On Haptotropic Rearrangements of Diphosphene and Diarsene Ligands in Titanium Complexes

Abstract

Dipnictenes of the type RE=ER (E = P, As, Sb, Bi) are the isovalence electronic heavier analogs of alkenes. Although diphosphenes and dipnictenes in general show a variety of binding modes in metal complexes, little is known about haptotropic shift reactions involving these ligands. Herein, we report an unprecedented η2 to η1 rearrangement of the dipnictene ligands in titanocene complexes of the type Cp2Ti(Pn2Ar2) (Pn = P, As; Ar = 2,4,6‐Me3‐C6H2, Mes; 2,6‐iPr2‐C6H3, Dip; 2,4,6‐iPr3‐C6H2, Tip), initiated by Lewis basic ligands (L = MeCN, PMe3, AdNC, CO). In the presence of L the dipnictene ligand changes its hapticity from η2 to η1 and complexes of the general form Cp2Ti(L)(Pn2Ar2) with a succinctly different electronic structure are obtained. Electronically, the new complexes are best described as biradicaloids with antiferromagnetically coupled (via a π‐bond) [Cp2TiIII]•+ and [Pn2Ar2]•− fragments. However, the biradical character of these systems is affected by the electronic features of the co‐ligand and significantly decreases moving from PMe3/MeCN (σ‐donors) to CNAd/CO (σ‐donors/π‐acceptors).