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Conceptual Extension of the Degradation–Transformation of N-Heterocyclic Carbenes: Unusual Rearrangements on Osmium
Organometallics ( IF 2.5 ) Pub Date : 2018-04-09 , DOI: 10.1021/acs.organomet.8b00110
Miguel A. Esteruelas 1 , M. Pilar Gay 1 , Enrique Oñate 1
Affiliation  

The range of processes of degradation–transformation of NHC ligands in the coordination sphere of a transition metal has been enlarged. The NHC-acyl ligand of the complex Os{κ2-C,C-[C(O)CH2ImMe]}Cl(PiPr3)2 (1) undergoes a complex rearrangement promoted by internal alkynes to give Os{κ2-C,N-[CH2ImMe]}Cl(CO)(PiPr3)2 (2). Mechanistic studies have revealed that the degradation involves a catalytic alkyne-mediated deinsertion of CO from the acyl moiety to afford Os{κ2-C,C-[CH2ImMe]}Cl(CO)(PiPr3)2 (3), followed by a thermally activated stoichiometric 1,2-methylene shift from N to C. The catalytic activity of the alkynes depends upon their substituents, decreasing in the sequence diphenylacetylene > 1-phenyl-1-propyne > 3-hexyne > 2-butyne. Phenylacetylene tautomerizes in the metal coordination sphere to afford the stable vinylidene Os{κ2-C,C-[C(O)CH2ImMe]}Cl(═C═CHPh)(PiPr3)2 (4), which experiences the coupling of the acyl moiety and the vinylidene ligand under a carbon monoxide atmosphere. The addition of HBF4·OEt2 to the resulting complex Os{κ2-C,C-[C(═CHPh)C(O)CH2ImMe]}Cl(CO)2(PiPr3) (5) leads to [Os{κ2-O,C-[O═C(CH═CHPh)CH2ImMe]}Cl(CO)2(PiPr3)]BF4 (6) containing an NHC-(α,β-unsaturated ketone) ligand.

中文翻译:

N-杂环卡宾降解-转化的概念延伸:O的异常重排

在过渡金属配位领域中,NHC配体的降解转化过程范围已扩大。复杂O的NHC酰基配体{κ 2 - ÇÇ - [C(O)CH 2 ImMe]}氯(P321)由内部炔烃促进经历一个复杂的重排,得到锇{ κ 2 - çñ - [CH 2 ImMe]}氯(CO)(P322)。机理的研究已经揭示,该降解涉及CO催化炔介导的脱嵌从酰基部分,得到锇{κ 2 - ÇÇ - [CH 2 ImMe]}氯(CO)(P323),然后从N到C进行热活化的化学计量的1,2-亚甲基转移。炔烃的催化活性取决于它们的取代基,顺序为二苯乙炔> 1-苯基-1-丙炔> 3-己炔> 2-丁炔。苯乙炔tautomerizes在金属配位球,得到稳定的偏二锇{κ 2 - ÇÇ - [C(O)CH 2ImMe]} Cl(═C═CHPh)(P i Pr 324),其在一氧化碳气氛下经历酰基部分和亚乙烯基配体的偶联。加入HBF的4 ·OET 2至所得复杂操作系统{κ 2 - ÇÇ - [C(═CHPh)C(O)CH 2 ImMe]}氯(CO)2(P3)(5)导致了[Os {κ 2 - öç - [O = C(CH═CHPh)CH 2 ImMe]}氯(CO)2(P3)] BF 46)含有NHC-(α,β-不饱和酮)配体。
更新日期:2018-07-14
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