Mechanistic insights from theory on the reduction of CO2, N2O, and SO2 molecules using tripodal diimine-enolate substituted magnesium(i) dimers. Issue 37 (12th August 2016)

• Record Type: Journal Article
• Authors: Kefalidis, Christos E.; Jones, Cameron; Maron, Laurent
• Is Part Of: Dalton transactions. Volume 45:Issue 37(2016)
• Page Start: 14789
• Page End: 14800
• Publication Date: 2016-08-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt02189a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The mechanistic investigation of the reductive coupling vs. reductive disproportionation of CO2 using magnesium(i ) dimers bearing tripodal ligands has been carried out using DFT computational methods. Abstract : The mechanistic investigation of the reductive coupling vs. reductive disproportionation of CO2 using magnesium(i ) dimers bearing tripodal ligands, [{Mg[κ 3 - N, N ′, O -(ArNCMe)2 (OCCPh2 )CH]}2 ] (Ar = C6 H3 Et2 -2, 6) has been carried out using DFT computational methods. We also elucidated the reduction of N2 O to form a μ-oxo magnesium complex which upon addition of CO2 affords the experimentally observed carbonate complex. Finally, the interesting reactivity towards SO2 is considered and some insights into the mechanistic aspects of such activation/homo-coupling reaction are given for both "Nacnac" substituted magnesium(i ) dimers ([{( Dip Nacnac)Mg}2 ] ( Dip Nacnac = [(DipNCMe)2 CH] −, Dip = C6 H3 Pr i 2 -2, 6)) and those bearing tripodal ligands. The analogy between the activation chemistry of low-valent f-block metal complexes with that of magnesium systems is highlighted.