Competitive Insertion of Isocyanide into Tantalum−Amido and Tantalum−Methyl Bonds

Competitive Insertion of Isocyanide into Tantalum−Amido and Tantalum−Methyl Bonds
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异氰化物竞争性插入钽氨基和钽甲基键

DOI：
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发表时间：
2002
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影响因子：
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通讯作者：
A. Tiripicchio
A. Tiripicchio
中科院分区：
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文献类型：
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作者：
Francisco Amor;J. Sánchez;P. Royo;H. Jacobsen;O. Blacque;H. Berke;M. Lanfranchi;M. Pellinghelli;A. Tiripicchio

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通过[Ta（η5-C5 Me 5）（NtBu）ClMe]（1）与适当的氨基锂反应，合成了（氨基）甲基配合物[Ta（η5-C5 Me 5）（NtBu）Me（NR 2）] [R = Ph（3），SiMe 3（4）]。尝试分离类似的NHMe衍生物，得到络合物[Ta（η5-C5 Me 5）（NtBu）Me（NHMe）]（5）和[Ta（η5-C5 Me 5）（NMe）Me（NHtBu）]（6）的混合物，其由酰胺基和亚氨基配体之间的氢交换产生。插入CN（2，6-Me 2C 6 H3）引入配合物3和4的Ta-Me键中，得到η1-亚氨酰基衍生物[Ta（η5-C5Me5）（NtBu）（NR2）{η1-C（Me）=N（2，6-Me 2C 6 H3）}] [R = Ph（7），SiMe 3（8）]，而插入到Ta-NRMe中[Ta（η5-C5 Me 5）（NtBu）Me（NRMe）] [R = H（5），Me（2）]的（R = H，Me）键，得到η2-亚氨基甲酰基化合物[Ta（η5-C5 Me 5）（NtBu）Me{η2-C（NRMe）=N（2，6-Me 2C 6 H3）}] [R = H（10），Me（9）].所有新化合物均经1H和13 C NMR谱表征。报道了9的X射线晶体结构。进行DFT计算以证明插入到Ta-C或Ta-N键中的偏好。（© Wiley-VCH Verlag GmbH，69451魏因海姆，德国，2002）
The (amido)methyl complexes [Ta(η5-C5Me5)(NtBu)Me(NR2)] [R = Ph (3), SiMe3 (4)] were prepared by reaction of [Ta(η5-C5Me5)(NtBu)ClMe] (1) with the appropriate lithium amides. Attempts to isolate the analogous NHMe derivative afforded a mixture of complexes [Ta(η5-C5Me5)(NtBu)Me(NHMe)] (5) and [Ta(η5-C5Me5)(NMe)Me(NHtBu)] (6), resulting from hydrogen exchange between the amido and imido ligands. Insertion of CN(2,6-Me2C6H3) into the Ta−Me bond of complexes 3 and 4 gave the η1-iminoacyl derivatives [Ta(η5-C5Me5)(NtBu)(NR2){η1-C(Me)=N(2,6-Me2C6H3)}] [R = Ph (7), SiMe3 (8)], while insertion into the Ta−NRMe (R = H, Me) bond of the complexes [Ta(η5-C5Me5)(NtBu)Me(NRMe)] [R = H (5), Me (2)] gave the η2-iminocarbamoyl compounds [Ta(η5-C5Me5)(NtBu)Me{η2-C(NRMe)=N(2,6-Me2C6H3)}] [R = H (10), Me (9)]. All of the new compounds were characterized by 1H and 13C NMR spectroscopy. The X-ray crystal structure of 9 is reported. DFT calculations were carried out to justify the preference of the insertion either into the Ta−C or the Ta−N bond. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)