Coordination chemistry of [CH{P(S)Ph2}2]−: x-ray diffraction studies of S,S-chelate complexes of iridium and rhodium

Faculty Advisor
bis-phosphorus ligands, nuclear magnetic-resonance, cyclopentadienyl-nickel-complexes, phosphine arsine sulfides
Abstract (summary)
Reactions of the chloro-bridged complexes, [M2Cl2(cod)2], M  Ir or Rh, with CHR(P(S)Ph2)2, R  H or Me, provide a synthetic route to the cations, [M(cod){CHR(P(S)Ph2)2-S,S}]+, which are isolated as fluoroborate or perchlorate salts. Treatment of these products with sodium hydride results in facile deprotonation to the neutral complexes, [M(cod){CR(P(S)Ph2)2-S,S}], and when R  H, the neutral complexes are also accessible via reactions of [M2Cl2(cod)2] with Li[CH{P(S)Ph2)2]. The complexes, [Ir(cod){CH(P(S)Ph2)2-S,S}], and [Rh(cod){CH(P(S)Ph2)2-S,S}], crystallize in the P1 (No. 2) space group (Z = 2) with respective unit cells: a = 11.570(4), b = 15.122(2), c = 9.919(3) Å, α = 79.86(4), β = 64.87(3), γ = 97.94(4)°; and α = 11.571(16), b = 15.078(2), c = 9.869(2) Å, α = 100.16(1), β = 64.97(1), γ = 82.10(1)°. Both structures consist of puckered 6-membered rings formed by coordination of the disulfide ligands via two sulfur atoms to the metal center. The rings lie in distorted boat conformations with the prows occupied by one sulfur and one phosphorus and the metal atoms in one side.
Publication Information
Browning, J., Bushnell, G., Dixon, K., & Hilts, R. (1992). Coordination Chemistry of [Ch(P(S)Ph2)2]- - X-Ray-Diffraction Studies of S,S-Chelate Complexes of Iridium and Rhodium. Journal of Organometallic Chemistry, 434(2), 241–252.
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