Synthesis and Reactivity of Transition Metal Alkyl and Nitrido Complexe

Reaction of [IrIII(dtbpy)(kappa2-CH 2CMe2C6H4)(C6H4 t-Bu-2)] (1) (dtbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) with NO2 (N2O4) led to para-selective nitration of the aryl ligands and the formation of bis-nitrated iridium(III) complex [IrIII(dtbpy)(kappa2-CH2CMe 2C6H3NO2-4){C6H3( t-Bu-2)(NO2-4)}] (2). Heating 1 with neat pentafluorothiophenol resulted in the formation of [IrIV (dtbpy)(SC6F5)4] (3). [RuIVR4] (6) has been synthesized from [RuIII(acac)3] and RMgX (R = 2-methyl-4-methoxyphenyl). 6 is capable of catalyzing the oxidation of benzyl alcohol with tert-butyl hydroperoxide (TBHP).;[LOEtRuVI(N)Cl2] underwent migratory insertion with [RhIII(mes)3] to afford [LOEt RuIVCl2(mu-N(2,4-Me2-6-CH 2C6H2))RhIII(mu-N(mes))L OEtRuIVCl2] (7). Activation of a methyl C-H bond in one of the mesityl ligands in [RhIII(mes) 3] was observed.;[LOEtRuVI(N)Cl2] reacted with [Ir III(dtbpy)(CH2SiMe3)(SiMe3)(Me)] and [IrIII(dtbpy)R3] to give [LOEtRu VICl2(mu-N)IrIII(dtbpy)(CH2SiMe 3)(SiMe3)(Me)] (8) and [LOEtRu VICl2(mu-N)IrIII(dtbpy)R3] (R = 2,5-dimethylphenyl (9); 2-methyl-4-methoxyphenyl (10)). Treatment of [PtII(ppyH)(ppy)Cl] (ppyH = 2-phenylpyridine) and [PtII(ItBu)(I tBu')][BArf 4] (ItBu = 1,3-di-tert-butylimidazol-2-ylidene; monometallated ItBu ligand represented as ItBu'; Arf = (3,5-trifluoromethyl)phenyl) with [LOEtRu VI(N)Cl2] afforded [LOEtRuVICl 2(mu-N)PtII(ppy)Cl] (12) and [LOEt RuVICl2(mu-N)PtII(I tBu)(ItBu')][BArf 4] (14), respectively. Oxidation of 12 by PhICl 2 gave [LOEtRuVICl2(mu-N)Pt IV(ppy)Cl3] (13). [LOEtRu VI(N)Cl2] reacted with trans-[Ir III{iPr2P(Se)NPiPr 2}2(H)] to yield [LOEtRuVICl 2(mu-N)IrIII{iPr2P(Se)NP iPr2}2(H)] (15).;Reactions of [LOEtRuVI(N)Cl2] with [Cp2OsII] and [(eta5-Ind) 2RuII] (Cp = eta5-cyclopentadienyl; Ind = indenyl) resulted in ring slippage of the cycloolefin ligands and the formation of [{LOEtRuVICl2(mu-N)} 2OsIICp(eta1]C5H 5)] (16) and [{LOEtRuVICl 2(mu-N)}2RuII(eta5-Ind)(eta 1-Ind)] (17), respectively. (Abstract shortened by UMI.).