Phosphanylphosphido and phosphanylphosphinidene complexes of zirconium(IV) supported by bidentate N,N ligands

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• 作者：Mateusz Zauliczny ; Rafał Grubba ; ^{grubba@pg.gda.pl} ; Łukasz Ponikiewski ; Jerzy Pikies
• 关键词：Coordination chemistry ; Zirconium complexes ; P-donor ligands ; Phosphido ligands ; Phosphinidene ligands
• 刊名：Polyhedron
• 出版年：2017
• 出版时间：17 February 2017
• 年：2017
• 卷：123
• 期：Complete
• 页码：353-360
• 全文大小：1204 K
• 卷排序：123

文摘

Phosphanylphosphido complexes of zirconium, [NacNacZrCl2(η2-R2P–PSiMe3)] (R = t-Bu, i-Pr), were synthesized in the reaction of R2P–P(SiMe3)Li·nTHF (R = t-Bu, i-Pr) with a β-diketiminate complex, [NacNacZrCl3], in toluene. Elimination of Me3SiCl from [NacNacZrCl2(η2-R2P–PSiMe3)] provided the phosphanylphosphinidene complexes [NacNacZrCl(η2-R2P–P)] (R = t-Bu, i-Pr). Moreover, the reaction of [NacNacZrCl2(η2-R2P–PSiMe3)] with R2P–P(SiMe3)Li·nTHF yielded the phosphanylphosphinidenoid complexes [NacNacZrCl2(η2-R2P–PLi)] (R = t-Bu, i-Pr). The same reaction, but in the presence of 12-crown-4, gave rise to the phosphanylphosphinidene complexes [NacNacZrCl(η2-R2P–P)]. The X-ray structures of [NacNacZrCl2(η2-i-Pr2P–PSiMe3)] and [NacNacZrCl(η2-t-Bu2P–P)] revealed that the R2P-P ligands exhibit side-on coordination to the metal center. From the reaction of i-Pr2P–P(SiMe3)Li·3THF with [{PhN(CH2)3NPh)}ZrCl2], a triple-core, anionic, phosphanylphosphinidene complex, [{PhN(CH2)3NPh)}Zr3Cl2(μ2-Cl)(μ2-i-Pr2P–P)2(μ3-i-Pr2P–P)2]−[Li(DME)3]+, was obtained in which the i-Pr2P–P ligands exhibit bridging coordination.