Reductive cyclotrimerization of CO and isonitriles with a highly reactive Ca ^I synthon

Whereas the small molecule activation with β-diketiminate (BDI)Mg^I complexes of type (BDI)Mg-Mg(BDI) is extensively investigated, lack of similar Ca^I reagents prevents studies on Ca^I reactivity. Herein, we report on small molecule activation with dinitrogen complexes of type (BDI)Ca(N₂)Ca(BDI) which acts as Ca^I synthon by release of N₂ and two electrons. Reaction of [(BDI*)Ca(THP)]₂(N₂) with CO led to formation of a deltate product with the cyclic C₃O₃ ^2- dianion (1); BDI* = HC[C(Me)N(DIPeP)]₂ (DIPeP = 2,6-(Et₂CH)-phenyl) and THP = tetrahydropyran. Reaction with the isonitrile CyN[triple bond, length as m-dash]C gave as the major product a complex with the triimino deltate C₃(NCy)₃ ^2- dianion (2) which is unstable in solution. Isolation of the side-product (BDI*)₂Ca·(CN-Cy) (3) indicates dynamic ligand exchange and Schlenk equilibria. Variation of the isonitrile reagent led to isolation of (BDI*)₂Ca·(CN-R) (4: R = xylyl, 5: R = <i>t</i>Bu). Crystal structures and NMR studies in solution are discussed for complexes 1-5. We also report an extensive DFT study on the reductive trimerization of MeN[triple bond, length as m-dash]C with this Ca^I synthon. The key intermediate (BDI)Ca(MeNC)Ca(BDI) contains dianionic MeNC^2-. Contrary to expectation, C-C coupling does not proceed by nucleophilic attack at a second MeNC reagent. Electron transfer results in two bridging MeNC˙^- radical anions. This rare singlet diradicaloid reacts further by radical coupling to [MeNC-CNMe]^2-. Differences with Mg^I reactivity are discussed.