Deprotonation of the nitrogen atoms of the two pyrrole rings of 1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyllbenzene with KH followed by further reaction with either VCl3(THF)3 or with VCl2(TMEDA)2 respectively gave the paramagnetic complexes [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyllbenzene]VCI(DME) (1) and [1,3-bis-([(1'-pyrrol-2-yl)-1,1'dimethyl]methyllbenzene]V(THF)(3) (2). Further reduction with the appropriate amount of KH afforded diamagnetic dinuclear [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl)benzene]V}(2)](3). In complex 3, the bridging interaction between the two metal centers is realized via the ligand central benzene ring. Density functional theory calculations have elucidated the nature of the electronic interaction between the two metals with the bridging, pi-system thus accounting for its visible structural distortion. Calculations also pointed out the presence of only a weak V-V bond in spite of the short V-V distance.