Magnesium(I) Dimers Bearing Tripodal Diimine-Enolate Ligands: Proficient Reagents for the Controlled Reductive Activation of CO2 and SO2.

The first examples of magnesium(I) dimers bearing tripodal ligands, [(Mg{κ(3) -N,N',O-(ArNCMe)2 (OCCPh2 )CH})2 ] [Ar=2,6-iPr2 C6 H3 (Dip) 7, 2,6-Et2 C6 H3 (Dep) 8, or mesityl (Mes) 9] have been prepared by post-synthetic modification of the β-diketiminato ligands of previously reported magnesium(I) systems, using diphenylketene, OCCPh2 . In contrast, related reactions between β-diketiminato magnesium(I) dimers and the isoelectronic ketenimine, MesNCCPh2 , resulted in reductive insertion of the substrate into the MgMg bond of the magnesium(I) reactant, and formation of [{(Nacnac)Mg}2 {μ-κ(2) -N,C-(Mes)NCCPh2 }] (Nacnac=[(ArNCMe)2 CH](-) ; Ar=Dep 10 or Mes 11). Reactions of the four-coordinate magnesium(I) dimer 8 with excess CO2 are readily controlled, and cleanly give carbonate [(LMg)2 (μ-κ(2) :κ(2) -CO3 )] 12 (L=[κ(3) -N,N',O-(DepNCMe)2 (OCCPh2 )CH](-) ; thermodynamic product), or oxalate [(LMg)2 (μ-κ(2) :κ(2) -C2 O4 )] 13 (kinetic product), depending on the reaction temperature. Compound 12 and CO are formed by reductive disproportionation of CO2 , whereas 13 results from reductive coupling of two molecules of the gas. Treatment of 8 with an excess of N2 O cleanly gives the μ-oxo complex [(LMg)2 (μ-O)] 14, which reacts facilely with CO2 to give 12. This result presents the possibility that 14 is an intermediate in the formation of 12 from the reaction of 8 and CO2 . In contrast to its reactions with CO2 , 8 reacts with SO2 over a wide temperature range to give only one product; the first example of a magnesium dithionite complex, [(LMg)2 (μ-κ(2) :κ(2) -S2 O4 )] 16, which is formed by reductive coupling of two molecules of SO2 , and is closely related to f-block metal dithionite complexes derived from similar SO2 reductive coupling processes. On the whole, this study strengthens previously proposed analogies between the reactivities of magnesium(I) systems and low-valent f-block metal complexes, especially with respect to small molecule activations.