TY - JOUR
T1 - A Novel Anionic Gold-Indium Cluster Compound
T2 - Synthesis and Molecular and Electronic Structure
AU - Gabbaï, François P.
AU - Chung, Sai Cheong
AU - Schier, Annette
AU - Krüger, Sven
AU - Rösch, Notker
AU - Schmidbaur, Hubert
PY - 1997
Y1 - 1997
N2 - The insertion of InBr into the Au - Br bond of [(Ph3P)AuBr] in tetrahydrofuran (thf) in the presence of [(CH2-PPh2)2] (dppe) leads to the formation of an orange complex [(dppe)2Au]+[(dppe)2Au3In 3Br7(thf)]-, 2. Analytical, spectroscopic, and X-ray structural investigations showed that this product is an anionic analogue of a neutral chloride complex [(dppe)2Au3In3Cl6(thf)3], 1, prepared recently. Both complexes have an Au3In3 cluster core of approximate C2v symmetry with one extremely short Au-Au bond [Au1-Au3 2.575(1) Å] as part of a quasilinear array P1- Au1- Au3-P4, suggesting the presence of a bis(phosphine) complex of the neutral Au2 molecule as part of the cluster. The third gold atom (Au2) is then assigned oxidation state +1. To gain deeper insight into the structure and bonding of this novel class of gold cluster compounds, regarding mainly the peculiar cluster geometry, the charge distribution, and the oxidation states, a series of scalar relativistic all-electron density functional (DF) calculations on model systems has been performed. As a model for 1, the neutral cluster {Au3(PH3)4[InCl2(H 2O)]3} was studied. For the examination of the geometry of complexes 1 and 2, the cluster Au3(PH3),4I3 has been considered as a further simplified model, where iodine replaces the InX2(thf) units. Experimental and calculated cluster geometries agree satisfactorily, and the formal oxidation states of the gold atoms (0 for Au1 and Au3, +1 for Au2) could be confirmed, but for the In centers no interpretable differences of the Mulliken charges were found.
AB - The insertion of InBr into the Au - Br bond of [(Ph3P)AuBr] in tetrahydrofuran (thf) in the presence of [(CH2-PPh2)2] (dppe) leads to the formation of an orange complex [(dppe)2Au]+[(dppe)2Au3In 3Br7(thf)]-, 2. Analytical, spectroscopic, and X-ray structural investigations showed that this product is an anionic analogue of a neutral chloride complex [(dppe)2Au3In3Cl6(thf)3], 1, prepared recently. Both complexes have an Au3In3 cluster core of approximate C2v symmetry with one extremely short Au-Au bond [Au1-Au3 2.575(1) Å] as part of a quasilinear array P1- Au1- Au3-P4, suggesting the presence of a bis(phosphine) complex of the neutral Au2 molecule as part of the cluster. The third gold atom (Au2) is then assigned oxidation state +1. To gain deeper insight into the structure and bonding of this novel class of gold cluster compounds, regarding mainly the peculiar cluster geometry, the charge distribution, and the oxidation states, a series of scalar relativistic all-electron density functional (DF) calculations on model systems has been performed. As a model for 1, the neutral cluster {Au3(PH3)4[InCl2(H 2O)]3} was studied. For the examination of the geometry of complexes 1 and 2, the cluster Au3(PH3),4I3 has been considered as a further simplified model, where iodine replaces the InX2(thf) units. Experimental and calculated cluster geometries agree satisfactorily, and the formal oxidation states of the gold atoms (0 for Au1 and Au3, +1 for Au2) could be confirmed, but for the In centers no interpretable differences of the Mulliken charges were found.
UR - http://www.scopus.com/inward/record.url?scp=0001256120&partnerID=8YFLogxK
U2 - 10.1021/ic970725c
DO - 10.1021/ic970725c
M3 - Article
AN - SCOPUS:0001256120
SN - 0020-1669
VL - 36
SP - 5699
EP - 5705
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 25
ER -