101. Azaallyl-derived ring formation via redox coupling in first row transition metals.
- Author
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Hulley, Elliott B., Heins, Spencer P., Wolczanski, Peter T., Lancaster, Kyle M., and Lobkovsky, Emil B.
- Subjects
- *
TRANSITION metals , *RING formation (Chemistry) , *OXIDATION-reduction reaction , *REDUCTIVE coupling reactions (Chemistry) , *PARAMAGNETISM - Abstract
Graphical abstract The reductive coupling of a chelated diimine ligand, Me 2 C(CH NCH 2 (2-py)) 2 (dmp(PM) 2), by (TMEDA)TiCl 2 afforded a Ti(IV) cyclopropanated species, Me 2 cPr(cis -2,3-NCH 2 (2-py) 2 TiCl 2 (1), while di-azaallyl precursors were used to generate 7-membered ring chelates [{DBM(PI− )(PI2−)}CrIII] 2 (4) and [{DBM(PI)(PI′)}Fe] 2 (5). Abstract The reductive coupling of a chelated diimine ligand, Me 2 C(CH NCH 2 (2-py)) 2 (dmp(PM) 2), by (TMEDA)TiCl 2 afforded a Ti(IV) species containing a cyclopropane ring, Me 2 cPr(cis -2,3-NCH 2 (2-py)) 2 TiCl 2 (1). Dimeric [{Me 2 C(CH 2 N CH(2-py)(CH 2 (µ-N)CH 2 (2-py)}Mg] 2 (3) was generated in the magnesium reduction of Me 2 C(CH 2 N 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−)}CrIII] 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. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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