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Combination of sp 2 ‐ and sp 3 ‐Type Phosphorus Atoms for Gold Chemistry: Preparation, Structure, and Catalytic Activity of Gold Complexes That Bear Ligated 2‐Silyl‐1,3‐diphosphapropenes
Author(s) -
Ito Shigekazu,
Zhai Lili,
Mikami Koichi
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100310
Subject(s) - chemistry , silylation , cycloisomerization , catalysis , silver salts , ligand (biochemistry) , phosphorus , medicinal chemistry , crystallography , atom (system on chip) , stereochemistry , inorganic chemistry , organic chemistry , biochemistry , receptor , computer science , embedded system
Kinetically protected 2‐silyl‐1,3‐diphosphapropenes that bear both sp 2 ‐ and sp 3 ‐type phosphorus atoms were employed in the preparation of gold complexes. The structural properties of the 1,3‐diphosphapropene digold(I) complexes were characterized by spectroscopic and crystallographic analyses, which revealed unique aurophilic interactions and conformational properties of the ligand. The 2‐silyl‐1,3‐diphosphapropene‐bis(chlorogold) complexes catalyzed cycloisomerization reactions of 1,6‐enyne derivatives even in the absence of silver co‐catalyst, and were able to be recovered after the reaction. The catalytic activity of the digold complexes primarily depended on the sp 2 ‐type phosphorus atom and the silyl group, and could be tuned by the sp 3 ‐phosphino group. Additionally, results on the catalytic activity of the digold complex in the presence and absence of silver salts showed considerable differences.