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
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
收藏
页码:3439 / 3446
页数:8
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