On the Variable Reactivity of Phosphine‐Functionalized [Ge9] Clusters: Zintl Cluster‐Substituted Phosphines or Phosphine‐Substituted Zintl Clusters

On the Variable Reactivity of Phosphine‐Functionalized [Ge9] Clusters: Zintl... The reaction of [(Ge9{Si(TMS)3}2PtBu2)]− with NHCMesCuCl yields [(Ge9{Si(TMS)3}2)(tBu2P)]Cu(NHCMes) (1), which is a new derivative of the recently reported monomeric zwitterionic tetrel cluster compounds [(Ge9{Si(TMS)3}2)(tBu2P)]M(NHCDipp) (M: Cu, Ag, Au). By contrast, the reaction of the same anion [(Ge9{Si(TMS)3}2PtBu2)]− with the more labile copper phosphine complex Cy3PCuCl leads to the formation of [Ge9{Si(TMS)3}2{(tBu)2PCu}2Ge9{Si(TMS)3}2] (2), which is a neutral dimeric twofold‐bridged [Ge9] cluster compound, with the exo‐bonded phosphine substituent being involved in the cluster bridging. In case of the presence of sterically more demanding phosphines in [Ge9{Si(TMS)3}2PR2]− [R: Mes (3) and NiPr2 (4)], reactions with NHCDippCuCl yielded the complexes NHCDippCu[η3‐Ge9{Si(TMS)3}2(PR2)] [R: Mes (5) and NiPr2 (6)], comprising exclusively Cu−Ge bonds. Compounds 5 and 6 show varying reactivity in dependence of the identity of the phosphine group and represent the first examples of fourfold‐substituted [Ge9] clusters with three different ligands bound to the [Ge9] cluster core. All compounds were characterized by 1H, 13C, 31P, and 29Si NMR spectroscopy. Additionally, compounds 3 and 4 were analyzed by ESI‐MS, and the structures of compounds 1, 2, and 5 were characterized by single‐crystal X‐ray diffraction. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemistry - A European Journal Wiley

On the Variable Reactivity of Phosphine‐Functionalized [Ge9] Clusters: Zintl Cluster‐Substituted Phosphines or Phosphine‐Substituted Zintl Clusters

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Publisher
Wiley
Copyright
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
0947-6539
eISSN
1521-3765
D.O.I.
10.1002/chem.201705678
Publisher site
See Article on Publisher Site

Abstract

The reaction of [(Ge9{Si(TMS)3}2PtBu2)]− with NHCMesCuCl yields [(Ge9{Si(TMS)3}2)(tBu2P)]Cu(NHCMes) (1), which is a new derivative of the recently reported monomeric zwitterionic tetrel cluster compounds [(Ge9{Si(TMS)3}2)(tBu2P)]M(NHCDipp) (M: Cu, Ag, Au). By contrast, the reaction of the same anion [(Ge9{Si(TMS)3}2PtBu2)]− with the more labile copper phosphine complex Cy3PCuCl leads to the formation of [Ge9{Si(TMS)3}2{(tBu)2PCu}2Ge9{Si(TMS)3}2] (2), which is a neutral dimeric twofold‐bridged [Ge9] cluster compound, with the exo‐bonded phosphine substituent being involved in the cluster bridging. In case of the presence of sterically more demanding phosphines in [Ge9{Si(TMS)3}2PR2]− [R: Mes (3) and NiPr2 (4)], reactions with NHCDippCuCl yielded the complexes NHCDippCu[η3‐Ge9{Si(TMS)3}2(PR2)] [R: Mes (5) and NiPr2 (6)], comprising exclusively Cu−Ge bonds. Compounds 5 and 6 show varying reactivity in dependence of the identity of the phosphine group and represent the first examples of fourfold‐substituted [Ge9] clusters with three different ligands bound to the [Ge9] cluster core. All compounds were characterized by 1H, 13C, 31P, and 29Si NMR spectroscopy. Additionally, compounds 3 and 4 were analyzed by ESI‐MS, and the structures of compounds 1, 2, and 5 were characterized by single‐crystal X‐ray diffraction.

Journal

Chemistry - A European JournalWiley

Published: Jan 15, 2018

Keywords: ; ; ; ;

References

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