Author: Cary R. Stennett

0000000000819874

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Cary R. Stennett

Molecular Complexes Featuring Unsupported Dispersion-Enhanced Aluminum–Copper and Gallium–Copper Bonds

The reaction of the copper(I) β-diketiminate copper complex {(Cu(BDIMes))2(μ-C6H6)} (BDIMes = N,N′-bis(2,4,6-trimethylphenyl)pentane-2,4-diiminate) with the low-valent group 13 metal β-diketiminates M(BDIDip) (M = Al or Ga; BDIDip = N,N′-bis(2,6-diisopropylphenyl)pentane-2,4-diiminate) in toluene afforded the complexes {(BDIMes)CuAl(BDIDip)} and {(BDIMes)CuGa(BDIDip)}. These feature unsupported copper–aluminum or copper–gallium bonds with short metal–metal distances, Cu–Al = 2.3010(6) Å and Cu–Ga = 2.2916(5) Å. Density functional theory (DFT) calculations showed that approximately half of the calculated association enthalpies can be attributed to London dispersion forces. peerReviewed

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Reductions of M{N(SiMe3)2}3 (M = V, Cr, Fe): Terminal and Bridging Low-Valent First-Row Transition Metal Hydrido Complexes and “Metallo-Transamination”

The reaction of the vanadium(III) tris(silylamide) V{N(SiMe3)2}3 with LiAlH4 in diethyl ether gives the highly unstable mixed-metal polyhydride [V(μ2-H)6[Al{N(SiMe3)2}2]3][Li(OEt2)3] (1), which was structurally characterized. Alternatively, performing the same reaction in the presence of 12-crown-4 affords a rare example of a structurally verified vanadium terminal hydride complex, [VH{N(SiMe3)2}3][Li(12-crown-4)2] (2). The corresponding deuteride 2D was also prepared using LiAlD4. In contrast, no hydride complexes were isolated by reaction of M{N(SiMe3)2}3 (M = Cr, Fe) with LiAlH4 and 12-crown-4. Instead, these reactions afforded the anionic metal(II) complexes [M{N(SiMe3)2}3][Li(12-crown-…

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