Synthesis of Stable Silicon Heterocycles by Reaction of Organic Substrates with a Chlorosilylene [PhC(NtBu)2SiCl]

被引:61
作者
Khan, Shabana [1 ]
Sen, Sakya S. [1 ]
Kratzert, Daniel [1 ]
Tavcar, Gasper [1 ]
Roesky, Herbert W. [1 ]
Stalke, Dietmar [1 ]
机构
[1] Univ Gottingen, Inst Inorgan Chem, D-37077 Gottingen, Germany
关键词
cycloaddition; N ligands; reactivity; small ring systems; X-ray diffraction; STRUCTURAL-CHARACTERIZATION; OXIDATIVE ADDITION; CRYSTAL-STRUCTURE; PENTACOORDINATE SILICON; DOUBLE-BONDS; SILYLENE; COMPLEXES; CARBENE; LIGANDS; DECAMETHYLSILICOCENE;
D O I
10.1002/chem.201001901
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Heteroleptic chlorosilylene (PhC(NtBu)(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 Si-N bond of the amidinato ligand is cleaved, resulting in tetracoordinate silicon, whereas with a diimine a penta-coordinate silicon is formed. Treatment of 1 with ArN=C=NAr (Ar=2,6-iPr(2)C(6)H(3)) yields silaimine complex 4 with cleavage of one of the C=N 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 tertbutyl isocyanate, cleavage of the C=O bond is observed, which leads to formation of the four-membered Si2O2 cycle 5. The same product is formed when 1 is allowed to react with trime-thylamine N-oxide. When 1 is treated with diphenyl disulfide, cleavage of the S-S 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.
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页码:4283 / 4290
页数:8
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