Bond energies complex hydrides

This type of side-on bending, which has been established by X-ray crystallographic methods for the related acyl complexes (r 5-C5H5)2Zr(COMe)Me (38) and (T>5-C5H5)2Ti(COMe)Cl (39), could overcome the thermodynamic objection, previously discussed, against the formation of a normal, linearly bonded formyl by CO insertion into a metal-hydride bond. Thermochemical data obtained from alcoholysis of zirconium tetralkyl species show that the mean bond energy of Zr—O is 50 kcal/mole greater than that of Zr—C (40). 

Lewis bases having two or more lone-pair-bearing atoms can exhibit a form of isomerism in H-bonding. This can be illustrated most simply with carbon monoxide, which has sigma-type lone pairs both on C and on O, and thus is expected to form n—>-cr H-bonds of either OC HA or CO HA type with a hydride-bearing Lewis acid. For example, complexation of CO with HF gives rise to distinct OC- -HF or CO- -HF complexes.39 The two possible isomeric forms are shown in Fig. 5.3, both bound by rather typical H-bond energies ... 

Besides these determinations of static structures, further studies of the kinetics of oxidative addition to Ir(I) complexes have been made. Beginning with Ir(CO)H(PPh3)3 (VIII), the first step is seen as dissociation to the four-coordinate planar intermediate (IX). This then deforms and undergoes concerted cis addition to yield the adduct (V) (179,224). In a comparison of group IV hydrides, PhsMH, the rates increased in the order Sibond energy but to the effects of differing polarizability and solvation of M-Ir products on the activation energy for addition. 

Sulfoxides C1CH2CH2C1 A good correlation of heterolytic benzylic C—H bond energies and alkylarene oxidation rates the formation of 9-phenylfluorene from triphenylmethane and other data imply rate-limiting hydride abstraction by POM-sulfoxide complex 536... 

M—H bond energies are approximately constant and negligible difference in AS, the thermodynamic preference of metal aryl hydride complexes and free alkane over metal alkyl hydride complexes and free aromatic substrate suggests that the ABDE for M Ar versus M—R is greater than the ABDE for Ar—H versus R—H (Chart 11.6). 

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