Platinum and palladium complexes of [R2PCH2P(Y)R′2] and [R2PCHP(Y)R′2]− ligands, Y = O,S, or Se: 13C, 31P, 77Se, and 195Pt nuclear magnetic resonance studies and the crystal and molecular structures of trans-[PtCl(PEt3){But2PCH2P(O)Me2}][ClO4] and trans-PtCl(PEt3){Ph2PCH2P(S)But2}|[ClO4]

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Abstract
Reactions of the bisphosphine monochalcogenides, [Ph2PCH2P(Y)R2], Y = O, S, or Se, R = Ph, Pri, or But, with the chloro-bridged dimers [M2Cl4(PR′3)2], M = Pd or Pt, R′ = Et or Bun, in the presence of either NaClO4 or NaBF4 yield perchlorate and fluoroborate salts of the complex cations cis- and trans-[PtCl(PR′3){Ph2PCH2P(Y)R2}]+. In many cases both cis and trans isomers (defined by the relative orientation of the two M—P bonds) are obtained and the precise isomer distribution is a sensitive function of the substituents. Corresponding neutral complexes, cis- and trans-[PtCl(PR′3){Ph2PCHP(Y)R2}], can be synthesized either by deprotonation of the cations using NaH or by use of the salts Li[Ph2PCHP(Y)R2] in the initial bridge cleavage reactions. These and related complexes are characterized by complete 13C, 31P, 77Se, and 195Pt NMR studies and by two crystal structure determinations. The complexes I, trans-[PtCl(PEt3){But2PCH2P(O)Me2}][ClO4], and II, trans-[PtCl(PEt3){Ph2PCH2P(S)But2}][ClO4], crystallize in the monoclinic space group P21/c, respective cell dimensions: a = 15.579(2), b = 13.590(3), c = 13.578(1) Å;β= 105.96(1)°; and a = 14.002(4), b = 16.366(5), c = 15.524(5) Å; β = 106.01 (3)°. Complete X-ray diffraction studies show that both complexes contain closely square planar platinum centres with the R2PCH2P(Y)R′2 ligands coordinated via phosphorus and the Y atom so as to form five-membered chelate rings. The molecular dimensions suggest that the bond to sulphur is stronger than that to oxygen and exerts a larger trans influence.

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