BIS-(PI-PENTAMETHYLCYCLOPENTADIENYL) (2-METHYLIDENE) TITANACYCLOBUTANE - SELECTIVE INSERTION OF ISONITRILES AND DIPHENYLKETENE - FORMATION OF 5-MEMBERED AND 6-MEMBERED METALLACYCLES

被引:21
作者
BECKHAUS, R
WAGNER, T
ZIMMERMANN, C
HERDTWECK, E
机构
[1] WISSENSCH ZENTRUM BERLIN ADLERSHOF,D-12484 BERLIN,GERMANY
[2] TECH UNIV MUNICH,INST ANORGAN CHEM,D-85747 GARCHING,GERMANY
关键词
D O I
10.1016/0022-328X(93)83144-K
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of isonitriles or diphenylketene with the titanacyclobutane derivative Cp(2)(star)TiC(=CH2)CH2CH2 (2) (Cp(star)=[C-5(CH3)(5)]) at room temperature afforded the five- and six-membered metallacycles Cp(2)(star)TiC(=CH2)CH2CH2C(=NR) (R = C6H11, 7a; C(CH3)(3), 7b) and Cp(2)(star)TiC(=CH2)CH2CH2C(=C(PH2)O (11), respectively, whose structures have been characterized by spectral data and X-ray analysis. By using other cumulene type molecules instead of Ph(2)C=C=O, e.g. carbon dioxide or isocyanates, no insertion reaction is observed. Only monoinsertions in the Ti-C(sp)3 bond of 2 are found, without further subsequent reactions. The insertion of a second isonitrile or ketene molecule is prevented by the absence of a free coordination site on the metal complexes 7 and 11. X-ray structure determination of 7a revealed that the heterocycle has an eta(1)-iminoacyl structure (Ti-N distance 3.080(3) Angstrom).
引用
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页码:181 / 189
页数:9
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