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A Trinuclear Au I Complex with Different R 3 P–Au Centers: Synthesis, Characterization, and Synergetic Catalysis for Hydration of Phenylacetylene
Author(s) -
Lai ShiJun,
Yang Da,
Li YongQi,
Zhao XiaoLi,
Lu Yong,
Liu Ye
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403150
Subject(s) - phenylacetylene , chemistry , acetophenone , crystallography , catalysis , ligand (biochemistry) , moiety , phosphine , molecule , stereochemistry , yield (engineering) , crystal structure , single crystal , medicinal chemistry , organic chemistry , biochemistry , materials science , receptor , metallurgy
A trinuclear Au I complex ( 3A ) was synthesized and fully characterized relative to mononuclear ( 1A ) and dinuclear ( 2A ) complexes. The single‐crystal X‐ray diffraction analyses show that the Au I ‐centered vectors in each of the Au I complexes ( 1A – 3A ) are all in a slightly distorted linear configuration, in which the Au I center is diagonally coordinated by one Cl – and one phosphine ligand. In 3A each P–Au–Cl vector is radially attached to the core of 1‐(thiazol‐2′‐yl)imidazolyl, which does not allow the short contact between the Au atoms to develop an aurophilic Au I –Au I interaction. Every P–Au–Cl moiety in 3A is different to each other in terms of Au–P and Au–Cl bond lengths, P–Au–Cl bond angles, and P–Au–Cl configurable orientation owing to the different coordinating ability of the involved phosphines. When 1A – 3A were employed as the precatalysts for the hydration of phenylacetylene in aqueous methanol media without the involvement of any auxiliary additive, and at the same benchmark Au concentration, the reaction over 3A proceeded selectively according to Markovnikov's rule with the highest yield of acetophenone relative to those over 2A and 1A . This indicates that the catalytic performance of 3A is the outcome of the synergetic effect of the three different R 3 P–Au centers, in which each R 3 P–Au site plays an individual role in activating the substrate molecule.