Synthesis, structural, characterization and Hirshfeld analysis of a bisselenide and a zinc complex of a new hemilabile ferrocenylbisphosphane, [Fe{C5H4P(C6H4CH2NMe2-o)2}2]

Abstract

The novel hemilabile ferrocenylbisphosphane 1,1'-bis(bis{2-[(dimethylamino)methyl]phenyl}phosphanyl)ferrocene, [Fe{C₅H₄P(C₆H₄CH₂NMe₂-o)₂}₂] (1), was synthesized by reacting bis(dichlorophosphanyl)ferrocene, [Fe{C₅H₄(PCl₂)}₂] with LiC₆H₄CH₂NMe₂-o. Treatment of 1 with gray selenium and anhydrous ZnCl₂ yielded, respectively, the bisselenide (ferrocene-1,1'-diyl)bis(bis{2-[(dimethylamino)methyl]phenyl}phosphine selenide), [Fe(C₂₃H₂₈N₂PSe)₂] (2), and the dizinc complex [μ-1,1'-bis(bis{2-[(dimethylamino)methyl]phenyl}phosphanyl)ferrocene-κ²N,P:κ²N',P']bis[dichloridozinc(II)] dichloromethane monosolvate, [FeZn₂Cl₄(C₂₃H₂₈N₂P)₂]·CH₂Cl₂ (3), and both have been structurally characterized. Both compounds crystallized with the asymmetric unit containing half a molecule and with the Fe atom on an inversion centre. A Hirshfeld surface analysis indicated that the most significant contributions to the crystal packing of 2 are from H...H (76.7%), C...H/H...C (13.2%) and Se...H/H...Se (7.1%) contacts, while those for 3 are from H...H (62.3%), Cl...H/H...Cl (24.4%) and C...H/H...C (10.9%) contacts.

Keywords: bisselenide; chelation; crystal structure; ferrocenylbisphosphane; hemilabile; zinc(II).