Synthesis of alkynyl-substituted 9,10-dimetallatriptycenes of group 14 and their application in the preparation of a novel class of organometallic oligomers

被引:17
作者
Dam, MA
Hoogervorst, WJ
de Kanter, FJJ
Bickelhaupt, F
Spek, AL
机构
[1] Vrije Univ Amsterdam, Scheikundig Lab, NL-1081 HV Amsterdam, Netherlands
[2] Univ Utrecht, Bijvoet Ctr Mol Res Crystal & Struct Chem, NL-3584 CH Utrecht, Netherlands
关键词
D O I
10.1021/om980073f
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The preparation of((trimethylsilyl)ethynyl)germanium trichloride (4) allowed the synthesis of various alkynyl-substituted 9,10-dimetallatriptycenes via a simple one-pot synthetic procedure. For example, reaction of 4 with o-phenylenemagnesium (1) gave access to 9, 10-(RC=C)(2)-9,10-digermatriptycenes (5, R = SiMe3; 6, R = H), while reaction of 4 with tris(o-(chloromagnesio)phenyl)phenylgermane (2a) furnished 9-(RC=C)-10-phenyl-9,10-digermatriptycenes (7, R = SiMe3; 8, R = H). The synthetic potential of these compounds in the preparation of rigid organometallic oligomers with conjugated spacers was demonstrated by the oxidative coupling of 8, which furnished 1,4-bis(9-(10-phenyl-9,10-digermatriptycyl))-buta-1,3-diyne (9), whose X-ray crystal structure was determined, and the hydrosilylation of 8 with 10-phenyl-10-germa-9-silatriptycene (3a), which yielded trans-1-(9-(10-phenyl-9,10-digermatriptycyl))-2-(9-(10-phenyl-9-sila-10-germatriptycyl))ethene (10).
引用
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页码:1762 / 1768
页数:7
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