Hwang Seung Jun, Tanushi Akira, Radosevich Alexander T
Department of Chemistry, POSTECH, Pohang 37673, Republic of Korea.
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2020 Dec 23;142(51):21285-21291. doi: 10.1021/jacs.0c11161. Epub 2020 Dec 11.
Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(-N(Ar)CH), tethered by a phenylene linker to a -PPr anchor, with group 10 complexes LM(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of with (cod)Pt(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ-)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.
据报道，三配位磷配体可插入晚期金属 - 碳键中。一种由非三角磷（即P(III)）三酰胺部分P(N(-N(Ar)CH)组成的P^P螯合配体，通过亚苯基连接基连接到 -PPr锚定基团，与第10族配合物LM(Me)Cl（M = Ni，Pd）进行金属化反应，导致非三角磷位点插入金属 - 甲基键中。由此形成的稳定的甲基金属磷烷化合物通过光谱和晶体学进行了表征。用（环辛二烯）Pt(Me)(Cl)对 进行金属化反应不会生成金属磷烷，而是生成标准的双膦螯合物（κ-）Pt(Me)(Cl)。通过参考M - C键焓的周期性变化，解释了第10族内这些不同的反应活性。
