Toggling the Z-type interaction off-on in nickel-boron dihydrogen and anionic hydride complexes.

Completing a series of nickel-group 13 complexes, a coordinatively unsaturated nickel-boron complex and its derivatives with a H, N, or hydride ligand were synthesized and characterized. The toggling "on" of a Ni(0)-B(III) inverse-dative bond enabled the stabilization of a nickel-bound anionic hydride with a remarkably low thermodynamic hydricity of kcal mol in THF. The flexible topology of the boron metalloligand confers both favorable hydrogen binding affinity and strong hydride donicity, albeit at the cost of high H basicity during deprotonation to form the hydride.

One-electron bonds in copper-aluminum and copper-gallium complexes.

Odd-electron bonds have unique electronic structures and are often encountered as transiently stable, homonuclear species. In this study, a pair of copper complexes supported by Group 13 metalloligands, M[N((-CH)NCHPPr)] (M = Al or Ga), featuring two-center/one-electron (2c/1e) σ-bonds were synthesized by one-electron reduction of the corresponding Cu(i) ⇢ M(III) counterparts. The copper bimetallic complexes were investigated by X-ray diffraction, cyclic voltammetry, electron paramagnetic spectroscopy, and density functional theory calculations.

Cooperative Bond Activation and Facile Intramolecular Aryl Transfer of Nickel-Aluminum Pincer-type Complexes.

Pincer-type nickel-aluminum complexes were synthesized using two equivalents of the phosphinoamide, [PhNCH P Pr ] . The Ni -Al complexes, {( PAlP)Ni} (μ-N ) and {( PAlP)Ni} (μ-COD), where PAlP is (Mes)Al(NPhCH P Pr ) , were structurally characterized. The (PAlP)Ni system exhibited cooperative bond cleavage mediated by the two-site Ni-Al unit, including oxidative addition of aryl halides, H activation, and ortho-directed C-H bond activation of pyridine N-oxide.

Carbodiimide Synthesis via Ti-Catalyzed Nitrene Transfer from Diazenes to Isocyanides.

Simple Ti imido halide complexes such as [BrTi(N Bu)py] are competent catalysts for the synthesis of unsymmetrical carbodiimides via Ti-catalyzed nitrene transfer from diazenes or azides to isocyanides. Both alkyl and aryl isocyanides are compatible with the reaction conditions, although product inhibition with sterically unencumbered substrates sometimes limits the yield when diazenes are employed as the oxidant. The reaction mechanism has been investigated both experimentally and computationally, wherein a key feature is that the product release is triggered by electron transfer from an -carbodiimide to a Ti-bound azobenzene.

Palladium(II) complexes of a bridging amine bis-(phenolate) ligand featuring κ and κ coordination modes.

Bidentate and tridentate coordination of a 2,4-di--butyl-substituted bridging amine bis-(phenolate) ligand to a palladium(II) center are observed within the same crystal structure, namely di-chlorido-({6,6'-[(ethane-1,2-diylbis(methyl-aza-nedi-yl)]bis-(methyl-ene)}bis-(2,4-di--butyl-phenol))palladium(II) chlorido-(2,4-di--butyl-6-{[(2-{[(3,5-di--butyl-2-hy-droxy-phen-yl)meth-yl](meth-yl)amino}-eth-yl)(meth-yl)amino]-meth-yl}phenolato)palladium(II) methanol 1.685-solvate 0.315-hydrate, [PdCl(CHNO)][PdCl(CHNO)]·1.