Publication detail

Reactivity of Monomeric N -> Ge Coordinated Germanium(II) Hydrides

Year: 2019

Type of publication: článek v odborném periodiku

Name of source: European Journal of Inorganic Chemistry

Publisher name: Wiley-VCH

Place: Weinheim

Page from-to: 1884-1894

Titles:

Language	Name	Abstract	Keywords
cze	Reaktivita monomerních Ge(II) hydridů	Byl připraven monomerní Ge(II) hydrid {(LGeH)M(CO)(5)} (M = Cr (1), W (2), L = [2-(CH2NEt2)-4,6-tBu(2)-C6H2](-), jehož reaktivity byla studována.	Reaktivita; monomerních; GeII; hydridů
eng	Reactivity of Monomeric N -> Ge Coordinated Germanium(II) Hydrides	Monomeric organogermanium(II) hydrides {(LGeH)M(CO)(5)} (M = Cr (1), W (2), L = [2-(CH2NEt2)-4,6-tBu(2)-C6H2](-)) were treated with ortho-quinones and terminal alkyne HC equivalent to CCO2Me to give {[(LH)Ge(kappa(2)-O-2-3,5-tBu(2)C(6)H(2))]M(CO)(5)} (M = Cr (3), W (4)), {[(LH)Ge(kappa(2)-O-2-3,4,5,6-Cl4C6)]M(CO)(5)} (M = Cr (5), W (6)) and {[LGeCH=CH(COOMe)]Cr(CO)(5)} (11). These reactions proceeded as catalyst-free reductions of C=O and C equivalent to C bonds. Experimental data demonstrated zwitterionic character of Ge(II) complexes 3-6, where the 1,3,2-benzodioxagermylenolato anion involving the GeO2C2 five membered ring coordinates the M(CO)(5) fragment. This anionic part is compensated by the NHEt2 counter cation that is part of ligand L. Reactions of 1 and 2 differ mutually in the case of reduction of HC equivalent to CCO2Me. The experimental and theoretical data suggest that compound 1 reacts with HC equivalent to CCO2Me to give vinyl germylene 11 as the product of the anti-Markovnikov cis-1,2-addition, while complex 2 is inactive. These results thus suggest that the reactivity of the terminal GeH bond may be tuned by its coordination to various transition metals.	Germanium; Hydrides; Density functional calculations; Reaction mechanisms

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