Azaallyl-derived ring formation via redox coupling in first row transition metals

The reductive coupling of a chelated diimine ligand, Me2C(CH=NCH2(2-py))(2) (dmp(PM)(2)), by (TMEDA) TiCl2 afforded a Ti(IV) species containing a cyclopropane ring, (Me2Pr)-Pr-c(cis-2,3-NCH2(2-PY))(2)TiCl2 (1). Dimeric [(Me2C(CH2N=CH(2-py)(CH2(mu-N)CH2(2-Py))Mg](2) (3) was generated in the magnesium reduction of Me2C(CH2N=CH(2-py))(2) (dmp(PI)(2)) as its reduction incurred HAT. A di-azaallyl precursor was used to generate 7-membered ring chelates [{DBM(PI-)(PI2-)Cr-III](2) (4) and [{DBM(PI)(PI')}Fe](2) (5). Structural studies of 1, 3 and 4 are included, as are electronic assessments of the reductive coupling to afford 1, and the paramagnetism of 3. (C) 2018 Elsevier Ltd. All rights reserved.