116352-04-6Relevant articles and documents
Platinum and palladium complexes of (1-) ligands, Y = O, S, or Se: (13)C, (31)P, (77)Se, and (195)Pt nuclear magnetic resonance studies and the crystal and molecular structures of trans-t2PCH2P(O)Me>> and trans-PtCl(PEt3)t2>>
Berry, David Eric,Browning, Jane,Dixon, Keith Roger,Hilts, Robert Wayne
, p. 1272 - 1282 (2007/10/02)
Reactions of the biphosphine monochalcogenides, , Y = O, S, or Se, R = Ph, Pri, But, with the chloro-bridged dimers , 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->(1+).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->, can be synthesized either by deprotonation of the cations using NaH or by use the salts Li in the initial bridge cleavage reactions.These and related complexes are characterized by complete (13)C, (31)P, (77)Se, and (195)Pt NMR studies and by two crystal structure determinations.The complexes I, trans-t2PCH2P(O)Me2>>, and II, trans-t2>>, crystallize in the monoclinic space group P21/c, respective cell dimensions: a = 15.579(2), b = 13.590(3), c = 13.578(1) Angstroem; β = 105.96(1) deg; and a = 14.002(4), b = 16.366(5), c = 15.524(5) Angstroem; β = 106.01(3) deg.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 to oxygen and exerts a larger trans influence.
