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Titration calorimetry has been used to determine the enthalpies of protonation (AHHM) of twenty two Cp'M(PR3)(PR'3)X complexes (Cp' = TI®. CgHgCCp) or i^S-CgMesCCp*); M = Ru, Os; PR3 = PPha, PPhgMe, PPhMe2, PMes, P(0Et)3, dppm, dppe, dppp; X = H, CI, Br, I) with CP3SO3H in 1,2dichloroethane solution at 25.0 °C to give Cp'M(PR3)(PR'3)(XXH)+CF3S03-. Systematically changing the ligands and/or the metal in these complexes has yielded AHHM values for protonation at the metal that range from -14.1 kcal/mol for CpOs(PPh3)2l to -39.2 kcal/mol for CpOs(PPh2Me)2H. Metal basicities (AHHM) of the CpOs(PPh3)2X complexes correlate linearly with the gas phase proton affinities of the X ligands, both of which increase in the order: I* < Br < CI" « H*. Substitution of a halide ligand with a hydride causes the metal basicity to increase by as much as 23.2 kcal/mol. The basiddties of CpOs(PPh3)(PR3)Br complexes increase in the order: P(0Et)3 < PPh3 < PMes. There is a linear correlation between the basidties (AHHM) of the CpOs(PR3)2Br complexes and the basidties (AHHP) of their PR3 ligands. In a series of complexes, the Cp* ligand increases the basidty of the metal by 5.5-9.0 kcal/mol over that of the corresponding Cp derivative, and Os complexes are 6.0-8.5 kcal/mol more basic than analogous Ru complexes. Basidties of the CpOs(PR3)2Br and CpRu(PR3)2H complexes are reduced when the protonated product is forced to have the cis, rather than trans, structure by a small-ring chelating diphosphine ligand (dppm). These studies

Ligand and metal effects on the heats of protonation of organometallic compounds