A new diphosphinite derived from cyclohexane-1,4-diol: oxidation reactions, metal complexes, P–O bond cleavage and X-ray crystal structures of Ph2P(E)O(C6H10)OP(E)Ph2 (E = S, Se)

The reaction of cyclohexane-1,4-diol with chlorodiphenylphosphine affords bis(phosphinite), Ph2PO(C6H10)OPPh2 (1) in good yield. The bis(phosphinite) (1) reacts with H2O2, 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, N3P(O)(OPh)2 gives the phosphinimine derivative, (PhO)2(O)PN=PPh2O(C6H10)OPh2P=NP(O)(OPh)2 (5) in quantitative yield. Treatment of the ligand 1 with CpRu(PPh3)2Cl results in a bis(phosphinite) bridged dinuclear complex, [CpRuCl(PPh3)]2(μ-PPh2O(C6H10)OPPh2) (7) whereas the reaction of 1 with Pd(II) and Pt(II) derivatives afford cis-chelate complexes, [MCl2 Ph2PO(C6H10)OPPh2 ] (M = Pd, 8; Pt, 9). The reaction of 1 with Mo(CO)6 in the presence of TMNO · 2H2O does not give the expected cis-[Mo(CO)4 Ph2PO(C6H10)OPPh2 ]; instead a cubane-shaped tetranuclear molybdenum(V) complex, [Mo4O4(μ3-O)4 (μ-O2PPh2)4] (6) was obtained due to water assisted cleavage of P–O bonds.© Elsevie