Synthesis and Reactivity of Coordinatively Unsaturated Dinuclear Ruthenium Bridging Imido Complexes
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- 作者：Shin Takemoto ; Tomoharu Kobayashi ; Takahiro Ito ; Akira Inui ; Kenji Karitani ; Sayuri Katagiri ; Yusaku Masuhara ; Hiroyuki Matsuzaka
- 刊名：Organometallics
- 出版年：2011
- 出版时间：April 25, 2011
- 年：2011
- 卷：30
- 期：8
- 页码：2160-2172
- 全文大小：1296K
- 年卷期：v.30,no.8(April 25, 2011)
- ISSN：1520-6041
文摘
[Cp*Ru(渭-NHPh)]2 (Cp* = 畏5-C5Me5) reacted with CO, t-BuNC, Ph2S鈺怌H2, or Me3SiC鈮H to give the dinuclear ruthenium bridging imido complexes [(Cp*Ru)2(渭-NPh)(渭-L)] (2a, L = CO; 2b, L = t-BuNC; 2c, L = CH2; 2d, L = CCHSiMe3). Protonolysis of 2d with t-BuOH produced the parent vinylidene complex [(Cp*Ru)2(渭-NPh)(渭-CCH2)] (2e). Treatment of 2e with HOTf or MeOTf afforded the cationic alkylidyne complexes [(Cp*Ru)2(渭-NPh)(渭-CR)]OTf (2f, R = Me; 2g, R = Et). Hydride abstraction from 2c with Ph3CBF4 gave the methylidyne complex [(Cp*Ru)2(渭-NPh)(渭-CH)]BF4 (2h). X-ray structures of 2a鈭?b>c and 2f revealed short Ru鈭扤 distances (1.876鈭?.894 脜) consistent with Ru鈭扤 multiple bonds, and the 渭-alkylidyne 2f also featured short Ru鈭扖 bonds (1.929(7) and 1.914(7) 脜). In addition to giving simple Lewis base adducts such as [(Cp*Ru)2(渭-NPh)(渭-CO)(PMe3)] and [(Cp*Ru)2(渭-NPh)(渭-CH2)(t-BuNC)2], these imido complexes provided an array of novel ligand coupling reactions. Thus, 2b underwent a tandem imido鈭抜socyanide coupling and C鈭扝 activation reaction to give an amidinate complex. Complexes 2c and 2e mediated imido鈭扖O鈭抦ethylene and imido鈭扖O鈭抳inylidene coupling to give [{Cp*Ru(CO)2}2(渭-PhNCOCH2)] (6) and [{Cp*Ru(CO)}2(渭-PhNCOC鈺怌H2)] (7), respectively. Complex 2c also underwent a selective coupling reaction with 2 equiv of Me3SiC鈮H to give the 渭-allenylimine complex [(Cp*Ru)2{渭-Me3SiCH鈺怌鈺怌(SiMe3)C(Me)鈺怤Ph}] (8). The imido methylidyne complex coupled with 2 equiv of alkynes to give [(Cp*Ru)2{渭-HC(R1CCR2)(R2CCR1)NPh}]OTf (9a鈭?b>c), a product of double alkyne cycloaddition to the Ru鈭扤 and Ru鈭扖 multiple bonds and C鈭扖 coupling of the resulting ruthena- and azaruthenacyclobutene moieties.