STABILISATION OF AND 9> BY SUBSTITUTION WITH BRIDGING DIPHOSPHORUS LIGANDS

Article abstract of DOI:10.1016/0022-328X(84)80583-5

Reaction of with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe, or OPrⁱ; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPrⁱ or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative >.Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex 2> but under thermal conditions in the formation of the mononuclear species >.Reaction of with an equimolar amount of (RO)2PN(R')P(OR)2 (R' = Me, R = Prⁱ or Et; R' = Et, R = Ph or Me) under either thermal or photochemical conditions produces > which reacts further with excess (RO)2PN(R')P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound 2>.The molecular structure of 2>, which has been determined by X-ray crystallography, is described.