TY - JOUR
T1 - On the Variable Reactivity of Phosphine-Functionalized [Ge9] Clusters
T2 - Zintl Cluster-Substituted Phosphines or Phosphine-Substituted Zintl Clusters
AU - Geitner, Felix S.
AU - Wallach, Christoph
AU - Fässler, Thomas F.
N1 - Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/3/15
Y1 - 2018/3/15
N2 - 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.
AB - 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.
KW - N-heterocyclic carbene
KW - coinage metal
KW - dimer
KW - phosphine
KW - zintl clusters
UR - http://www.scopus.com/inward/record.url?scp=85044027109&partnerID=8YFLogxK
U2 - 10.1002/chem.201705678
DO - 10.1002/chem.201705678
M3 - Article
C2 - 29322565
AN - SCOPUS:85044027109
SN - 0947-6539
VL - 24
SP - 4103
EP - 4110
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 16
ER -