PH-funktionelle Zirkonocen-Phosphido-komplexe—synthese und molekülstruktur von cis-[Cp′ 2Zr(μ-PHR)] 2 (Cp′  C 5H 4Me, R  C 4H 9 ( tBu), C 10H 15 (Ad))

Abstract

The phosphido-bridged dinuclear zirconocene(III) complexes cis-[Cp′ 2Zr(μ-PHR)] 2 (Cp′ 2  C 5H 4Me, R  tBu ( 1), Ad ( 2)) are isolated from the reaction of Cp′ 2ZrCl 2 with solvent-free LiPHR (R  C 4H 9( tBu), C 10H 15 (Ad)). It can be shown by 31P NMR spectroscopy that the complexes Cp′ 2Zr(PHR) 2 and ▪ are also formed, as well as the oxidation products of LiPHR, meso- and d,l-P 2H 2R 2. 1 and 2 were characterized spectroscopically (NMR, IR, MS) and by X-ray structure determination. Only one isomer ( cis) is present in the solid state and in solution. The ZrP bond lengths range from 2.6161(8) Å to 2.6452(8) Å in 1, and from 2.6512(10) Å to 2.6714(12) Å in 2. The central Zr 2P 2 ring of 1 and 2 is slightly puckered (dihedral angle: 15.32° ( 1), 17.42° ( 2)). The long Zr3·Zr distance of 3.76 Å ( 1) and 3.81 Å ( 2) indicates the absence of Zrinteraction.