TY - JOUR
T1 - Mechanistic insights from theory on the reduction of CO2, N2O, and SO2 molecules using tripodal diimine-enolate substituted magnesium(i) dimers
AU - Kefalidis, Christos E.
AU - Jones, Cameron
AU - Maron, Laurent
PY - 2016
Y1 - 2016
N2 - The mechanistic investigation of the reductive coupling vs. reductive disproportionation of CO2 using magnesium(i) dimers bearing tripodal ligands, [{Mg[κ3-N,N′,O-(ArNCMe)2(OCCPh2)CH]}2] (Ar = C6H3Et2-2,6) has been carried out using DFT computational methods. We also elucidated the reduction of N2O 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 ([{(DipNacnac)Mg}2] (DipNacnac = [(DipNCMe)2CH]-, Dip = C6H3Pri 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.
AB - The mechanistic investigation of the reductive coupling vs. reductive disproportionation of CO2 using magnesium(i) dimers bearing tripodal ligands, [{Mg[κ3-N,N′,O-(ArNCMe)2(OCCPh2)CH]}2] (Ar = C6H3Et2-2,6) has been carried out using DFT computational methods. We also elucidated the reduction of N2O 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 ([{(DipNacnac)Mg}2] (DipNacnac = [(DipNCMe)2CH]-, Dip = C6H3Pri 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.
UR - http://www.scopus.com/inward/record.url?scp=84988648804&partnerID=8YFLogxK
UR - http://pubs.rsc.org.ezproxy.lib.monash.edu.au/en/content/articlepdf/2016/dt/c6dt02189a?page=search
U2 - 10.1039/c6dt02189a
DO - 10.1039/c6dt02189a
M3 - Article
AN - SCOPUS:84988648804
SN - 1477-9226
VL - 45
SP - 14789
EP - 14800
JO - Dalton Transactions
JF - Dalton Transactions
IS - 37
ER -