Reactivity of vinylidene complexes of ruthenium with hydrazines and hydroxylamines

被引：12

作者：

Albertin, Gabriele ^{[1
]}

Antoniutti, Stefano ^{[1
]}

Bortoluzzi, Marco ^{[1
]}

Botter, Alessandra ^{[1
]}

Castro, Jesus ^{[2
]}

机构：

[1] Univ Ca Foscari Venezia, Dipartimento Sci Mol & Nanosistemi, I-30123 Venice, Italy

[2] Univ Vigo, Fac Quim, Dept Quim Inorgan, Vigo 36310, Galicia, Spain

来源：

DALTON TRANSACTIONS | 2015年 / 44卷 / 07期

关键词：

N-N BOND; TRANSITION-METAL VINYLIDENE; EFFECTIVE CORE POTENTIALS; EQUIVALENT-TO-C; TERMINAL ALKYNES; BASIS-SETS; MOLECULAR CALCULATIONS; NUCLEOPHILIC-ADDITION; CATALYTIC-REDUCTION; SELECTIVE SYNTHESIS;

D O I：

10.1039/c4dt03464c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Vinylidene complexes [Ru(eta(5)-C5H5){=C=C(H)R}(PPh3)L]BPh4 (1, 2) [L = P(OMe)(3), P(OEt)(3); R = Ph, p-tolyl, Bu-t, H] react with hydrazine R1NHNH(2) (R1 = H, Me, Ph) to afford nitrile derivatives [Ru(eta(5)-C5H5)( N=CCH2R)(PPh3)L]BPh4 (3, 4) and amine R1NH(2). Hydroxylamine NH2OH also reacts with vinylidenes 1, 2 to yield nitrile derivatives 3, 4 and H2O. Studies with N-15-labeled hydrazine and DFT calculations allowed a reaction path to be proposed. The complexes were characterized by spectroscopy (IR, H-1, P-31, C-13 and N-15 NMR) and by X-ray crystal structure determination of [Ru(mu(5)-C5H5)(N=CCH2Ph)(PPh3){P(OEt)(3)}] BPh4 (4a).

引用

页码：3439 / 3446

页数：8

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