Synthesis of a Gallaarsene {HC[C(Me)N-2,6-i-Pr₂-C₆H₃]₂}GaAsCp* Containing a Ga═As Double Bond

Abstract

Cp*AsCl (Cp* = CMe) reacts with one equivalent of LGa (L = HC[C(Me)N(2,6- i-PrCH)]) with formation of L(Cl)GaAs(Cl)Cp* 1, whereas the reaction with two equivalents of LGa yielded gallaarsene LGaAsCp* 2 containing a Ga═As double bond and (η-Ga(Cp*)L(η-GaL)(μ-As) 3. Compounds 2 and 3 were structurally characterized by single crystal X-ray diffraction, and the π-bonding contribution in 2 was analyzed by temperature-dependent H NMR spectroscopy (9.65 kcal mol) and by quantum mechanical computation.

The unique β-diketiminate ligand in aluminum(i) and gallium(i) chemistry

“…6). 37 To evaluate the reduction potential of Dipp NacNacGa(I) (2) in detail, Schulz et al studied the reactions of Dipp NacNacGa(I) (2) with other Sb III reagents. Dipp NacNacGa(I) (2) reacted with SbX 3 (X = NMe 2 , Cl) in a 2 : 1 molar ratio to form Ga-substituted distibenes [( Dipp NacNacGaX) 2 Sb 2 ] (X = NMe 2 58, Cl 59) (Scheme 15).…”

A General Pathway for the Synthesis of Gallastibenes containing Ga=Sb Double Bonds

“…To the best of our knowledge, [{Li(thf) 3 } 2 Ga 2 {As(Si‐ i Pr 3 )} 4 ] A , LGaAsCp* {L=HC[C(Me)N(2,6‐ i Pr 2 C 6 H 3 )] 2 , Cp* = C 5 Me 5 } B , resulting from the reaction of Cp*AsCl 2 with two equivalents of LGa, and LGa=SbGa(Cl)L C , which was formed by single electron reduction of the stibinyl radical L(Cl)Ga) 2 Sb . with KC 8 (Scheme ), represent the only structurally characterized compounds containing Ga=E (E=As, Sb) double bonds, to date.…”

“…Electronic stabilization by coordination of the electron lone pair of the group 15 element to an electron acceptor( Lewisa cid), [7] or by intermolecularo ri ntramolecular coordination of aL ewis base to the Lewis acidic group13metal centerh ave both been successfully applied. [4] To the best of our knowledge, [{Li(thf) 3 } 2 Ga 2 {As(Si-iPr 3 )} 4 ] A, [8] LGaAsCp* {L = HC[C(Me)N(2,6-iPr 2 C 6 H 3 )] 2 ,C p* = C 5 Me 5 } B, [9] resultingf rom the reaction of Cp*AsCl 2 with two equivalents of LGa, and LGa=SbGa(Cl)L C, [10] which was formed by single electron reduction of the stibinyl radical L(Cl)Ga) 2 SbC with KC 8 (Scheme 1), represent the only structurally characterizedc ompounds containing Ga=E(E= As, Sb) double bonds, to date.…”

Trendbericht Anorganische Chemie: Bioanorganische und Koordinationschemie

“…Wolf und Goicoechea berichteten über eine ungewöhnliche Aktivierung des 2-Phosphaethynolations und des 2-Ar sa ethy no lat an ions an Nickel(I)-Cyclopentadienkomplexen mit NHC-Liganden (Abbildung 7). 15 (20) aktionen waren μ 2 :η 2 -sowie η 2 -P 2oder μ 2 :η 2 , η 2 -As 2 -verbrückte Dinickelcarbonyl-NHC-Komplexe ( (13) und (14)). Werden 2 bar CO zugefügt, eignen sich diese Komplexe als Synthone für reaktive P 2 -Moleküle oder graues Arsen.…”