CO2 conversion to isocyanate via multiple N-Si bond cleavage at a bulky uranium(III) complex

Abstract

The reaction of the sterically saturated uranium(iii) tetrasilylamido complex [K(18c6)][U(N(SiMe3)2)4] with CO2 leads to CO2 insertion into the U-N bond affording the stable U(iv) isocyanate complex [K(18c6)][U(N(SiMe3)2)3(NCO)2]n that was crystallographically characterized. DFT studies indicate that the reaction involves the [2+2] cyclo-addition of a double bond of OCO to the U-N(SiMe3)2 bond and proceeds to the final product through multiple silyl migration steps.