Ruthenium Complexes of a Triphosphorus-Coordinating Pincer Ligand: Ru-P Ligand-Substituent Exchange Reactions Driven by Large Variations of Bond Energies.

The reaction of [( p -cymene)RuCl ₂ ] ₂ with the triphosphine ligand bis(2-di- tert -butylphosphinophenyl)phosphine ( ^tBu P ^H PP) results in an unusual exchange reaction in which a chloride ligand and a phosphorus-bound H atom are exchanged ("H-P/Ru-Cl exchange") to give the (chlorophosphine)ruthenium hydride complex ( ^tBu P ^Cl PP)RuHCl [ 1 ^Cl -HCl ; ^tBu P ^Cl PP = bis(2-di- tert -butylphosphinophenyl)chlorophosphine]. Density functional theory calculations indicate that the presumed initial product of metalation, ( ^tBu P ^H PP)RuCl ₂ ( 1 ^H -Cl2 ), undergoes an H-P/Ru-Cl exchange via sequential P-to-Ru α-H migration to give the intermediate ( ^tBu PPP)RuHCl ₂ , followed by Ru-to-P α-Cl migration to give the observed product 1 ^Cl -HCl (crystallographically characterized). Dehydrochlorination of 1 ^Cl -HCl under a H ₂ atmosphere gives ( ^tBu P ^Cl PP)RuH ₄ ( 1 ^Cl -H4 ), which then can undergo a second dehydrochlorination and addition of H ₂ to give ( ^tBu P ^H PP)RuH ₄ ( 1 ^H -H4 ). This reaction may proceed via the reverse of the intramolecular exchange by 1 ^H -Cl2 , i.e., loss of H ₂ from 1 ^Cl -H4 to give 1 ^Cl -H2 , which could undergo Cl-P/Ru-H exchange to give ( ^tBu P ^H PP)RuHCl ( 1 ^H -HCl ). Accordingly, the thermodynamics of Cl-P/Ru-H exchange are found to be highly dependent on the nature of the ancillary anionic ligand (H or Cl), which is not directly involved in the exchange. The origin of this thermodynamic dependence can be explained in terms of the high stability of complexes ( ^R P ^X PP)RuHCl (X = H, Cl; R = Me, ^t Bu), in which the hydride is approximately trans to a vacant coordination site and the central phosphine group is approximately trans to the weak-trans-influence chloride ligand. This conclusion has general implications for five-coordinate d ⁶ complexes, both pincer- and nonpincer-ligated.