88762-38-3Relevant academic research and scientific papers
Bimetallic Systems. Part 2. Synthesis and Interconversion of Monodentate- and Bridging-bis(diphenylphosphino)methane Platinum, Diplatinum, and Mercury-Platinum Acetylides
Langrick, C. Richard,McEwan, David M.,Pringle, Paul G.,Shaw, Bernard L.
, p. 2487 - 2494 (2007/10/02)
Treatment of (PtCl2(dppm-PP')) (dppm = bis(diphenylphosphino)methane) with LiCCR gives good yields of the diplatinum 'face-to-face' complexes trans,trans-(Pt2(CCR)4(υ-dppm)2) (2a), (2b), (2d), or (2e), with R = C6H4Me-p, Ph, CH2CH2Ph, or C(Me)=CH2 respectively.These diplatinum complexes react with more dppm to give the mononuclear fluxional complexes trans-(Pt(CCR)2(dppm-P)2) (3a), (3b), (3d), or (3e).A more convenient method of making the mononuclear complexes (3a)-(3e) is to treat (PtCl2(dppm-PP')) with LiCCR in the presence of dppm.Treatment of (Pt(dppm-PP')2)Cl2 with LiCCPh gives (3b) but deprotonation to give (Pt(Ph2PCHPPh2)2) also occurs.Treatment of (PtCl2(dppm-PP')) with an excess of LiCCPh gives (3b) and (Pt(CCPh)4)(2-), isolated as its (NBun4)(+) salt.Treatment of (Pt(dppm-PP')2)Cl2 with Hg(CCR)2 rapidly gives the platinum-mercury complexes((RCC)2Pt(υ-dppm)2HgCl2) (4a)-(4d) in very high yields, with R = C6H4Me-p, Ph, Me, or Prn respectively.Treatment of the platinum-mercury complexes (4a)-(4c) with Na2S*9H2O gives HgS and high yields of the mononuclear complexes trans-(Pt(CCR)2(dppm-P)2) (3a)-(3c), with R = C6H4Me-p, Ph, or Me respectively.More conveniently, when (Pt(dppm-PP')2)Cl2 is treated with Hg(O2CMe)2 + RCCH the platinum-mercury complexes (4a)-(4c) are formed in excellent yields.Preliminary work shows that ((HOCH2CH2CC)2Pt(υ-dppm)2HgCl2) (4e) is formed from (Pt(dppm-PP')2)Cl2 + Hg(O2CMe)2 + HOCH2CH2CCH.Treatment of the complex trans-(Pt(CCPh)2(dppm-P)2) (3b) with HgCl2 gives ((PhCC)2Pt(υ-dppm)2HgCl2) (4b).The fluxional monodentate-dppm complexes trans-(Pt(CCR)2(Ph2PCH2PPh2)2) (3a)-(3c), R = C6H4Me-p,Ph, or Me respectively, are oxidised by hydrogen peroxide to give the non-fluxional phosphine oxide complexes trans-(Pt(CCR)2(Ph2PCH2P(=O)Ph2)2) (5a)-(5c) or quaternised by methyl iodide to give trans-(Pt(CCR)2(Ph2PCH2PMePh2)2)I2 (6a)-(6c).Complex (6b;R=Ph) is deportonated by lithium propan-2-oxide probably to give the di-ylide trans-(Pt(CCPh)2(Ph2PCH=PMePh2)2) (7) which hydrolyses to trans-(Pt(CCPh)2(PMePh2)2).I.r., and 1H, 31P, and 195Pt n.m.r. data are given.
