π-Indenyl substituted zirconium compounds containing terminal bonded phosphanylphosphido ligands [Ind2Zr(Cl){(Me3Si)P–PR2-κP1}]. Synthesis, X-ray analysis and NMR studies

Dichloro-bis(indenyl)zirconium(IV) reacts with lithium derivatives of diphosphanes R2P–P(SiMe3)Li (R = tBu, Et2N, iPr2N) to form complexes with terminal phosphanylphosphido ligands – [Ind2Zr(Cl)-{(PSiMe3)P-PR2-κP1}]. These compounds are extremely sensitive towards moisture and oxygen. The solid state structures of these complexes were established by single crystal X-ray diffraction. The nitrogen bearing groups R (Et2N or iPr2N) significantly lengthen the P–P distances in the related complexes and change the geometry around the phosphido phosphorus in such a way that it becomes less planar.

Graphical abstractThe synthesis of the first bisindenyl substituted zirconium complexes with terminal phosphanylphosphido ligands.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The synthesis of phosphanylophosphido complexes. ► NMR and X-ray studies of phosphanylphosphido complexes of Zr(IV). ► Reactivity of [Ind2ZrCl2] towards lithium derivatives of diphosphanes.