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Synthesis of Stable Silicon Heterocycles by Reaction of Organic Substrates with a Chlorosilylene [PhC(N t Bu) 2 SiCl]
Author(s) -
Khan Shabana,
Sen Sakya S.,
Kratzert Daniel,
Tavčar Gašper,
Roesky Herbert W.,
Stalke Dietmar
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001901
Subject(s) - diimine , chemistry , bond cleavage , cycloaddition , medicinal chemistry , lone pair , oxidative addition , synthon , ligand (biochemistry) , moiety , stereochemistry , photochemistry , crystallography , organic chemistry , molecule , catalysis , biochemistry , receptor
Heteroleptic chlorosilylene (PhC(N t Bu) 2 SiCl) ( 1 ) reacts with unsaturated organic compounds under oxidative addition. Reactions of 1 with cyclooctatetraene (COT) and a diimine afford [1+4]‐cycloaddition products 3 and 6 , respectively. In the case of COT, one SiN bond of the amidinato ligand is cleaved, resulting in tetracoordinate silicon, whereas with a diimine a pentacoordinate silicon is formed. Treatment of 1 with ArNCNAr (Ar=2,6‐ i Pr 2 C 6 H 3 ) yields silaimine complex 4 with cleavage of one of the CN bonds. The facile isolation of silaimine complexes is probably due to the kinetic protection afforded by the bulky Ar moiety. When 1 is treated with tert ‐butyl isocyanate, cleavage of the CO bond is observed, which leads to formation of the four‐membered Si 2 O 2 cycle 5 . The same product is formed when 1 is allowed to react with trimethylamine N ‐oxide. When 1 is treated with diphenyl disulfide, cleavage of the SS bond occurs to form 7 . All products have been characterized by multinuclear NMR spectroscopy, EI mass spectrometry, and elemental analysis. In addition, the molecular structures of 3 – 6 have been determined by single‐crystal X‐ray diffraction studies. Collectively, these results suggest that owing to the presence of the lone pair of electrons, the propensity of 1 to undergo oxidative addition is very high.