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Carbene Formation and Transfer at a Dinickel Active Site
Organometallics ( IF 2.8 ) Pub Date : 2018-06-22 , DOI: 10.1021/acs.organomet.8b00261 Arnab K Maity 1 , Mathias Zeller 1 , Christopher Uyeda 1
Organometallics ( IF 2.8 ) Pub Date : 2018-06-22 , DOI: 10.1021/acs.organomet.8b00261 Arnab K Maity 1 , Mathias Zeller 1 , Christopher Uyeda 1
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The synthesis and reactivity of a dinickel bridging carbene is described. The previously reported [i-PrNDI]Ni2(C6H6) complex (NDI = naphthyridine–diimine) reacts with Ph2CN2 to generate a metastable diazoalkane adduct, which eliminates N2 at 60 °C to yield a paramagnetic Ni2(μ-CPh2) complex. The Ni2(μ-CPh2) complex undergoes carbene transfer to t-BuNC via an initial isonitrile adduct, which upon heating releases free t-BuNCCPh2. On the basis of this sequence of stoichiometric reactions, a catalytic carbene transfer reaction is demonstrated.
中文翻译:
Dinickel 活性位点的卡宾形成和转移
描述了二镍桥联卡宾的合成和反应性。先前报道的[ i- Pr NDI]Ni 2 (C 6 H 6 )络合物(NDI =萘啶-二亚胺)与Ph 2 CN 2反应生成亚稳态重氮烷加合物,该加合物在60°C消除N 2产生顺磁Ni 2 (μ-CPh 2 )络合物。Ni 2 (μ-CPh 2 )络合物通过初始异腈加合物发生卡宾转移至t -BuNC,加热后释放出游离的t -BuNCCPh 2。在这一系列化学计量反应的基础上,证明了催化卡宾转移反应。
更新日期:2018-06-22
中文翻译:
Dinickel 活性位点的卡宾形成和转移
描述了二镍桥联卡宾的合成和反应性。先前报道的[ i- Pr NDI]Ni 2 (C 6 H 6 )络合物(NDI =萘啶-二亚胺)与Ph 2 CN 2反应生成亚稳态重氮烷加合物,该加合物在60°C消除N 2产生顺磁Ni 2 (μ-CPh 2 )络合物。Ni 2 (μ-CPh 2 )络合物通过初始异腈加合物发生卡宾转移至t -BuNC,加热后释放出游离的t -BuNCCPh 2。在这一系列化学计量反应的基础上,证明了催化卡宾转移反应。