Enthalpies of formation of complexes [M(η-C5H5)2(SR)2](M = Mo, W, or Ti; R = C3H7, C4H9, or C6H5); metal–sulphur bond enthalpies

Abstract
Standard enthalpies of formation (kJ mol–1) at 298.15 K were determined by reaction-solution calorimetry: ΔHf {[Mo(η-C5H5)2(SC6H5)2],c}= 309.4 ± 4.8; ΔHf {[W(η-C5H5)2{SC3H7-n)2],c}= 23.5 ± 5.6; ΔHf {[Ti(η-C5H5)2(SC3H7-n)2],c}=–253.0 ± 9.7; ΔHf {[Ti(η-C5H5)2(SC6H5)2],c}= 65.8 ± 7.9; and ΔHf {[Ti(η-C5H5)2(S2C6H3CH3)]}= 1.9 ± 9.4. From these data the metal–sulphur mean bond-dissociation enthalpies ( text-decoration:overlineD) and bond-enthalpy terms (E) have been derived, using extended-Hückel molecular-orbital calculations to take account of changes in structure upon dissociation.

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