Alkaline-Earth Metal Mediated Benzene-to-Biphenyl Coupling.

Abstract

Complex [(DIPeP BDI)Ca]2 (C6 H6 ), with a C6 H6 2- dianion bridging two Ca2+ ions, reacts with benzene to yield [(DIPeP BDI)Ca]2 (biphenyl) with a bridging biphenyl2- dianion (DIPeP BDI=HC[C(Me)N-DIPeP]2 ; DIPeP=2,6-CH(Et)2 -phenyl). The biphenyl complex was also prepared by reacting [(DIPeP BDI)Ca]2 (C6 H6 ) with biphenyl or by reduction of [(DIPeP BDI)CaI]2 with KC8 in presence of biphenyl. Benzene-benzene coupling was also observed when the deep purple product of ball-milling [(DIPP BDI)CaI(THF)]2 with K/KI was extracted with benzene (DIPP=2,6-CH(Me)2 -phenyl) giving crystalline [(DIPP BDI)Ca(THF)]2 (biphenyl) (52 % yield). Reduction of [(DIPeP BDI)SrI]2 with KC8 gave highly labile [(DIPeP BDI)Sr]2 (C6 H6 ) as a black powder (61 % yield) which reacts rapidly and selectively with benzene to [(DIPeP BDI)Sr]2 (biphenyl). DFT calculations show that the most likely route for biphenyl formation is a pathway in which the C6 H6 2- dianion attacks neutral benzene. This is facilitated by metal-benzene coordination.