Addition of BH 3 .thf to 1-alkylimidazoles (alkyl=methyl, butyl) and 1-methylbenzimidazole leads to BH 3 adducts, which are deprotonated by BuLi to yield the organolithium compounds (L)Li + (1b-d) - . In the solid state (thf)Li + 1b - is dimeric. The acyl-iron complexes (thf) 3 Li + (3b,d) - are formed from (thf)Li + (1b,d) - and Fe(CO) 5 . (L)Li + (1a-c) - react with [CpFe(CO) 2 X], however, the only complex obtained is [CpFe(CO) 2 1a] (5a). The analogous reaction of (L)Li + 1a - with the pentadienyl complex [(C 7 H 1 1 )Fe(CO) 2 Br] yields the corresponding iron compound 6a. Their compositions follow from spectroscopic data. Treatment of Cp 2 TiCl with (L)Li + 1a - leads to [Cp 2 Ti1a] (7a), which could not be oxidized with PbCl 2 to give the corresponding Ti(IV) complex. The compounds [Li(py) 4 ] + 9a - and [Li(L) 4 ] + (10b-d) - are obtained when (L)Li + 1 - are reacted with VCl 3 and ScCl 3 . The X-ray structure analysis of the vanadium complex reveals a distorted tetrahedron of the anion [V(1a) 4 ] - with two smaller and four larger C V C angles. The scandium compound [Li(dme) 2 + 10c - ] has a different structure: the distorted tetrahedron of the anion [Sc(1c) 4 ] - contains two larger (140.2 and 142.9 o ) and four smaller C Sc C angles (93.9-98.7 o ). This arrangement allows the formation of four bridging B H Sc 3c,2e bonds to give an eight-fold coordination. The anion 10c - is formally a 16e complex.