Synthesis and Reactivity of Heterotrinuclear Platinum Cyclometalated Complexes Containing Bridging Nitrido Ligands

摘要

The treatment of [M(L_(OEt))(N)Cl2](L_(OEt)~-=[Co(η~5-C5H5){P(O)(OEt)2}3]~-)with the Pt(II)bis(cyclometalated)complex [Pt(CNCBu)(DMSO)](H2CNCBu=2,6-di(4-tert-butylphenyl)pyridine;DMSO=dimethylsulfoxide)afforded the heterotrinuclear nitrido complexes [L_(OEt)Cl2M(μ-N)Pt(CNCBu)](M=Ru(1-Ru),Os(1-Os)).The Pt-N(nitrido)(1.821(5)A)and Ru-N(1.673(5)A)distances in 1-Ru are consistent with the Ru=N=Pt bonding description.The Pt-N(nitrido)distance in 1-Os(1.859(7)A)is longer than that in 1-Ru,suggesting the π interaction between Pt(II)and Os±N is weaker than that for the Ru counterpart.Oxidation of 1-Ru with PhICl2 afforded the Pt(IV)dichloride complex [L_(OEt)Cl2Ru(μ-N)Pt(CNCBu)Cl2](2)that has a longer Pt-N distance(1.893(3)A)than that in 1-Ru,indicating the weakening of the Pt-N(Ru)π bonding upon oxidation of Pt(II)to Pt(IV).Treatment of [Pt(CNCBu)(DMSO)] with [nBu4N][Ru(N)Cl4] in tetrahydrofuran(THF)afforded [nBu4N][(THF)Cl4Ru(μ-N)Pt(CNCBu)](3),which reacted with K[N(Ph2PS)2] and K[N(iPr2PO)2] to yield [Cl{N(Ph2PS)2}2Ru(μ-N)Pt(CNCBu)](4)and [nBu4N][Cl3{N(iPr2PO)2}Ru(μ-N)Pt(CNCBu)](5),respectively.The short Pt-N(nitrido)distances in 3(1.816(5)A)and 4(1.809(2)A)are indicative of Pt=N double bond character.