P—Η-funktionelle Zirkonocen-Phosphido-Komplexe und Struktur eines Diazoalkan-Insertionsprodukts / P—H Functionalized Zirconocene Phosphido Complexes and the Crystal Structure of a Diazoalkane Insertion Product

Abstract

The reaction of Cp2ZrCl2 with [Li(THF)2PHMes]n(1) Mes = 2,4,6-Me3–C6H2) at –78°C yields Cp2Zr(PHMes)(X), with X = Cl (2) (1:1 reaction), X = PHMes (3) (1:2 reaction). Although 2 and 3 could not be obtained in a pure state, NMR spectroscopic investigations confirm the proposed formulae. 2 reacts with diphenyldiazomethane at ambient temperature with insertion of the N2CPh2 molecule into the Zr–P bond and formation of [xxx] (4). An X-ray structure determination of 4 shows the η2-bonding mode of the phosphinohydrazonido(1–) ligand to the Zr atom (Zr–N(1) 2.181(6) A; Zr–N(2) 2.205(6) A). Crystal data: space group P21/n, Z = 4, (2581 observed independent reflexions, R = 0.063). Cell dimensions (19°C): a = 11.820(2), b = 18.361(2), c = 13.758(2) Å, β = 103.86(2)°.