Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory.
Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory.
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DOI：
10.1002/chem.201504792
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发表时间：
2016-03
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影响因子：
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通讯作者：
Adrien T. Normand;C. Daniliuc;B. Wibbeling;G. Kehr;Pierre Le Gendre;G. Erker
中科院分区：
文献类型：
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作者：
Adrien T. Normand;C. Daniliuc;B. Wibbeling;G. Kehr;Pierre Le Gendre;G. Erker
中性磷杂茂络合物 [Cp2Zr(PR2)Me]（Cp=环戊二烯基；1a：R=环己基 (Cy)；1b：R=异三叉基 (Mes)；1c：R=tBu）通过不可烯醇化的羰基结构单元 (O=CR'R'')（例如二苯甲酮、醛类、多聚甲醛或CO2，得到[Cp2Zr(OCR'R''PR2)Me] (3-7)。根据 P 周围的空间体积，配合物 3-7 与 B(C6F5)3 反应生成 O 桥接的阳离子锆茂二聚体，该二聚体表现出典型的受挫路易斯对 (FLP)/两亲配体行为。因此，{[Cp2Zr(μ-OCHPhPCy2)][MeB(C6F5)3]}2 (10a) 与查尔酮的反应导致 Zr(+)/P FLP 的 1,4 加成，而 {[Cp2Zr(μ-OCHFcPCy2)][MeB(C6F5)3]}2 (11a; Fc=(C5H4)CpFe) 的反应与[Pd(η(3)C3H5)Cl]2 反应生成独特的Zr-Fe-Pd 三金属配合物13a，并通过XRD 分析对其进行了表征。
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.