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The preparation of a new tridentate diphosphinosulfinyl ligand is described as well as the synthesis and properties of some of its Rh, Ir, Ni, Pd, and Pt complexes. The ligand binds in a κ^3-PS(O)P fashion in all cases. The M–S lengths in (SOP_2)RhCl and (SOP_2)IrCl (2.1340(8) and 2.1341(5) A, respectively) are the shortest of all crystallographically characterized Rh– and Ir–S(O)R_2 complexes, which illustrates the significant M–S(O) π-backbonding for these metals. Akin to Vaska’s complex, (SOP_2)IrCl binds O_2 to yield a peroxide complex with an O–O length of 1.465(3) A and ^ν(O–O) = 847 cm^(–1). The C–O stretches of (SOP_2)M(CO) (M = Ni, Pd, Pt) are ~30-40 cm^(–1) higher than those of the analogous (PPh_3)_3M(CO). A number of divalent group 10 complexes of the form [(SOP_2)MX]^+ for Ni (X = Cl), Pd (X = Cl, Me), and Pt (X = Cl, Me) are reported, as well as the highly electrophilic complex [(SOP_2)Pd(NCCH_3)]^(2+). An analysis of the S–O length as a function of the M–S length for all d^8 SOP_2 Rh, Ir, Pd, and Pt complexes reveals that the electron-withdrawing capabilities of the sulfinyl group are mediated largely through π-backbonding for Rh and Ir and mostly through poor σ-donation for Pd and Pt.

Late-Metal Diphosphinosulfinyl S(O)P2 Pincer-type Complexes

Late-Metal Diphosphinosulfinyl S(O)P₂ Pincer-type Complexes