Synthesis and Reactivity of New Niobocene Hydride-Stibine and Hydride-Stilbene Complexes. X-ray Crystal Structure of [Nb(畏5-C5H4SiMe3)2(H)(tra

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• 作者：Antonio Anti帽olo ; Juan-Carlos P茅rez-Flores ; Maria Jes煤s Herv谩s ; Santiago Garc铆a-Yuste ; Maria Isabel L贸pez-Solera ; Antonio Otero ; Ana Rodr铆guez Fern谩ndez-Pacheco ; Maria Teresa Tercero-Morales
• 刊名：Organometallics
• 出版年：2013
• 出版时间：February 11, 2013
• 年：2013
• 卷：32
• 期：3
• 页码：862-868
• 全文大小：368K
• 年卷期：v.32,no.3(February 11, 2013)
• ISSN：1520-6041

文摘

The synthesis of a stable hydride triphenylstibine derivative, Nb(畏⁵-C₅H₄SiMe₃)₂(H)(SbPh₃) (1), has been achieved through the formation of the transient coordinatively unsaturated 16-electron species [Nb(畏⁵-C₅H₄SiMe₃)₂(H)] by thermolytic loss of H₂ from Nb(畏⁵-C₅H₄SiMe₃)₂(H)₃ (2) followed by the coordination of a triphenylstibine ligand. Low-temperature protonation of 1 with a slight excess of CF₃COOD led to the 畏²-dihydrogen complex 3 as the monodeuterated H鈥揇 isotopomers of [Nb(畏⁵-C₅H₄SiMe₃)₂(畏²-HD)(SbPh₃)]⁺CF₃CO₂^{鈥?/sup> (3-d₁). When the temperature was increased to room temperature, complex 3 was converted into the transoid dihydride [Nb(畏5-C₅H₄SiMe₃)₂(H)₂(SbPh₃)]CF₃CO₂ (4). Surprisingly, when CF₃COOH in deuterated solvents was used in the protonation process, the final 畏2-dihydrogen product always contained a substantial amount of deuterated isotopomers. Furthermore, a new hydrido olefin niobocene complex, [Nb(畏5-(C₅H₄SiMe₃)₂(H)(trans-畏2-C,C-PhCH鈺怌HPh)] (5), can be synthesized by elimination of the stibine ligand from 1 followed by the addition of cis or trans stilbene. Complex 5 can also be obtained by reaction of 2 in the presence of cis or trans stilbene by the thermolytic loss of H₂. All of these compounds were characterized by IR and multinuclear NMR spectroscopy, and the molecular structure of 5 was determined by single-crystal X-ray diffraction.}