CO Release from Norbornadiene Iron(0) Tricarbonyl Complexes: Importance of Ligand Dissociation
CO Release from Norbornadiene Iron(0) Tricarbonyl Complexes: Importance of Ligand Dissociation
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DOI：
10.1021/om300419w
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发表时间：
2012-08-27
期刊：
影响因子：
2.8
通讯作者：
Lynam, Jason M.
中科院分区：
文献类型：
--
作者：
Atkin, Anthony J.;Fairlamb, Ian J. S.;Lynam, Jason M.
研究了一系列三羰基铁、四羰基铬和四羰基钼配合物的CO释放性能。含有2，S-双环[2.2.1]-庚烯（降冰片二烯）配体的三羰基铁络合物被证明是有效的CO释放分子，其中CO释放的速率和程度可以通过改性降冰片二烯框架来调节。含有母体降冰片二烯的物质和在有机配体的7-位具有取代基的物质表现出CO释放;在2-和/或3-位含有酯取代基的物质不具有CO释放。CO释放在这个物种的机制，提出了涉及初始降冰片二烯解离，这是由光谱数据和观察，过量的取代降冰片二烯的加入延缓CO释放速率的支持的建议。从含降冰片二烯二酯复合物中释放的CO可以被光化学促进，并且细胞活力研究表明，在没有光的情况下，这种复合物是无毒的，使其成为进一步研究作为光-CO-RM的优秀候选物。铬和钼四羰基络合物都释放CO，在钼类似物的情况下，这是快速的。
An investigation into the CO-releasing properties of a range of iron tricarbonyl and chromium and molybdenum tetracarbonyl complexes is presented. Iron tricarbonyl complexes containing the 2,S-bicyclo[2.2.1]-heptene (norbornadiene) ligand are shown to be effective CO-releasing molecules, in which the rate and extent of CO release may be modulated by modification of the norbornadiene framework. Species containing the parent norbornadiene and those with a substituent at the 7-position of the organic ligand exhibit CO release; those containing ester substituents at the 2- and/or 3-positions do not. A mechanism for CO release in this species is proposed which involves initial norbornadiene dissociation, a suggestion which is supported by the spectroscopic data and the observation that the addition of excess substituted norbornadiene retards the rate of CO release. CO release from the diester-containing norbornadiene complex may be promoted photochemically, and cell viability studies indicate that in the absence of light this complex is nontoxic, making it an excellent candidate for further study as a photo-CO-RM. Both the chromium and molybdenum tetracarbonyl complexes release CO, which in the case of the molybdenum analogue is rapid.