Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe(2)R')(Pyr)(2)(bipy) (1a-1g; R = 2,6-i-Pr(2)C(6)H(3) (Ar), adamantyl (Ad), 2,6-Me(2)C(6)H(3) (Ar'), 2-i-PrC(6)H(4) (Ar(iPr)), 2-ClC(6)H(4) (Ar(Cl)), 2-t-BuC(6)H(4) (Ar(t) (Bu)), and 2-MesitylC(6)H(4) (Ar(M)), respectively; R' = Me, Ph) have been prepared using three different methods. Up to th...

The synthesis of the first terminal imido complex of cobalt, [PhBP3]CoN-p-tolyl, is reported. Its synthesis proceeds by oxidative group transfer from cobalt(I) upon addition of tolyl azide at room temperature. This species and a related eta1-diazoalkane adduct have been structurally characterized. The diamagnetic imido complex [PhBP3]CoN-p-tolyl reacts with CO to liberate isocyanate and the cob...

Compounds of the late transition metals with M=X multiple bonds (X=CR2, NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but with noticeable gaps in the second- and third-row elements. For example, there are no isolated examples of terminal imido rhodium complexes known to date. Described herein is the isolation, characterization, and some preliminary reactivity ...

The three-coordinate imidos (dtbpe)Ni═NR (dtbpe = (t)Bu2PCH2CH2P(t)Bu2, R = 2,6-(i)Pr2C6H3, 2,4,6-Me3C6H2 (Mes), and 1-adamantyl (Ad)), which contain a legitimate Ni-N double bond as well as basic imido nitrogen based on theoretical analysis, readily deprotonate HC≡CPh to form the amide acetylide species (dtbpe)Ni{NH(Ar)}(C≡CPh). In the case of R = 2,6-(i)Pr2C6H3, reductive carbonylation result...

An efficient protocol for post-functionalization of organo-imido polyoxometalates is developed via creating a remote tertiary “N” atom over the surface of organo-imido hexamolybdates and subsequently post-functionalizing it with the help of allyl or alkyl halides to afford stoichiometric, “in situ” crystalline products at moderate temperatures. The parent organo-imido product 2 and post-functio...

Molybdenum imido adamantylidene complexes with different substituents on the ligand (dipp=2,6-diisopropylphenyl, ArF5=C6F5, and tBu) having distinct electron donating abilities were investigated for metathesis of internal terminal olefins, both molecular silica-supported species using standardized protocols. Here we show that surface immobilization these compounds results in dramatically increa...