A new diphosphinite derived from cyclohexane-1,4-diol: oxidation reactions, metal complexes, P–O bond cleavage and X-ray crystal structures of Ph 2P(E)O(C 6H 10)OP(E)Ph 2 (E = S, Se)

Abstract

The reaction of cyclohexane-1,4-diol with chlorodiphenylphosphine affords bis(phosphinite), Ph 2PO(C 6H 10)OPPh 2 ( 1) in good yield. The bis(phosphinite) ( 1) reacts with H 2O 2, elemental sulfur or selenium to give the corresponding dichalcogenide; the structures of the disulfide ( 3) and diselenide ( 4) derivatives are confirmed by X-ray crystal structure analysis. The reaction of 1 with phosphoryl azide, N 3P(O)(OPh) 2 gives the phosphinimine derivative, (PhO) 2(O)PN PPh 2O(C 6H 10)OPh 2P NP(O)(OPh) 2 ( 5) in quantitative yield. Treatment of the ligand 1 with CpRu(PPh 3) 2Cl results in a bis(phosphinite) bridged dinuclear complex, [CpRuCl(PPh 3)] 2(μ-PPh 2O(C 6H 10)OPPh 2) ( 7) whereas the reaction of 1 with Pd(II) and Pt(II) derivatives afford cis-chelate complexes, [MCl 2{Ph 2PO(C 6H 10)OPPh 2}] (M = Pd, 8; Pt, 9). The reaction of 1 with Mo(CO) 6 in the presence of TMNO · 2H 2O does not give the expected cis-[Mo(CO) 4{Ph 2PO(C 6H 10)OPPh 2}]; instead a cubane-shaped tetranuclear molybdenum(V) complex, [Mo 4O 4(μ 3-O) 4 (μ-O 2PPh 2) 4] ( 6) was obtained due to water assisted cleavage of P–O bonds.