Carborane Substituents Promote Direct Electrophilic Insertion over Reduction-Metalation Reactions.
Carborane Substituents Promote Direct Electrophilic Insertion over Reduction-Metalation Reactions.
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DOI：
10.1002/anie.201600635
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发表时间：
2016-03
影响因子：
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通讯作者：
Wing Y. Man;D. Ellis;G. Rosair;A. J. Welch
中科院分区：
文献类型：
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作者：
Wing Y. Man;D. Ellis;G. Rosair;A. J. Welch
与[Ru(η-mes)Cl2]2反应得到[8-(1'-1',2'-closo- c2 B10 H11)-4-(η-mes)-4,1,8-closo- ruc2 B10 H11]。随后对该物质进行双电子还原，并与[Ru（η-芳烃）Cl2]2处理，通过直接亲电插入，在13顶点/12顶点前驱体中的碳硼烷取代基促进下，得到14顶点/12顶点物质[1-(η-mes)-9-(1'-1',2'- close -C2 B10 H11)-13-（η-芳烃）-1,13,2,9- close - ru2 C2 B10 H11]。当芳烃=间三甲苯（mes）时，二钌在室温下在溶液中流动，这一过程使金属配体片段等效。提出了这种流动性的独特机制，并证明与先前报道的一系列14顶点二巴甲碳硼烷的观察到的流动性或非流动性完全一致。
Two-electron reduction of 1,1'-bis(o-carborane) followed by reaction with [Ru(η-mes)Cl2 ]2 affords [8-(1'-1',2'-closo-C2 B10 H11 )-4-(η-mes)-4,1,8-closo-RuC2 B10 H11 ]. Subsequent two-electron reduction of this species and treatment with [Ru(η-arene)Cl2 ]2 results in the 14-vertex/12-vertex species [1-(η-mes)-9-(1'-1',2'-closo-C2 B10 H11 )-13-(η-arene)-1,13,2,9-closo-Ru2 C2 B10 H11 ] by direct electrophilic insertion, promoted by the carborane substituent in the 13-vertex/12-vertex precursor. When arene=mesitylene (mes), the diruthenium species is fluxional in solution at room temperature in a process that makes the metal-ligand fragments equivalent. A unique mechanism for this fluxionality is proposed and is shown to be fully consistent with the observed fluxionality or nonfluxionality of a series of previously reported 14-vertex dicobaltacarboranes.