Abstract
The Rh(I) and Rh(III) hydrides HRh(dppb)2 and [HRh(dppb)2(NCCH3)](BF4)2 (where dppb is 1,2-(bis(diphenylphosphino)benzene) have been prepared, and a structural study of [HRh(dppb)2(NCCH3)](BF4)2 has been completed. The latter complex is an octahedral complex with a trans arrangement of the hydride and acetonitrile ligands. A pKa value of 9.4 was measured for this complex by equilibration of [Rh(dppb)2](BF4) with 4-bromoanilinium tetrafluoroborate in acetonitrile. [Rh(dppb)2](BF4) reacts with H2 in the presence of Pt(dmpp)2, which acts as a base, to form HRh(dppb)2 and [HPt(dmpp)2](BF4) (where dmpp = 1,2-bis(dimethylphosphino)propane). An equilibrium constant of 0.42 ± 0.2 was measured for this reaction. Using this equilibrium measurement and a thermodynamic cycle, the hydride donor ability (ΔG°H-) of HRh(dppb)2 was determined to be 34 kcal/mol. This value indicates that HRh(diphosphine)2 complexes are powerful hydride donors. Similarly the pKa value of HRh(dppb)2 was calculated to be 35 from a thermodynam...
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