Diversity and design of metal-based carbon monoxide-releasing molecules (CO-RMs) in aqueous systems: revealing the essential trends.
Diversity and design of metal-based carbon monoxide-releasing molecules (CO-RMs) in aqueous systems: revealing the essential trends.
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DOI：
10.1039/b822157j
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发表时间：
2009-05
影响因子：
4
通讯作者：
Wei-Qiang Zhang;Anthony J. Atkin;R. Thatcher;A. Whitwood;I. Fairlamb;Jason M. Lynam
中科院分区：
文献类型：
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作者：
Wei-Qiang Zhang;Anthony J. Atkin;R. Thatcher;A. Whitwood;I. Fairlamb;Jason M. Lynam
已使用脱氧肌红蛋白-碳单氧基肌红蛋白测定评估了初级金属羰基络合物的不同库的CO释放能力。一氧化碳释放过程中观察到在水溶液中的广泛的速率。对于八面体d（6）配合物，其释放速率顺序为FeI（2）（CO）（4）> [NEt（4）][V（CO）（6）] > MnBr（CO）（5）> Cr（CO）（6），表明CO的释放不受金属-碳键强度的控制。在系列[NEt（4）][MX（CO）（5）]（M = Cr、Mo、W; X =Cl、Br、I）中，发现CO释放速率随组降低（Cr > Mo > W），而在铬系列中，对于卤化物观察到类似的趋势（Cl > Br > I）。d（4）配合物[NEt（4）][MI（3）（CO）（4）]（M = Mo，W）的释放速度比d（6）配合物快。对[NEt（4）][MX（CO）（5）]系列的机理研究揭示了[[M（CO）（5）]（2）（mu-X）]（-）在CO释放过程中的中间性，并且M-X键的水解，而不是M-CO键的内在强度，控制了水体系中的CO释放速率。
The CO-releasing ability of a diverse library of primary metal carbonyl complexes has been assessed using a deoxymyoglobin-carbonmonoxymyglobin assay. A wide spectrum of rates for the CO-release process was observed in aqueous systems. For octahedral d(6) complexes, the rate was found to decrease in the sequence FeI(2)(CO)(4) > [NEt(4)][V(CO)(6)] > MnBr(CO)(5) > Cr(CO)(6) implying that CO-release is not controlled by the metal-carbon bond strengths. Within the series, [NEt(4)][MX(CO)(5)] (M = Cr, Mo, W; X =Cl, Br, I), the rate of CO-release was found to decrease down the group (Cr > Mo > W), whilst within the chromium series a similar trend was observed for the halide (Cl > Br > I). The d(4) complexes [NEt(4)][MI(3)(CO)(4)] (M = Mo, W) exhibit faster release than their d(6) congeners. A mechanistic investigation into the [NEt(4)][MX(CO)(5)] series revealed the intermediacy of [[M(CO)(5)](2)(mu-X)](-) in the CO-release process and that the hydrolysis of the M-X bond, rather than the intrinsic strength of M-CO bonds, controls the rate of CO-release in aqueous systems.