A 2,2′-bipyridyl calcium complex: synthesis, structure and reactivity studies

Abstract

A 2,2′-bipyridyl calcium complex based on a tridentate ligand [CH₃C(N-2,6-ⁱPr₂C₆H₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂]Ca(bipy)(THF) (1) was prepared by the reduction of {[CH₃C(N-2,6-ⁱPr₂C₆H₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂]CaI(THF)}₂ with potassium graphite in the presence of 2,2′-bipyridine (bipy). Complex 1 is a good Ca(I)synthon, as shown by its reactivity with I₂, PhCH₂SSCH₂Ph, PhCH₂SeSeCH₂Ph and 9-fluorenone, yielding the calcium iodide complex [CH₃C(N-2,6-ⁱPr₂C₆H₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂]CaI(bipy) (2), calcium thiolate [CH₃C(N-2,6-ⁱPr₂C₆H₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂]Ca(SCH₂Ph)(bipy) (3), calcium selenolate [CH₃C(N-2,6-ⁱPr₂C₆H₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂]Ca(SeCH₂Ph)(bipy) (4), and calcium ketyl complex [CH₃C(N-2,6-ⁱPr₂C₆H₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂]Ca[O-(9-C₁₃H₈˙)](bipy)·2THF (5·2THF), respectively. In addition, reactions of complex 5 with CS₂, CH₂CHCH₂Br and PhCH₂Br give the corresponding dimeric bis(thiolate) complex {[S₂CC(CMe(NAr))C(Me)NCH₂CH₂NMe₂]Ca(DME)}₂ (6), dimeric calcium bromide complex {[(9-CH₂CHCH₂-C₁₃H₈-9)-O]CaBr(THF)(bipy)}₂ (7) and {[(9-C₆H₅CH₂-C₁₃H₈-9)-O]CaBr[O-(9-C₁₃H₈)](bipy)}₂ (8). These results demonstrated that the calcium ketyl complex 5 can also be employed as a single-electron transfer reagent. All the new compounds were characterized by various spectroscopic methods, and their solid-state structures were further confirmed by single-crystal X-ray diffraction analyses.