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首页> 外文期刊>Chemistry: A European journal >Reactivity studies of iridium pyridylidenes [TpMe2Ir(C 6H5)2(C(CH)3C(R)N H] (R=H, Me, Ph)
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Reactivity studies of iridium pyridylidenes [TpMe2Ir(C 6H5)2(C(CH)3C(R)N H] (R=H, Me, Ph)

机译：吡啶吡啶鎓[TpMe2Ir（C 6H5）2（C（CH）3C（R）N H]的反应性研究（R = H，Me，Ph）

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摘要

The reactivity of a series of iridium-pyridylidene complexes with the formula [Tp~(Me2)Ir(C_6H_5)_2(C(CH) _3C(R)NH] (1 a-1 c) towards a variety of substrates, from small molecules, such as H_2, O_2, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e~- unsaturated [Tp ~(Me2)Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H_2 is heterolytically split to give hydride~-pyridylidene complexes, whilst CO, CO_2, and H _2C?￡O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five~-membered metallacycles with an IrCH_2CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four-membered iridacycles with the IrC(?￡CH_2)N moiety. C_6H_5(C?￡O)H and C_6H _5C?￡CH react with formation of Ir-C_6H _5 and Ir-C?￡CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a-1 c against O_2 is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported. Sweet 16 e~-: Many pyridylidenes 1 react with a diverse range of reagents via 16 e~- phenyl-pyridyl intermediates A (see scheme), which, in general, behave as internally frustrated Lewis pairs (FLPs).
机译：一系列具有式[Tp〜（Me2）Ir（C_6H_5）_2（C（CH）_3C（R）NH]（1 a-1 c）的铱-吡啶基亚配合物对各种底物的反应性描述了H_2，O_2，碳氧化物和甲醛等分子对烯烃和炔烃的反应，观察到的大多数反应性可以通过调用16 e〜-不饱和[Tp〜（Me2）Ir（苯基）（吡啶基）来最好地解释。中间体，表现为内部受阻的路易斯对（FLP），H_2杂分解生成氢化物〜吡啶亚基络合物，而CO，CO_2和H _2C ￡ O分别提供羰基，碳酸盐和醇盐。丙烯形成具有IrCH_2CH（R）N（R = H，Me）基序的五元金属环，而相反，乙炔提供具有IrC（？CHCH_2）N部分的四元铱环。 O）H和C_6H _5C？￡ CH反应生成Ir-C_6H _5和Ir-C ￡￡ CPh键，并同时消除吡啶和苯分子。描述了针对O_2的化合物1a-1c的制备。还报告了为这些实验观察提供理论支持的密度泛函理论计算。甜16 e--：许多吡啶基1通过16 e--苯基-吡啶基中间体A（请参见方案）与多种试剂反应，这些中间体通常表现为内部受阻的Lewis对（FLP）。

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