

indicated that only one pyridine was bound, and therefore the formula

CrCl(py)[N(SiMe2CH2PPh2)2] (l'py) is suggested. The formation of five-coordinate, labile

monomers is consistent with both the solid-state structural data and the vastly increased

solubility in coordinating solvents such as THF; this general reaction is typified in equation 2.2.

Similar behaviour has been observed in the system [(dippe)CrCl]2(p-Cl)2 and the formation of

the monomer Cr(NCCH3)Cl2(dippe) by reaction with acetonitrile. 20

The adducts all have substantially different colors, depending on the binding ligand, and

hence equilibrium constants for ligand binding could be determined by spectrophotometric

titration. All UV-vis titrations showed single isosbestic points, implying that the five-coordinate

species was a final product; no six-coordinate monomer was formed.

Table 2.2 UV-vis spectral data, equilibrium constants (equation 2.2) and solution magnetic
moments for {[(Ph2PCH2SiMe2)2N]Cr}2(p-Cl)2 (1) and its adducts with various
ligands.

Ligand Colour UV-Vis (nm) logK lieff (B.M.)

- Purple 284, 342(sh), 4.8

522(w), 688(w)

py Dark Green 290, 352(sh), 3.1±0.4 4.7

600(w, broad)
CO Bright Yellow 294, 390 2.5 ± 0.3 2.7
THF Navy Blue 304,562(w) 1.0±0.1 -
CH CN
3 Baby Blue 296 0.7 ± 0.05 4.7

39 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Table 2.2 shows the UV-vis data, equilibrium constants and adduct solution magnetic

moments (measured by Evans' method) for a series of ligands. The equilibrium constant data

shows that strong rj-donors such as pyridine have a much higher affinity (by two orders of

magnitude) than the more weakly basic C H 3 C N and THF. Although there is a lack of

comparable data in the literature, a more in-depth study of this equilibrium was not attempted.

The magnetic moments observed follow what could be predicted from the ligand

spectrochemical series; of the ligands tested, i.e CO is the strongest field ligand and thus it is able

to force a low-spin configuration.

(iii) Synthesis and structure of CoX[N(SiMe2CH PPh )2] (X = Cl, Br, I)

2 2

Addition of one equiv of LiN(SiMe2CH2PPh )2 to a THF suspension of CoX (X = Cl,

2 2

Br) results in the rapid formation of a dark blue solution. Removal of the THF and

recrystallization from hexanes/toluene (95:5) yields blue crystals of CoX[N(SiMe2CH2PPh2)2]

(X = Cl (2); X = Br (3)) in high yield (equation 2.3).

Ph 2

T H F , rt
Co-^X [2.3]
/
P

X = CI 2 Ph 2

X = Br 3

40 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

A solution magnetic moment measurement (Evans' method) 23,24

showed a value of u\ ff =
e

4.2 B.M., consistent with a high-spin tetrahedral Co(II) complex with some orbital contribution

via second-order spin-orbit coupling (d u , 7

so = 3.89 B.M.). 25
The dark, intense blue colour is

also consistent with most high-spin tetrahedral Co(II) complexes. ' 2 1,26,27
The visible spectrum of

chloride 2 has three bands at 506, 602 and 786 nm; for the bromide these bands shift to 518, 616

and 792 nm (Table 2.3).

Table 2.3 UV-vis spectral data for CoX[N(SiMe2CH PPh )2]. 2 2

X UV-vis spectrum (nm, (e, M^cm )) -1

Cl 506 (330), 602 (700), 786 (290)

Br 518 (310), 616 (530), 792 (270)

I 538 (230), 634 (560), 806 (290)

Although paramagnetic, the H NMR spectrum of chloride 2 shows two broad peaks at
l

15.0 and -5.4 ppm (the spectrum of bromide 3 is similar) with an integration ratio of 2:1.

Obviously several peaks are too broad to be observed, and although the assignment of these two

peaks as the meta and para protons on the phosphorus phenyl substituents may be correct (these

protons are farthest from the metal centre and the integration is consistent) without a detailed

labelling study any examination of the NMR spectrum for purposes other than fingerprinting the

compound would be fairly speculative. Knowledge of the spectrum is, however, useful in

compound identification. Other high-spin Co(II) complexes have been characterized by H l

NMR spectroscopy. 28

In order to obtain a representative crystal structure of the starting halide complexes, a

solution of CoI[N(SiMe CH PPh ) ] (4) (preparation described in Chapter 4) in toluene was

2 2 2 2

41 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

allowed to evaporate to near-dryness, depositing crystals suitable for X-ray diffraction. The

structure, shown in Figure 2.2, reveals the tetrahedral coordination sphere around cobalt; selected

bond lengths and angles are in Table 2.4. The dihedral angle between the planes defined by

P(l)-Co-N and P(2)-Co-I is 71.2° (90° is ideal), indicating the extent of the distortion from pure

tetrahedral coordination.

Examples of other tetrahedral high-spin Co(II) phosphine halide complexes (X = Cl, Br,

I) include CoX (PR3)2 (R = Ph, C6Hn),

2
26
CoX (dppe) and CoX (dppp), and CoCl (dippe),
2 2
27
2
20

some of which have been structurally characterized. Reported magnetic moments range from

3.9-4.6 B.M. A typical high-spin Co(II)-P bond length is 2.384(1) A, in C o ( P P h 3 ) X ; 2 2

29
in

trigonal Co[N(SiMe3) ] PPh3 an unusually long Co-P bond length of 2.479(5) A is observed.
2 2
30

These compare well with those observed in iodide 4, 2.348(3) and 2.373(3) A. Note that these

Co-P bond distances are substantially shorter than the corresponding Cr-P distances in the

chromium analogue 1; this is partly a reflection of the smaller size of Co(II) relative to Cr(II),

although steric considerations (dimer vs. monomer) could play a part. Effective ionic radii for

octahedral Cr(II) vs. Co(II) (high spin) centres are 0.94 vs 0.885 A . - 3 1 3 2
Due to the different

coordination number and geometry of these two systems a detailed comparison is probably not

worthwhile.

Cobalt(II) silylamides that have been structurally characterized include trigonal planar

Co[N(SiMe3) ] PPh , [Co (N(SiMe ) ) ] - and two coordinate Co[N(SiMePh ) ] . All

2 2 3
30
2 3 2 4
33 34
2 2 2
35

are high-spin complexes and have Co-N bond lengths ranging from 1.898(3) and 1.904(3) A in

Co[N(SiMePh ) ] 2 2 2
35
to 1.931(14) and 1.924(13) A in Co[N(SiMe ) ] PPh . 3 2 2 3
30
The Co-N bond

length of 1.936(6) A in iodide 4 is comparable to these values; the N-Si bond lengths of 1.717(7)

and 1.704(7) A are similar to those observed in the other systems mentioned. The Co-I distance

of 2.571(1) A is unremarkable.

42 References begin on page 100

 Chapter 2: Cr(II) and Co(H) Halide and Alkyl Complexes

Table 2.4 Selected bond lengths and angles in CoI[N(SiMe CH PPh2)2] (4).
2 2

Atom Atom Distance (A) Atom Atom Distance (A)

Co P(l) 2.348(3) Co N 1.936(6)

Co P(2) 2.373(3) N Si(l) 1.717(7)

Co I 2.571(1) N Si(2) 1.704(7)

Atom Atom Atom Angle (1 Atom Atom Atom Angle (")

N Co P(2) 88.5(2) P(l) Co P(2) 120.26(9)

N Co I 125.7(2) P(l) Co I 116.40(7)

P(2) Co I 108.14(7) P(D Co N 95.6(2)

Co N Si(l) 114.3(4) Si(l) N Si(2) 132.5(4)

C(3)

Figure 2.2 Molecular structure (ORTEP, 50% ellipsoids) and numbering scheme for
CoI[N(SiMe CH PPh2)2] (4).
2 2

43 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Upon comparison of the precursor ligated metal halide complexes for Cr(II) and Co(II)

some geometric differences can be observed. The Cr(II) halides prefer pentacoordination,

obtained either by dimerization or base coordination, while the Co(II) system is tetrahedral; no

evidence for dimerization is observed. The higher coordination number observed in the

chromium(II) system is likely a reflection of the extreme electronic unsaturation of the chromium

system relative to the cobalt system. Both types of complexes are high-spin, that is, have the

maximum possible number of unpaired electrons.

(iv) Reactivity of CoCl[N(SiMe CH PPh2)2] (2) with donor ligands

2 2

The reaction of tetrahedral cobalt chloride 2 with donor ligands is much less interesting

than that of the chromium analogue. Addition of pyridine, THF and acetonitrile to cobalt

chloride 2 results in essentially no change in the UV-vis spectra, indicating little or no binding is

occurring. Only in the case of CO addition does binding occur, but there is certainly no major

colour change; there is no spin-state change like that observed in the chromium(II) halide system.

A v c o stretch at 1981 cnr was observed in the solution IR spectrum. This binding is also
1

reversible; if the CO atmosphere is removed the adduct slowly releases CO over a matter of

hours to regenerate the original cobalt chloride complex 2.

2.3 Synthesis and Characterization of Chromium(II) and Cobalt(II) Alkyl

Complexes

(i) Synthesis and structure of CrMe[N(SiMe CH PPh ) ] (5)

2 2 2 2
3 6

The dimer {[(Ph PCH SiMe2)2N]Cr}2(p:-Cl)2 (1) reacts with MeMgBr or MeLi in THF
2 2

at -78 °C to yield red-brown CrMe[N(SiMe2CH2PPh )2] (5) in high yield, by alkali metal halide
2

44 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

salt metathesis (equation 2.4). Solid-state Gouy and solution Evans' method 23,24
magnetic

susceptibility measurements of the methyl complex 5 were consistent with a high-spin d 4

complex, indicating a monomelic compound. This derivative is soluble in aromatic solvents

25

and THF but only slightly soluble in hexanes. X-ray quality crystals of 5 could be grown by

cooling a saturated hexanes/toluene solution.

Ph 2

•P

M'R M e
2 S i
\

{[(Ph PCH SiMe ) N]Cr} (Li-CI)

2 2 2 2 2 2
: N - Cr CH 3

-78 °C /
Me SK 2
1
-P
Ph 2

M'R = MeLi, M e M g B r 5

The structural analysis confirms that 5 is monomeric and square planar in the solid state

(Figure 2.3), this being the preferred geometry for four-coordinate Cr(II). Hence a geometry 2a

change from trigonal bipyramidal to square planar has occurred upon methylation, although the

spin state remains unchanged.

What is particularly unique about this twelve-electron species is that it contains the

stoically undemanding methyl ligand; this is in stark contrast to other reported four coordinate

neutral organochromium(II) complexes that contain bulky alkyl or aryl ligands such as

CH2CMe3 or mesityl, respectively. 21,37

" 41
Anionic, square planar, formally 14-electron Cr(II)

alkyls are known. For example, the Cr(II) anion in the complex [Me4Cr][]Li(TMEDA)2]

appears to be stabilized by the associated lithium counterions; a similar system with bulky 42

neosilyl groups has also been structurally characterized 4 3

The few other Cr(II) alkyls are

dimeric with "supershort" Cr-Cr bonds (e.g. Li2Cr2Me8»4THF, [(Me2PCH2)4]Cr2) " and/or 44 46

45 References begin on page 100

 Chapter 2: Cr(II) and Co(H) Halide and Alkyl Complexes

bridging alkyl or aryl groups. - 47 48

Metal-metal bonding also provides the stability in the series of

chromium alkyls [Cp*Cr(u,-R)] . 2

49
A n octahedral Cr(II) alkyl, C r M e ( d m p e ) .
2 2
50,51
, has also

been reported.

In the methyl complex 5 there is some distortion from pure square planar geometry

(selected bond lengths and angles in Table 2.5); the P(l)-Cr-P(2) and N-Cr-C(31) angles of

154.77(4)° and 174.8(1)° respectively (180° is ideal) indicate the extent of the distortion. In

addition, the dihedral angle between the planes defined by Cr-P(2)-C(31) and Cr-N-P(2) is 23.9°,

and this represents the extent of the twist in what should ideally be a flat square planar core. The

Cr-P distances of 2.485(1) and 2.451(1) A and the Cr-C distance of 2.151(3) A are both

comparable with known square-planar neutral high-spin d Cr(II) a l k y l s . 4 20,37

Anionic Cr(II)-C

bonds are approximately 0.1 A longer, as would be expected. 42,43

The Cr-N bond length of

2.117(3) A is extremely l o n g 21,40

and this could indicate that there is very little, if any, amide

lone pair - metal prc-drc interaction.

Figure 2.3 Molecular structure (ORTEP) and numbering scheme for

CrMe[N(SiMe CH PPh )2] (5).
2 2 2

46 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

The electron density difference map revealed the Cr-methyl hydrogens to be one to one

disordered, and in a normal geometry. In addition, there is no IR evidence for any C r - C - H bond

agostic interaction. 52
This lack of such an interaction in neutral Cr(II) alkyls, despite the

coordinative and electronic unsaturation, has been previously noted as being due to the

unavailability of an appropriate empty orbital to interact with the C-H bond electron density, 37

although a static agostic interaction was observed in [Cr2(CH2SiMe3)6] ~ by *H NMR 2

spectroscopy. 43

(ii) Synthesis and structure of CoMe[N(SiMe CH PPh )2] (6) 2 2 2

In a similar manner to the synthesis of CrMe[N(SiMe2C H2PPh2)2] (5),

CoCl[N(SiMe2CH2PPh2)2] (2) reacts with MeLi or MeMgBr in THF or toluene to form the

desired CoMe[N(SiMe2CH2PPh2)2] (6) complex, which is a bright yellow colour, in stark

contrast to the intense blue precursor 2. Hence, although the methylation can be done in THF at

low temperatures (-78 °C), it is easier to simply titrate 2 in toluene at room temperature with

alkyl reagent until the blue colour has changed to yellow-orange (equation 2.5). This option is

not available for the chromium system. CoMe[N(SiMe2CH2PPh2)2] (6) is fully soluble in

aromatic solvents and moderately soluble in hexanes.

Ph 2 Ph 2

Toluene
Co—CI + M'R Co CH
: N
[2.5]
/
3

rt

Ph 2 Ph 2

Tetrahedral, high spin Square planar, low spin

2 M'R = MeLi, MeMgBr 6

47 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Table 2.5 Selected bond lengths and angles in MCH3[N(SiMe2CH2PPh2)2] (M= Cr, Co).

Atom Atom Distance (A)

M = Cr(5) M = Co (6)

M P(l) 2.485(1) 2.191(2)

M P(2) 2.451(1) 2.201(2)

M N. 2.117(3) 1.954(6)

M C(31) 2.151(3) 2.031(7)

N Si(l) 1.697(3) 1.711(6)

N Si(2) 1.699(3) 1.716(6)

Atom Atom Atom Angle O

M = Cr (5) M = Co (6)

P(l) M P(2) 154.77(4) 169.64(8)

N M C(31) 174.8(1) 178.4(3)

P(l) M N 88.13(7) 91.4(2)

N M P(2) 83.82(7) 92.2(2)

P(2) M C(31) 95.1(1) 88.9(2)

P(l) M C(31) 94.87(9) 87.7(2)

Si(l) N Si(2) 121.9(2) 123.0(3)

The colour change is an indication of the geometry and spin-state change that occurs

upon halide for alkyl metathesis. The solution room temperature magnetic moment for 6 is 2.2

B.M., consistent with a low-spin d centre with some second-order spin-orbit coupling. This
7 25

indicates a geometry change from tetrahedral to square planar has occurred, in contrast to the

chromium system where no spin state change was observed upon alkylation.

48 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

X-ray quality crystals of CoMe[N(SiMe2CH2PPh2)2] (6) were grown by slow

evaporation of a hexanes solution. The result is shown in Figure 2.4; selected bond lengths and

angles are in Table 2.5 beside the data for the analogous chromium system. The structural

analysis confirms that 6 is monomeric and square planar; this complex is nearly isostructural to

the chromium analogue already prepared. There is less distortion in the cobalt complex than in

the chromium case. The Co(II) coordination sphere is reasonably flat; the dihedral angle

between the planes defined by Co-P(2)-N and Co-P(l)-C(31) is only 9.8° in 6, a slight twist

compared to the 23.9° observed in chromium methyl 5.

Structurally characterized examples of Co(II) alkyls are uncommon. 53

Five coordinate

CoMe2(PMe3)3, [CoMe(OMe)(PMe3)2]2> and octahedral CoMe(acac)(PMe3)2 are known but 54

no X-ray structures have been reported. Structurally characterized compounds with Co(II)-C

bonds include the cobalt(II) aryl complexes Co(PEt2Ph)2(mesityl)2 " 55 57

and bis(p-

mesityl)dimesityldicobalt(EI) 58
which are low-spin square planar and high-spin trigonal

respectively, with Co-C(sp ) distances of 1.994(3) and 1.988(7) A .

2
A series of bulky cobalt

alkyls stabilized by TMEDA have also been structurally characterized. 59

These are high-spin

and tetrahedral, with Co-C distances ranging from 2.025(7) - 2.151(8) A . In comparison, the Co-

C bond length of 2.031(7) A in low-spin, square planar methyl 6 is shorter than in the high-spin

alkyls but not as short as for the low-spin, stronger aryl bond. This difference is rationalized by

the smaller size of a low-spin Co(II) centre vs. the high-spin case. For octahedral Co(II),

effective ionic (crystal) radii of 0.79 and 0.885 A for low and high-spin Co(II) respectively are

reported. 31,32
Metal-phosphorus bond lengths are particularly sensitive to spin state; this is partly

a reflection of the metal's size differences in different spin states. In the case of Co(II), a typical

high-spin Co(II)-P bond length is 2.373(3) A in iodide 4 and 2.384(1) A in Co(PPh )2X ; . 3 2
29

Low-spin Co(II)-P bond lengths are substantially shorter, as observed in Co(PEt2Ph)2(mesityl)2

(2.232(4) A ) 5 6 , 5 7
and CoMe[N(SiMe CH2PPh )2] (6) (2.191(2), 2.201(2)
2 2 A ) .

49 References begin on page 100

 Chapter 2: Cr(II) and Co(H) Halide and Alkyl Complexes

CI15)

Figure 2.4 Molecular structure (ORTEP, 50% ellipsoids) and numbering scheme for
CoMe[N(SiMe CH PPh )2] (6).
2 2 2

Known Co(II) silylamide complexes are all high-spin complexes and have Co-N bond

lengths ranging from 1.898(3) and 1.904(3) A in C o [ N ( S i M e P h ) ] 2 2 2

35
to 1.931(14) and

1.924(13) A in Co[N(SiMe ) ] PPh3

3 2 2
3 0
In methyl 6 the Co-N bond length of 1.954(6) A is much

shorter than the 2.117(3) A observed in chromium methyl 5. This could be due to the difference

in size between high-spin Cr(II) (octahedral ionic radius 0.94 A) and low-spin Co(II) (octahedral

ionic radius 0.79 A) centres (see Table 2 . 5 ) . 31,32

(iii) Paramagnetic H NMR spectrum of CoMe[N(SiMe CH PPh ) ] (6)

l
2 2 2 2

Despite the fact that Co(II) alkyls are paramagnetic, H N M R spectra can be observed.
l 60

In the absence of a detailed labelling study definitive assignments are challenging but integration

ratios, peak shifts with variable temperature and comparison of a series of similar complexes

allows for some assignments to be made. 61

In addition, the H N M R spectrum of a given
A

50 References begin on page 100

 Chapter 2: Cr(H) and Co(II) Halide and Alkyl Complexes

compound serves as an excellent fingerprint for its identification in reactivity studies. Note that
3 1
P NMR spectra are not observed for any paramagnetic complex in this thesis.

Figure 2.5 *H NMR spectrum of CoMe[N(SiMe CH PPh )2] (6) in C D (*).

2 2 2 6 6

The iff NMR spectrum of CoMe[N(SiMe CH PPh ) ] (6), shown in Figure 2.5, has five
2 2 2 2

peaks present; the C0-C//3 peak is not observed. The assignments are based on integration (60

°C spectrum, CgDg), the direction of shifting peaks upon increased temperature (peaks shift

towards their diamagnetic values) and the inherent broadness of each peak (resonances due to

protons closer to the metal are broader). The SiMe peak at -3.3 ppm is easily identified by its
2

unique integration (12H). Although the resonances due to the phenyl ortho and meta protons

have the same integration (8H), the ortho proton resonance (closer to the metal centre) at 9.8 ppm

is very broad (340 Hz width at half-height), much broader than the meta proton resonance at 6.5

ppm (40 Hz width at half-height). Similarly the para proton and the backbone methylene

resonances (both integrate to 4H) can be distinguished by the fact that the para proton peak at 8.4

ppm is sharp while the much closer methylene proton peak is observed at -6.3 ppm (260 Hz

width at half-height).

51 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

(iv) Synthesis and structure of M(CH2Ph)[N(SiMe CH PPh2)2] (M = Cr (7), Co (8))

2 2

Reaction of the chromium chloride dimer 1 with KCH2Ph or Mg(CH2Ph)2*2THF

(Scheme 2.1) yields the purple compound Cr(CH2Ph)[N(SiMe2CH2PPh2)2l (7) which has a

magnetic moment of 5.1 B . M . , 36

consistent with a monomeric, high-spin d complex. 4 25
The

analogous cobalt(II) benzyl complex, Co(CH2Ph)[N(SiMe2CH2PPh2)2] (8) was prepared in a

similar manner. Complex 8 is orange in colour, with a magnetic moment of 2.1 B.M., consistent

with a low-spin Co(II) centre. Crystals of 7 and 8 suitable for X-ray analysis were grown by

slow evaporation of saturated hexanes solutions.

Scheme 2.1

.p * Ph
7
M = Cr (1) Me Si
2

CH;
• I - - - \ ^

M C I [ N ( S i M e C H 2 P P h ) ] + M'R
2 2 2

M'R= KCH Ph2 Me Si(

2

Mg(dH Ph) .2THF

2 2 M = C o (2) : \

Me S 2
; /

The X-ray structures reveal distorted square-planar, monomeric metal centres for both the

chromium (7) and cobalt (8) benzyl compounds (Figure 2.6); this distortion from square planar is

more pronounced than in the methyl complexes (Table 2.5 and 2.6). In particular, the chromium

benzyl complex 7 appears highly distorted. The P(l)-Cr-P(2) and N-Cr-C(31) angles of

145.18(3) and 157.8(1)° show greater "bending-back" than in chromium methyl 5. The dihedral

52 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

angle between the Cr-P(l)-C(31) and Cr-P(2)-N planes is 38.7° (vs. 23.9° in 5), indicating again,

the increased twist in chromium benzyl 7 from an ideal flat core compared to the chromium

methyl complex 5. The Cr-P distances of 2.4758(9) and 2.4808(8) A are similar to 5 and to other

known square-planar Cr(II) alkyls. 37

The Cr-N bond of 2.067(2) A, shorter than in 5, coupled

with comparatively slightly longer Si-N bonds of 1.707(2) and 1.706(2) A suggest that the lone-

pair on nitrogen is interacting with the metal to a slightly greater extent than in the methyl

complex 5.

The cobalt benzyl complex 8, on the other hand, is much more similar to its methyl

analogue (6) than in the chromium case. There is still more distortion from square planar in the

cobalt benzyl vs. the cobalt methyl complex as shown by the P(l)-Co-P(2) and N-Co-C(31)

angles of 162.93(3)° and 173.6(1)° (closer to ideal 180° in 8) and the dihedral angle between the

planes defined by Co-P(2)-N and Co-P(l)-C(31) of 14.3° (9.8° in methyl 8).

Figure 2.6 Molecular structure (ORTEP) and numbering scheme for

M(CH Ph)[N(SiMe2CH2PPh )2] (M= Cr (7), Co (8)).
2 2

53 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Table 2.6 Selected bond lengths and angles in M(CH Ph)[N(SiMe2CH PPh )2] (M= Cr, Co).
2 2 2

Atom Atom Distance (A)

M = Cr (7) M = Co (8)
M P(l) 2.4758(9) 2.2127(8)
M P(2) 2.4808(8) 2.2162(8)
M N 2.067(2) 1.982(2)
M C(31) 2.132(3) 2.009(3)
N Si(D 1.707(2) 1.702(2)
N Si(2) 1.706(2) 1.707(2)
M C(32)ip SO 2.576(3) >3
M C(33) hoort
3.093(3), 3.364(3) -
C(31) C(32)ip SO 1.456(4) 1.480(4)
C(33) C(34) 1.380(5) 1.383(5)
C(34) C(35) 1.366(6) 1.359(6)
C(35) C(36) 1.359(5) 1.361(7)
C(36) C(37) 1.379(4) 1.410(7)
C(32)ip SO C(33) hoort
1.402(4) 1.378(5)
C(32)i DSO C(37) h ort 0
1.394(4) 1.393(4)

Atom Atom Atom Angle O

M = Cr (5) M = Co (6)
P(l) M P(2) 145.18(3) 162.93(3)
N M C(31) 157.8(1) 173.6(1)
P(l) M N 84.31(6) 82.83(6)
P(2) M N 87.96(6) 86.98(6)
P(2) M C(31) 99.42(1) 95.55(9)
P(l) M C(31) 100.4(1) 96.01(9)
Si(l) N Si(2) 122.3(1) 126.3(1)
M C(31) C(32)jp SO 89.7(2) 100.1(2)
M C(31) H(37) 109(1) 111.8 (idealized)
M C(31) H(38) 116(1) 111.8 (idealized)

54 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

The increased distortion from ideal square planar geometry could be due to the steric bulk

of the benzyl moiety as compared to the methyl ligand and this is likely the case for the cobalt

benzyl complex. However, the large distortion in the chromium case has another source: the

weak interaction of the benzyl ip so-carbon with the metal center. This type of interaction has

been represented in the literature as an T] -bound benzyl, and is fundamentally distinct from
62 2

either an r^-a-bonded benzyl or an rj^-benzyl complex.

Several structural features have been highlighted as key in characterizing rj -benzyls2 62,63

and these have, for the most part, been recognized in the chromium benzyl complex 7. Firstly,

the Cr-Qp o distance of 2.576(3) A is short enough to consider the presence of a weak metal-
S

carbon bond. On the other hand, the Cr-C rtho distances of 3.093(3) and 3.364(3) A are clearly
0

too long to consider any interaction as would exist in an r) -bonding mode. The C r - C H 2 - Q
3
pso

angle of 89.7(2)° indicates the extent of the pull of the ipso-carbon towards the metal, resulting in

an angle much more acute than the expected tetrahedral 109°. The C H 2 - Q p S0 distance of

1.456(4) A is comparable to the values found in other r| -benzyls ' and this length is shorter
2 62 64

than in r^-benzyls. Four of the C-C bonds in the phenyl ring of the benzyl ligand are similar in

length: 1.380(5), 1.366(6), 1.359(5) and 1.379(4) A , indicating a delocalized system consistent

with rj -bonding, as shown below:

2

55 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

An r) -bound benzyl group normally forces localization of the bonding in the phenyl ring and
3

this is not observed. Also consistent with r| -coordination, the Qp -C ho bond lengths are 2
SO ort

elongated relative to the rest of the benzyl ring, being 1.402(4) and 1.394(4) A . In fact, one

could almost consider this complex to be pentacoordinate. In terms of total electron count,

chromium benzyl 7 can be considered as a fourteen electron system if one takes into account the

ri -benzyl formulation. The possibility of an agostic interaction between the benzyl C H 2 and the
2

chromium centre can be discounted. The methylene hydrogens were located and refined and the

Cr-C(31)-H angles of 109(1)° and 116(1)° clearly show no distortion characteristic of agostic

interactions. 52

The Cr-C(31) bond length of 2.132(3) A is shorter than that found in methyl 5. This

length compares well with other short Cr-C bonds recorded, for example, 2.131(2) A for

Cr (CH SiMe3) (PMe3)2 and 2.128(4) A for Cr(CH SiMe3) (dippe). -

2 2 4 2 2
37 65
A comparison of the

structural features of the rj -benzyl in 7 with other chromium benzyl complexes reveals the
2

predominance of the r\ -binding mode. 1

The formation of the Cr(II) bis (benzyl) complex

Cr(CH Ph) (TMEDA) has been reported; the solid state structure clearly shows r^-benzyl type
2 2
38

ligands with Cr-C bond lengths of 2.177(2) A and C r - C H - C i 2 pso bond angles of 111.9(1)°. The

Cr(II) benzyl complex Cp*Cr(CH Ph)bipy also shows simple T J coordination (Cr-CH -Qp
2
1
2 S0

bond angle is 114.3(4)°). 66

Chromium(III) benzyls are certainly known as compounds such as

Cr(CH Ph)Cl (THF), Cr(CH Ph)Cl (py) and [Cp*Cr(CH Ph)Cl] illustrate; ' all contain r| l-
2 2 2 2 3 2 2
67 70

benzyl groups. Especially well studied are the [Cr(CH Ph)(OH )5] cations but the only 2 2
2+ 71

crystal structure of such a cation is that of [p-BrC6H4CF£ CrL(H 0)](C104) (L = [15]aneN4). 2 2 2

72

Here the sterically enlarged Cr-CH -Qp angle of 123°, slightly longer Cr-CH bond length of
2 S0 2

2.14(2) A and longer C H - Q 2 p s o bond length of 1.48(2) A all are indicative of a standard ri - 1

benzyl. There is one example of a chromium-based T| -benzyl complex, namely 2

Cr(NR) (CH Ph) , a Cr(VI) complex

2 2 2
7 3
This compound contains both an r | and an t] benzyl 2 1

ligand. The C r - C H - C 2 ipso bond angles are 82.16(11) and 114.73(13)° for the T ] and rj benzyls 2
1

56 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

respectively. The r | - b e n z y l is further structurally characterized by a C r - C i

2
p s o bond length of

2.357(2) A, a C H - C 2

ipso bond distance o f 1.443(3) A and elongated Cip -C tho distances of

SO or

1.409 A (vs. 1.395(3) A (average) i n the rest o f the ring). These data suggest an even greater

interaction with chromium i n this r | - b e n z y l than that observed i n 7 ; this is likely due to the
2

extremely high-valent Cr(VI) centre i n Cr(NR)2(CH2Ph)2 vs. the high spin Cr(II) centre i n

benzyl 7. Comparison with known Mo, W and Z r T] -benzyls shows that the structural features
2

are similar, however, a meaningful, quantitative comparison may be difficult to m a k e . ' ' 6 2 6 4 7 4

Complex 7 appears to be the first example of a paramagnetic r\ -benzyl complex. 2

The cobalt benzyl complex 8, which contains the same ligand set and gross geometry as

the chromium benzyl 7 , does not show any evidence o f an rj -benzyl interaction. The electron
2

deficient chromium complex (12 electron system) binds the benzyl group i n an ri -fashion in an 2

attempt to satisfy the metal's electronic unsaturation. O n the other hand, the more electron-rich

15-electron cobalt system does not require the extra electron density for stabilization and hence

remains bound in an r^-fashion, as illustrated by the Co-C(31)-C(32) bond angle o f 100.1(2)°

and C o - Q p S O distance of over 3 A. Note that cobalt methyl 6 and benzyl 8 are the only examples

of structurally characterized low-spin square planar Co(II) silylamide complexes.

(v) Synthesis of M(CH SiMe )[N(SiMe CH PPh ) ] (M = Cr (9), Co (10))

2 3 2 2 2 2

The reaction o f L i C H 2 S i M e 3 (neosilyl lithium) with c h r o m i u m chloride 1 proceeds

(equation 2.6) to generate the expected compound Cr(CH2SiMe3)[N(SiMe2CH2PPh2)2] (9),

however, it was not isolated as a solid, but rather as a purple o i l and thus was not characterized

fully. One feature o f 9 that was noted in passing was the temperature dependence of its colour.

A t room temperature 9 is purple in toluene but becomes brown at -78 °C; this is fully reversible.

This compound was used in situ for a variety of redox reactions.

57 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Ph 2

P
LiCH SiMe M e
2Si
\
2 3

MCI[N(SiMe CH PPh )2]

2 2 2 M CH SiMe
2 3 [2.6]

-78 °C
Me Si
/
2

P
Ph 2

M = Cr 9

M = Co 10

On the other hand the cobalt derivative, Co(CH2SiMe3)[N(SiMe2CH2PPh2)2] ( 1 0 ) can be

isolated by crystallization from hexanes. This cobalt(II) alkyl is also yellow and low-spin (u, ff = e

2.0 B.M.) and is likely identical in structure to 6 and 8 , the other cobalt(II) alkyls. The H NMR l

spectrum of 1 0 shows four peaks only; the backbone methylene and the neosilyl-methylene

protons are probably too close to the metal centre to be observed.

(vi) Synthesis of M(ri -C5H )[N(SiMe2CH PPh2)2] and structure of the Cr(II) derivative
5
5 2

The addition of NaCp^DME to the starting chromium chloride 1 gives the

cyclopentadienyl compound Cr(T| -C5H5)[N(SiMe2CH2PPh2)2] ( 1 1 ) which has a magnetic

5

moment of 2.7 B.M., consistent with a low-spin configuration (equation 2.7). The same

compound can also be synthesized by reaction of the methyl complex 2 in toluene with freshly

cracked cyclopentadiene, forming 1 1 with concomitant loss of CH4 (equation 2.8). 36

58 References begin on page 100

 Chapter 2: Cr(H) and Co(II) Halide and Alkyl Complexes

r
Me Si2
T H F , -78 °C

2 Ph 2 [2.7]
MeoSi 2 NaCp-DME
Ph P
2

HIGH spin 6 A
1 LOW spin d' 11

The magnetic moment of 11 is comparable to the similar compound Cp*CrMe(dmpe),

which has a reported magnetic moment of 2.79 B . M . 14

This is an example of a spin state change

upon alkylation of the Cr(II) halide precursor. The coordination of the Cp ligand was deduced to

be T ] , as an r^-Cp would be expected to be high-spin, as found for complexes 5 and 7, the other
5

Cr(II) alkyls. The analogous cobalt complex, Co(C5H5)[N(SiMe2CH2PPh2)2] (12) can be made

in similar fashion and has been characterized by elemental analysis and NMR spectroscopy

(see below). The hapticity of the Cp in this compound is unknown, although it is also low spin,

withpeff = 1.9 B.M.

59 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

With regard to the chromium cyclopentadienyl compound 11, the preference for a low-

spin environment can be rationalized by invoking a comparison with Cp2Cr, chromocene, which

is also a 16-electron, low-spin d system. The tridentate ancillary ligand, -N(SiMe2CH2PPh2)2,

4

formally an anionic, six-electron donor, can qualitatively be considered as isoelectronic to a

"C5H5 moiety. One could, therefore, envision the MO-diagram for 11 to be similar to

chromocene, with the appropriate removals of degeneracy for the reduction in symmetry. Thus

chromocene has an E2 , doubly degenerate ground state with two unpaired electrons; Cr(r) -
g
75 5

C5H5)[N(SiMe2CH2PPh2)2] (11) would be expected to have a similar pair of SOMO's and from

this its low-spin nature is derived.

Dark red prismatic crystals of 11 were grown by slow evaporation of a saturated hexanes

solution. The crystal structure (Figure 2.7), shows a pseudo-octahedral three-legged piano-stool-

like monomeric Cr(II)-Cp complex with C symmetry. Selected bond lengths and bond angles
s

are given in Table 2.7.

The Cr-N bond length of 2.066(7) A is considerably shorter (0.05 A) than in the methyl

complex 5 but comparable to benzyl 7; this bond length is also very similar to that found in the

chloride dimer 1 (2.078(8) A). The N-Si bond lengths of 1.687(8) and 1.689(8) A are

comparable to those in Cr[N(SiMe3)2]2(THF) (1.674(17) A ) .

2
21

The Cr-P distances in 11 are 2.353(3) and 2.366(3) A, much shorter (approx. AO.lA) than

the analogous distances in methyl 5 or benzyl 7. This can easily be rationalized as being due to

the low-spin nature of 11 as compared to the other, high-spin compounds. The sensitivity of the

Cr-P distance to metal spin-state and environment has been previously noted both in the

literature and in this thesis.37

The octahedral, low spin CrX2(dmpe)2 (X = Cl, Me, O2CCF3)

complexes have Cr-P distances ranging from 2.345-2.387 A; compound 11 is within this

60 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Table 2.7 Selected bond lengths and angles in Cr(Ti -C5H5)[N(SiMe CH2PPh2)2] (11).
5
2

Atom Atom Distance (A) Atom Atom Distance (A)

Cr P(D 2.353(3) Cr N 2.066(7)

Cr P(2) 2.366(3) N Si(l) 1.687(8)

Cr Cp 1.86 N Si(2) 1.689(8)

Atom Atom Atom Angle (°) Atom Atom Atom Angle (°)

N Cr P(2) 89.0(2) P(l) Cr P(2) 103.9(1)

P(l) Cr Cp 120.5 Si(l) N Si(2) 132.7(4)

P(2) Cr Cp 121.7 PCD Cr N 83.9(2)

Figure 2.7 Molecular structure (ORTEP) and numbering scheme for

C r ( r f - C H ) [N(SiMe CH PPh2)2] (11)-
5 5 2 2

61 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

(vii) Paramagnetic H NMR spectra of M(C H )[N(SiMe CH PPh )2] complexes

A
5 5 2 2 2

Unlike the other chromium(II) alkyls prepared, the Cr(II) cyclopentadienyl complex 11

possesses an observable H NMR spectrum. However, only two peaks are visible and both are
A

very broad. The two resonances, at 3.3 and 10.3 ppm, integrate in a 1:2 relative ratio and are

highly temperature-dependent. These are likely the meta and para protons on the phenyl ring but

in the absence of a detailed study, a definitive assignment is impossible.

n*

T-| i • i i | i i i i | • • i i i • • i • i • • • • i i i i ii •1
1 1
i 1
• ' • i •1 1 1
i 1 1 1
'l 1
' 1 1
i ' • ' 1
i 1 1 1 1
i • 1 1 1
i 1
1 1
• i 1 1 1 1
) 1
1
• r
1

85 7.5 6.5 5.5 4.5 D D .. 3.5 2.5 1.5 0.5

Figure 2.8 A
H N M R spectrum of C o ( C 5 H ) [ N ( S i M e 2 C H P P h ) 2 ] (12) i n C 6 D ( * ) .
5 2 2 6

On the other hand, the H NMR spectrum of Co(C5H )[N(SiMe2CH PPh )2] (12) can be
l
5 2 2

tentatively assigned (Figure 2.8). Resonances for all six sets of protons are observed. Notably,

the resonance due to the C0-C5//5 protons at -25 ppm is visible, but is very broad (1000 Hz

width at half-height). The fact that there is only one resonance for the Cp group indicates either

that theringis T] -bound or is highly fluxional. In the absence of a crystal structure, the hapticity
5

of the Cp ring is difficult to ascertain. The SiMe2 resonanace at 1.0 ppm is uniquely identified by

62 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

its integration (12H). The meta and ortho protons are difficult to distinguish but integration

identifies them as the resonances at 7.6 and 8.1 ppm. The ortho proton is likely further

downfield (8.1) as it is quite broad (0.6 ppm) while the peak at 7.6 ppm is quite sharp. The sharp

peak at 7.0 is the para-proton while the broad peak at -10.2 ppm is likely due to the backbone

methylenes; both integrate to four protons.

In general, then, low-spin cobalt(II) complexes provide reasonable paramagnetic *H

NMR spectra but neither high or low-spin chromium(II) systems presented here possess

assignable spectra.

(viii) Electronic structure and magnetism of CrR[N(SiMe2CH2PPh2)2]

High-spin, four-coordinate Cr(II) complexes have been shown to electronically prefer a

square-planar environment as the four lowest energy d-orbitals are half-filled, similar to that

found for the spin-paired d systems such as Rh(I) and Pt(II).

8 2e

The chromium alkyls synthesized illustrate a wide variety of hapticity and total electron-

donating ability. The Cp ligand binds in an T) fashion to enable donation of its full six electrons
5

(using oxidation state formalism). As well, the benzyl ligand binds in an r j fashion, formally
2

acting as a four-electron donor as opposed to an r) , two-electron donor. Steric constraints may

1

restrict T | or higher coordination of the benzyl ligand but this seems unlikely given the existence
3

of the cyclopentadienyl complex 11 having the ancillary tridentate ligand bound in a facial

manner. However, it could be that the high-spin state Cr(II) centre cannot electronically bind the

benzyl in a higher hapticity mode without a change in spin state. ' '* The fact that the benzyl
1 19 0

derivative 7 remains a high-spin compound indicates that the T J mode of coordination is

2

insufficient to force spin-pairing.

63 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

A ZINDO 8 1 , 8 2
restricted open shell Hartree F o c k ( R O H F ) calculation study confirms the

stability o f the experimentally observed spin states. T h e ability o f the Z I N D O method to

successfully describe the ground states o f simple transition metal complexes has been noted

earlier. 81-83
U s i n g a simplified coordination sphere as a calculation model (Figure 2.9), the total

energy for each compound i n a singlet, triplet and quintet ground state multiplicity was

calculated (Table 2.8). The bond lengths o f each model were taken from the relevant crystal

structure and were fixed for each calculation; i n this way a meaningful comparison based on spin

state c o u l d be made. The assumption o f a fixed structure, while obviously not ideal (spin

changes cause geometry changes i n many cases), nevertheless suffices. T o test this, the C r - P

bond lengths i n the model compound fran^-Cr(CH3)NH2(PH3)2 were fixed to both typical high

and typical l o w spin values and the multiplicity calculations repeated. Although the absolute

energy values were different, the stability o f the quintet state relative to the triplet and singlet

state did not change, nor did the approximate magnitude o f the relative stability. In addition, the

calculations were performed on a tetrahedral model o f Cr(CFf3)NH2(PH3)2 without any change

in the qualitative order o f stability. Ideally, a geometry optimization with total energy should be

performed, however this feature is not available with this relatively low-level calculation

program.

The graph i n Figure 2.10 shows the energy differences between the three possible

multiplicities for the models based o n the crystal structures o f the hydrocarbyl compounds 5, 7

and 11, where the most stable multiplicity is set at 0 kJ/mol and the energy difference between

the most stable multiplicity and the others is plotted on the y-axis. The results show that for

methyl 5 and benzyl 7, there is a substantial stabilization of the quintet state relative to the singlet

of 309 and 276 kJ/mol respectively. The stabilization from the triplet state is 205 and 192 kJ/mol

respectively. Calculations on the cyclopentadienyl derivative 11, however, show that the triplet

64 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

Table 2.8 ZINDO relative total energy calculations for the simplified complexes
CrR(NH2)(PH3)2 in the indicated geometries. All values given are in kJ/mol.

Spin State CH 3
a
CH Ph
2
a
C H
5 5
a
CH^b CH 3
C

1 -114261 -212564 -181548 -114633 -114311

3 -114365 -212648 -181686 -114734 -114369

5 -114570 -212840 -181623 -114926 -114512

a. model based on the crystal structure

b. crystal structure geometry with Cr-P and Cr-N bond lengths altered to 2.36 and 2.06 A
respectively; typical low-spin Cr(II) values taken from the crystal structure of 11
c. mechanics minimized tetrahedral structure

Figure 2.9 Simplified coordination sphere models for complexes 2, 5 and 11 (left to right)
used in ZINDO ROHF MO-energy calculations.

65 References begin on page 100

 Chapter 2: Cr(II) and Co(II) Halide and Alkyl Complexes

1 1 T
1 3 5

Multiplicity

Figure 2.10 Graph of calculated relative energies vs. spin multiplicity.

state is the most preferred state, with stabilizations over the singlet and quintet states of 138 and

63 kJ/mol, respectively. As expected, for a high-spin square planar d system, the unpaired
4

electrons in 5 and 7 occupy the lower four d-orbitals, leaving the d -y orbital empty.
x
2 2

Calculations on the analogous model system using a cobalt centre instead of a chromium

centre resulted in less convincing results. In this case, the energy difference between a spin

doublet and a spin quartet was calculated. The vital difference is in geometrical possibilities; in

the chromium case, a square planar ligand arrangement is generally observed, but in the cobalt

case both tetrahedral and square planar coordination spheres are common. Since the level of

theory used in these calculations is not sufficient to geometry-optimize a transition metal

complex, assumptions about the cobalt-centre geometry become necessary. Given the correct

66 References begin on page 100

 Chapter 2: Cr(H) and Co(Il) Halide and Alkyl Complexes

geometry o f a given system (and the appropriate bond lengths), the correct spin state was

predicted. For example, a square planar model of the cobalt methyl complex 6 was calculated to

prefer a spin doublet by 80 kJ/mol over the S = 3/2 state. However, upon changing the geometry

to a tetrahedral system, the quartet became the preferred spin-state, although the absolute energy

was substantially lower for the square-planar case. Essentially, i n the situation where geometry

becomes a factor, the simple calculation method described demands prior knowledge of the

structure i n order to make any sort of prediction. A higher level of theory would substantially

improve this situation. In essence, the concept of using theoretical calculations to predict the

spin state o f a given complex is viable given an appropriate level o f theory (which we lack here)

and a geometry optimization routine which can deal with transition metal complexes. Such

calculations have been reported for the molybenum(III) system Cp*MoCl(PH3)2 and successfully

predict the stability of the triplet state over the singlet state. Calculations indicating that spin-

state change and the associated geometry changes are important thermodynamic factors with

regard to reactivity were also i n c l u d e d . 79

2.4 Synthesis and Structure of Cr(SiMes H)[N(SiMe2CH PPh2)2] (13)

2 2

G i v e n the synthetic success and stability of paramagnetic metal-carbon bonds observed

up to this point, it was o f interest to examine the stability of the heavier congener, silicon bonds

to paramagnetic metals, particularly in the electron-deficient chromium system.

Metal-silicon bonds have been thoroughly examined and examples utilizing both early

and late metals in high and l o w oxidation states exist, but there are relatively few paramagnetic

examples. 84
There is a series of lanthanide-silyl complexes, [Cp2M(SiMe3)2][Li(DMF)3] ( M =

Sm , L u
85 8 6
structurally characterized, other M = D y , H o , E r , T m ) . 8 7 , 8 8
Some paramagnetic

transition metal-silyl complexes include Cp Nb(SiMe3)(r| -C2H4),

2
2 89
Cp*Ta(SiMe3)(PMe3)Cl2, 90

Cp Ti(SiH Ph)(PEt3) and C p T i ( S i H P h ) ( P M e ) ,

2 2 2 2 3
91
all o f which are d 1
systems.

67 References begin on page 100