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By Mellor J.W

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The “methyl rotation” (process A ) in these compounds is found to be insensitive to L, being -11 kcal mol-’ for all the q-CSMeScomplexes. 5 kcal mol-’. The reason for these trends is not clear. It may be related to the observation while the q - G H j , that all the PR3, P(OR), ligands are cis to q-C5Mejligands are trans to HdgO,t,C. The barriers listed for process B involve interchange of C,, C,, or, in the ‘H NMR experiment, when coupled with the faster process A , scrambling of all five hydrogens.

The distorted alkylidene species have been characterized structurally and spectroscopically. The agostic M-H-C moieties exhibit ‘J(C-H) values in the range 45-105 Hz, and a low frequency u(C-H) stretch in the IR spectrum, 2200-2700 cm-’. 03 A in 18-electron complexes such as [Ta(q-C5H,)2(CH2)(CH,)1 (1 12). The T;i-C,-C, angles are in the range 154-170”, much larger than would be expected from steric opening of such angles by interaction between the tantalum center and the substituent on the alkylidene carbon.

8-Agostic Alkyl Complexes The characterization of agostic M-H,,-C3, bonds in the simple alkyl complexes [Ti(dmpe)Cl,(q’-Et)] (13) and [Co(q-C5Me5)(q-C2H4)(q2-Et)] (14) was important in the development ot the appreciation of agostic interactions. The P-agostic alkyls of the general structure 47 can also be viewed as bridged ethylene-hydride complexes and are often in rapid equilibrium with the olefin-terminal hydride 48 and/or the unsaturated alkyl complex 49. Eq. 2. 47 49 As is clear from dynamic studies summarized below, those P-agostic alkyl complexes that involve d oearly transition metal systems are no doubt closer in energy to the 16-electron metal-alkyl formulation, (49) (A<;* -< hG R).

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