Mixed dinitrogen-organocyanamide complexes of molybdenum(0) and their protic conversion into hydrazide and amidoazavinylidene derivatives

被引：33

作者：

Cunha, SMPRM ^{[1
]}

da Silva, MFCG ^{[1
]}

Pombeiro, AJL ^{[1
]}

机构：

[1] Univ Tecn Lisboa, Ctr Quim Estrutural, Inst Super Tecn, P-1049001 Lisbon, Portugal

来源：

INORGANIC CHEMISTRY | 2003年 / 42卷 / 06期

关键词：

D O I：

10.1021/ic026176e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Organocyanamides, NdropCNR(2) (R = Me or Et), react with trans-[Mo(N-2)(2)(dppe)(2)] (1, dppe = Ph2PCH2CH2PPh2), in THF, to give the first mixed molybdenum dinitrogen-cyanamide complexes trans-[Mo(N-2) (NCNR2)(dppe)(2)] (R = Me 2a or Et 2b) which are selectively protonated at N-2 by HBF4 to yield the hydrazide(2-) complexes trans[Mo(NNH2)(NCNR2)(dppe)(2)][BF4](2) (R = Me, 3a, or Et, 3b). On treatment with Ag[BF4], oxidation and metal fluorination occur, and the ligating cyanamide undergoes an unprecedented beta-protonation at the unsaturated C atom to form trans-[MoF(NCHNR2)(dppe)(2)][BF4](2) (R = Me, 4a, or Et, 4b) compounds which present the novel amidoazavinylidene (or amidomethyleneamide) ligands. Complexes 4 are also formed from the corresponding compounds 3, with liberation of ammonia and hydrazine. The crystal structure of 2b was determined by single-crystal X-ray diffraction analysis which indicates that the N atom of the amide group has a trigonal planar geometry.

引用

页码：2157 / 2164

页数：8

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