a Department of Chemistry, University of Missouri, Columbia MO 65211 USA.; b Universite de Toulouse, CNRS, INSA, UMR, UMR 5215, LPCNO 135 Avenue de Ranguiel, 31077 Toulouse France
Abstract:
The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(iii) complex, [(C5Me5)2U(O-2,6-tBu2-4-MeC6H2)], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C5Me5)2(MesO)U (THF)], Mes = 2,4,6-Me3C6H2, reaction with CO forms the bridging ethynediolate species, [{(C5Me5)2(MesO)U}2(μ2-OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C5Me5)2(MesO)U}2(μ2:κ2:η1-C3O3)], which can be further reacted with CO2 to yield a ketene dicarboxylate complex, [{(C5Me5)2(MesO)U}2(μ2:κ2:κ2-C4O5)]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C5Me5)2U}2(OC(CPh2)C(O)CO)] with concomitant formation of [(C5Me5)2U(OMes)2]. Surprisingly, reaction with SO2 shows rare S–O bond cleavage to yield the unusual [(O2CC(O)(SO)]2− bridging ligand between two U(iv) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO2.Functionalization of CO from C1 to C4 is acheived using a heteroleptic uranium(iii) complex.
