Reactivity of Monomeric N→Ge Coordinated Germanium(II) Hydrides

Jakub Tremmel, Milan Erben, Libor Dostál, Zdeňka Růžičková, Jan Turek, Roman Jambor

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6 Citations (Scopus)
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Abstract

Monomeric organogermanium(II) hydrides {(LGeH)M(CO) 5 } (M = Cr (1), W (2), L = [2-(CH 2 NEt 2 )-4,6-tBu 2 -C 6 H 2 ] ) were treated with ortho-quinones and terminal alkyne HC≡CCO 2 Me to give {[(LH)Ge(κ 2 -O 2 -3,5-tBu 2 C 6 H 2 )]M(CO) 5 } (M = Cr (3), W (4)), {[(LH)Ge(κ 2 -O 2 -3,4,5,6-Cl 4 C 6 )]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≡C bonds. Experimental data demonstrated zwitterionic character of Ge(II) complexes 3–6, where the 1,3,2-benzodioxagermylenolato anion involving the GeO 2 C 2 five membered ring coordinates the M(CO) 5 fragment. This anionic part is compensated by the NHEt 2 counter cation that is part of ligand L. Reactions of 1 and 2 differ mutually in the case of reduction of HC≡CCO 2 Me. The experimental and theoretical data suggest that compound 1 reacts with HC≡CCO 2 Me 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.

Original languageEnglish
Pages (from-to)1884-1894
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Volume2019
Issue number14
DOIs
Publication statusPublished - 16 Apr 2019

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