中性磷基锆茂配合物的插入反应：通往受阻路易斯酸碱对领域的便捷途径
Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory.
作者信息
Normand Adrien T, Daniliuc Constantin G, Wibbeling Birgit, Kehr Gerald, Le Gendre Pierre, Erker Gerhard
机构信息
Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
ICMUB, Université de Bourgogne Franche-comté, UFR Sciences et Techniques, 9 avenue Alain Savary - BP, 47870 21078, Dijon Cedex, France.
出版信息
Chemistry. 2016 Mar 14;22(12):4285-93. doi: 10.1002/chem.201504792. Epub 2016 Feb 11.
Neutral phosphidozirconocene complexes [Cp2Zr(PR2)Me] (Cp=cyclopentadienyl; 1a: R=cyclohexyl (Cy); 1b: R=mesityl (Mes); 1c: R=tBu) undergo insertion into the Zr-P bond by non-enolisable carbonyl building blocks (O=CR'R''), such as benzophenone, aldehydes, paraformaldehyde or CO2, to give [Cp2Zr(OCR'R''PR2)Me] (3-7). Depending on the steric bulk around P, complexes 3-7 react with B(C6F5)3 to give O-bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {[Cp2Zr(μ-OCHPhPCy2)][MeB(C6F5)3]}2 (10a) with chalcone results in 1,4 addition of the Zr(+)/P FLP, whereas the reaction of {[Cp2Zr(μ-OCHFcPCy2)][MeB(C6F5)3]}2 (11a; Fc=(C5H4)CpFe) with [Pd(η(3)C3H5)Cl]2 yields the unique Zr-Fe-Pd trimetallic complex 13a, which has been characterised by XRD analysis.
中性磷桥联二茂锆配合物[Cp2Zr(PR2)Me]（Cp = 环戊二烯基；1a：R = 环己基（Cy）；1b：R = 均三甲苯基（Mes）；1c：R = 叔丁基）可被不可烯醇化的羰基结构单元（O=CR'R''），如二苯甲酮、醛、多聚甲醛或CO2插入Zr-P键，生成[Cp2Zr(OCR'R''PR2)Me]（3 - 7）。根据磷周围的空间位阻，配合物3 - 7与B(C6F5)3反应生成O桥连的阳离子二茂锆二聚体，表现出典型的受阻路易斯对（FLP）/双亲性配体行为。因此，{[Cp2Zr(μ - OCHPhPCy2)][MeB(C6F5)3]}2（10a）与查耳酮反应导致Zr(+)/P FLP发生1,4加成，而{[Cp2Zr(μ - OCHFcPCy2)][MeB(C6F5)3]}2（11a；Fc = (C5H4)CpFe）与[Pd(η(3)C3H5)Cl]2反应生成独特的Zr - Fe - Pd三金属配合物13a，该配合物已通过XRD分析进行了表征。
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