Oxotrimesityliridium(V), (mes)3Ir=O (mes = 2,4,6-trimethylphenyl), and trimesityliridium(III), (mes)3Ir, undergo extremely rapid degenerate intermetal oxygen atom transfer at room temperature. At low temperatures, the two complexes conproportionate to form (mes)3Ir-O-Ir(mes)3, the 2,6-dimethylphenyl analogue of which has been characterized crystallographically. Variable-temperature NMR measurem...

Reactions of [TaCp*Cl4] with two, three and four equivalents of LiNH Bu give the haloand amido-imido complexes [TaCp*Cl2(N Bu)] (1a), [TaCp*Cl(NBu)(NHBu)] (2) and [TaCp*(NBu)(NHBu)2] (3), respectively. The related complex [TaCp*Cl2{N(2,6-Me2C6H3)}] (1b) is prepared by a similar reaction using two equivalents of Li[NH(2,6-Me2C6H3)]. Complex 3 can be transformed into 2 and further into 1a by reac...

Reaction of [(Me3tacn)V(CF3SO3)3] (Me3tacn = N,N',N''-trimethyl-1,4,7-triazacyclononane) with LiCN in DMF results in oligomerization of cyanide to form [(Me3tacn)2V2(CN)4(mu-C4N4)]. The structure of this binuclear complex features a planar tetracyanide unit bridging two VIV centers via imido type linkages. The conjugated pathway provided by the bridging ligand leads to strong antiferromagnetic ...

Novel mixed amido/imido/guanidinato complexes of niobium are reported. The complexes were synthesized by insertion of two equivalents of di-isopropylcarbodiimide (i-Pr-cdi) or bis-cyclohexylcarbodiimide (Cy-cdi) respectively, into the niobium-amido bonds of [Nb(NR(2))(3)(N-t-Bu)] (, R = Me; , R = Et) starting out from [NbCl(3)(N-t-Bu)(py)(2)] and the respective LiNR(2) reagent (py = pyridine). ...

Transition-metal complexes capable of mediating multielectron transformations are critical components for a variety of small-molecule transformations. For example, the oxidation of C H bonds and the reduction of protons to H2 are both two-electron transformations. The oxidation of water to O2 is a four-electron process and the reduction of nitrogen to ammonia is an overall six-electron process....