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Douglas W. Agnew Curtis E. Moore Arnold L. Rheingold Joshua S. Figueroa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(43):12864-12868
The 17e− monoradical [Mn(CO)5] is widely recognized as an unstable organometallic transient and is known to dimerize rapidly with the formation of a Mn Mn single bond. As a result of this instability, isolable analogues of [Mn(CO)5] have remained elusive. Herein, we show that two sterically encumbering isocyanide ligands can destabilize the Mn Mn bond leading to the formation of the isolable, manganese(0) monoradical [Mn(CO)3(CNArDipp2)2] (ArDipp2=2,6‐(2,6‐(iPr)2C6H3)2C6H3). The persistence of [Mn(CO)3(CNArDipp2)2] has allowed for new insights into nitrosoarene spin‐trapping studies of [Mn(CO)5]. 相似文献
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Amos J. Rosenthal Marc Devillard Karinne Miqueu Ghenwa Bouhadir Didier Bourissou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(32):9330-9334
The P‐coordinated boryl radical [Ph2P(naphthyl)BMes]. (Mes=mesityl) was prepared by (electro)chemical reduction of the corresponding borenium salt or bromoborane. Electron paramagnetic resonance (EPR) analysis in solution and DFT calculations indicate large spin density on boron (60–70 %) and strong P–B interactions (P→B σ donation and B→P negative hyperconjugation). The radical is persistent in solution and participates in a Gomberg‐type dimerization process. The associated quinoid‐type dimer has been characterized by single‐crystal X‐ray diffraction. 相似文献
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