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Issue 5, 1984
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Rhodium-(I) and -(III) complexes of diphenylphosphinous acid and secondary phosphites

Abstract

After shaking [{RhCl(C8H12)}2](C8H12= cyclo-octa-1,5-diene) with PPh2Cl in methanol–water (7 : 1 v/v) for 15 min, addition of MCl gave high yields of the triple-chloride-bridged anionic complex M[Rh2Cl5{(PPh2O)2H}2][M = AsPh4+(2a) or PPh3(CH2Ph)+(2b)]. The structure of (2a)(CH2Cl2 trisolvate) has been verified by X-ray analysis. The crystals are triclinic, space group P[1 with combining macron] with a= 12.157(4), b= 16.191(5), c= 20.523(8)Å, α= 96.02(3), β= 99.88(2), γ= 96.10(2)°, and Z= 2. Variable-temperature 31P-{1H} n.m.r. spectroscopy indicates that (2a) undergoes facile intramolecular scrambling of the phosphorus nuclei at ambient temperature. Reaction of the anion (2) with BF3·Et2O leads to the formation of the [Rh2Cl5{(PPh2O)2BF2}2] anion (3). In contrast, reaction of [{RhCl(C8H12)}2] with PPh2Cl in methanol–water (15 : 1 v/v) gives the cations [Rh{PPh2(OMe)}4]+ and [RhH(Cl){PPh2(OMe)}4]+, which do not undergo hydrolysis of the co-ordinated PPh2(OMe) ligand. The [Rh{PPh2(OEt)}4]+ cation is also formed by reaction of [RhL2(C8H12)]Y (Y = ClO4 or BPh4; L2= Ph2AsCH2CH2AsPh2, PhSCH2CH2SPh, or 2,2′-bipyridyl) with PPh2(OEt) whereas with the [Rh(Ph2PCH2CH2PPh2)(C8H12)]+cation, [Rh(Ph2PCH2CH2PPh2){PPh2(OEt)}2][BPh4](4) is isolated. However, reaction of [RhL2(diene)][ClO4][L2= diphosphine or bis(phosphine)] with H2 followed by addition of P(OR)2(O)H (R = Me or Et) gives the unstable cations [RhL2{P(OR)2OH}2]+.

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Article type: Paper
DOI: 10.1039/DT9840000801
Citation: J. Chem. Soc., Dalton Trans., 1984,0, 801-807
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    Rhodium-(I) and -(III) complexes of diphenylphosphinous acid and secondary phosphites

    J. A. S. Duncan, T. A. Stephenson, M. D. Walkinshaw, D. Hedden and D. M. Roundhill, J. Chem. Soc., Dalton Trans., 1984, 0, 801
    DOI: 10.1039/DT9840000801

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