TY - JOUR
T1 - Derivatization of Phosphine Ligands with Bulky Deltahedral Zintl Clusters - Synthesis of Charge Neutral Zwitterionic Tetrel Cluster Compounds [(Ge9{Si(TMS)3}2)tBu2P]M(NHCDipp) (M: Cu, Ag, Au)
AU - Geitner, Felix S.
AU - Dums, Jasmin V.
AU - Fässler, Thomas F.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/8/30
Y1 - 2017/8/30
N2 - Reactions of silylated clusters [Ge9{Si(TMS)3}3]- or [Ge9{Si(TMS)3}2]2- with dialkylhalophosphines R2PCl (Cy, iPr, tBu) at ambient temperature yield the first tetrel Zintl cluster compounds bearing phosphine moieties. Varying reactivity of the dialkylhalophosphines toward the silylated clusters is observed depending on the bulkiness of the phosphine's alkyl substituents and on the number of hypersilyl groups at the tetrel cluster. Reactions between phosphines with small cyclohexyl- (Cy) or isopropyl- (iPr) groups and the tris-silylated cluster [Ge9{Si(TMS)3}3]- yield the novel neutral cluster compounds [Ge9{Si(TMS)3}3PR2] (R: Cy (1), iPr (2)) with discrete Ge-P exo bonds. By contrast, the bulkier phosphine tBu2PCl does not react with [Ge9{Si(TMS)3}3]- due to steric crowding. However, the reaction with the bis-silylated cluster [Ge9{Si(TMS)3}2]2- yields the novel cluster compound [Ge9{Si(TMS)3}2PtBu2]- (3). Subsequent reactions of compound 3 with NHCDippMCl (M: Cu, Ag, Au) yield the charge neutral zwitterionic compounds [(Ge9{Si(TMS)3}2)tBu2P]M(NHCDipp) (M: Cu, Ag, Au) (4-6), in which compound 3 acts as a phosphine ligand bearing a bulky tetrel Zintl cluster moiety. Compounds 4-6 also represent the first uncharged examples for 3-fold substituted tetrel Zintl clusters.
AB - Reactions of silylated clusters [Ge9{Si(TMS)3}3]- or [Ge9{Si(TMS)3}2]2- with dialkylhalophosphines R2PCl (Cy, iPr, tBu) at ambient temperature yield the first tetrel Zintl cluster compounds bearing phosphine moieties. Varying reactivity of the dialkylhalophosphines toward the silylated clusters is observed depending on the bulkiness of the phosphine's alkyl substituents and on the number of hypersilyl groups at the tetrel cluster. Reactions between phosphines with small cyclohexyl- (Cy) or isopropyl- (iPr) groups and the tris-silylated cluster [Ge9{Si(TMS)3}3]- yield the novel neutral cluster compounds [Ge9{Si(TMS)3}3PR2] (R: Cy (1), iPr (2)) with discrete Ge-P exo bonds. By contrast, the bulkier phosphine tBu2PCl does not react with [Ge9{Si(TMS)3}3]- due to steric crowding. However, the reaction with the bis-silylated cluster [Ge9{Si(TMS)3}2]2- yields the novel cluster compound [Ge9{Si(TMS)3}2PtBu2]- (3). Subsequent reactions of compound 3 with NHCDippMCl (M: Cu, Ag, Au) yield the charge neutral zwitterionic compounds [(Ge9{Si(TMS)3}2)tBu2P]M(NHCDipp) (M: Cu, Ag, Au) (4-6), in which compound 3 acts as a phosphine ligand bearing a bulky tetrel Zintl cluster moiety. Compounds 4-6 also represent the first uncharged examples for 3-fold substituted tetrel Zintl clusters.
UR - http://www.scopus.com/inward/record.url?scp=85028632758&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b05834
DO - 10.1021/jacs.7b05834
M3 - Article
C2 - 28745883
AN - SCOPUS:85028632758
SN - 0002-7863
VL - 139
SP - 11933
EP - 11940
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 34
ER -