A homoleptic triamidoamine zirconium complex featuring a metalated trimethylsilyl substituent, [κ 5 -(Me 3 SiNCH 2 CH 2 ) 2 NCH 2 CH 2 NSiMe 2 CH 2 ]Zr (1), was synthesized by reaction of Zr(CH 2 Ph) 4 with N(CH 2 CH 2 NHSiMe 3 ) 3 followed by sublimation. Complex 1 is a general precursor to a family of complexes with the formulation (N 3 N)ZrX (N 3 N ) N(CH 2 CH 2 NSiMe 3 ) 3 3-, X ) anionic ligand) by reactions that parallel expected reactivity of a hydride derivative. Treatment of 1 with phosphines, amines, thiols, alkynes, and phenol resulted in the formation of new, pseudo-C 3V -symmetric (N 3 N)ZrX complexes (X ) phosphido, amido, alkynyl, thiolate, or phenoxide) via element-H bond activation. Thus, the reactivity of complex 1 is that best described as a hydride surrogate. For example, complex 1 reacted with PhPH 2 at ambient temperature to provide (N 3 N)ZrPHPh (2) in 86% yield. Density functional theory studies and X-ray crystal structures provide a general overview of the bonding in these complexes, which appears to be highly ionic. In general, there is little evidence for ligand-to-metal π-bonding for the pseudoaxial X ligand in these complexes except for strongly π-basic terminal amido ligands. The limited π-bonding appears to be the result of competitive π-donation by the pseudoequatorial amido arms of the triamidoamine ancillary ligand. Thus, the relative Zr-X bond energies are governed by the basicity of the anionic ligand X. Solid-state structures of phosphido (3, 4, 5), amido (10), and thiolate (15) complexes support the computational results.

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An atom-economical synthesis of arsaalkenes via a net coupling of aryl arsines with aryl or alkyl isocyanides at zirconium is presented. Reaction of zirconium arsenido complexes (N3N)ZrAsHAr [N3N = N(CH2CH2NSiMe3)3(3-); Ar = Ph, (2) Mes (3)] with aryl and alkyl isocyanides yields arsaalkene products of the general form (N3N)Zr[NRC(H)═As(Ar)]. Two examples (5: R = Mes, Ar = Ph; 6: R = CH2Ph, Ar = Mes) were structurally characterized. Observation of intermediates in the reaction and structural characterization of the previously reported 1,1-insertion product benzylisocyanide with (N3N)ZrAsPh2 (8), (N3N)Zr[η(2)-C(PPh2)=NCH2Ph] (9), support the mechanistic hypothesis that these reactions occur via 1,1-insertion followed by rearrangement.