Hering Florian, Nitsch Jörn, Paul Ursula, Steffen Andreas, Bickelhaupt F Matthias, Radius Udo
Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email:
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling , VU University Amsterdam , De Boelelaan 1083 , NL-1081 HV Amsterdam , The Netherlands.
Chem Sci. 2015 Feb 1;6(2):1426-1432. doi: 10.1039/c4sc02998d. Epub 2014 Dec 3.
Synthesis, characterization and investigations on the reactivity of the novel metal basic, yet isolable 14 VE NHC-complexes [M(iPrIm)] (M = Pd , Pt ; iPrIm = 1,3-di-isopropyl-imidazolin-2-ylidene; VE = valence electron; NHC = N-heterocyclic carbene) is reported and compared to the chemistry of the corresponding nickel complex. Quantum chemical analyses reveal that differences in the reactivity of group 10 NHC complexes are caused by differences in the rigidity and thus activation strain associated with bending the corresponding d-[M(NHC)] fragments during reaction. These results should have implications for the understanding of the fundamental steps in catalytic cycles, in which such complex fragments are employed.
本文报道了新型金属碱性但可分离的14价电子NHC配合物[M(iPrIm)]（M = Pd、Pt；iPrIm = 1,3 - 二异丙基咪唑啉 - 2 - 亚基；VE = 价电子；NHC = N - 杂环卡宾）的合成、表征及其反应活性研究，并与相应镍配合物的化学性质进行了比较。量子化学分析表明，第10族NHC配合物反应活性的差异是由刚性差异导致的，进而与反应过程中相应d - [M(NHC)]片段弯曲时的活化应变有关。这些结果对于理解使用此类配合物片段的催化循环中的基本步骤具有重要意义。
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