Stabilisation of [Fe2(CO)9] and [Ru2(CO)9] bu substitution with bridging diphosphorus ligands |
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| Authors: | Gerard de Leeuw John S Field Raymond J Haines Beth McCulloch Elsie Meintjies Christiaan Monberg Gillian M Olivier Praveen Ramdial Clifford N Sampson Beate Sigwarth Nick D Steen Kandasamy G Moodley |
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| Institution: | C.S.I.R. Unit of Metal Cluster Chemistry, Department of Chemistry, University of Natal, P.O. Box 375 Pietermaritzburg 3200 Republic of South Africa;Department of Chemistry, University of Durban-Westville, Private Bag X54001, Durban 4000 Republic of South Africa |
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| Abstract: | Reaction of Fe2(CO)9] 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 Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species Fe(CO)3{R2PYPR2}]. Reaction of Ru3(CO)12] 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 Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described. |
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