Secondary phosphine chalcogenides XI. The reaction of the bis(2,4-pentanedionato) complexes of the nickel triade with secondary phosphane sulfides, R 2P(S)H (R=Ph, Bu t). Crystal structure of [Pd 2(μ-SPBu t2) 2(η 2-SPBu t2) 2]. A comparison of the η 2- and the μ-coordination mode of the R 2PS − ligand

Abstract

Treatment of [M(acac) 2] (M=Ni, Pd, Pt) with the secondary phosphane sulfides R 2P(S)H (R=Ph, Bu t) affords the complexes [M 2(μ-SPR 2) 2(η 2-SPR 2) 2] whose structure markedly depends on the organic substituents at phosphorus. Thus, the phosphorus atoms around the metal atoms are mutually cis positioned for R=Ph and trans positioned for R=Bu t, respectively. These metal(II) complexes (M=Pd; R=Ph) undergo redox reactions with the metal(O) complexes [M′(PPh 3) 2L](M′=Pd, Pt; L=2PPh 3, C 2H 4) to produce homo- and heterodinuclear metal(I) complexes [PdM′(μ-SPPh 2) 2(PPh 3) 2] (M′=Pd, Pt). The structure of [Pd 2(μ-SPBu t 2) 2(η 2-SPBu t 2) 2] has been determined by single crystal X-ray diffraction. The complex crystallizes in the triclinic space group P 1 with a=10.315(3), b=10.668(3), c=11.181(3) Å, α=72.95(2), β=75.20(2), γ=71.97(2)°, Z=1, D exp=1.38(1), D calc=1.392 g cm −3. The structure was solved by heavy atom method and refined by full-matrix least-squares treatment to R=0.053 ( R w=0.052). The structure represents a centrosymmetric dinuclear complex with a six-membered (PdPS) 2 core. The Bu t 2PS − ligands are coordinated in the bridging as well as in the dihapto mode.