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Anionic N-heterocyclic carbenes with weakly coordinating borate, aluminate, and gallate moieties of the type [(F5C6)3E-NHC]- (E = B, Al, Ga) were isolated as lithium salts by the lithiation of 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes) or 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (IDipp) followed by the addition of E(C6F5)3 (E = B, Al, Ga). Treatment with elemental selenium afforded the lithium salts of the corresponding anionic selenourea derivatives [(F5C6)3E-NHCSe]- (NHC = IMes, E = B; NHC = IDipp, E = B, Al,