The low-temperature reaction of [CrCl 3 (thf) 3 ] with LiC 6 H 3 Cl 2 -2,6 yields the organochromium(III) compound [Li(thf) 4 ][Cr III (C 6 H 3 Cl 2 -2,6) 4 ] (1) in 48% yield. The homoleptic, anionic species [Cr III (C 6 H 3 Cl 2 -2,6) 4 ] − is electrochemically related to the neutral one [Cr IV (C 6 H 3 Cl 2 -2,6) 4 ] (2) through a reversible one-electron exchange process (E 1/2 =0.16V, ΔE p =0.09V, i pa /i pc =1.18). Compound 2 was isolated in 74% yield by chemical oxidation of 1 with [N(C 6 H 4 Br-4) 3 ][SbCl 6 ]. Attempts to prepare the salt [NBu 4 ][Cr III (C 6 Cl 5 ) 4 ] (4) by direct arylation of [CrCl 3 (thf) 3 ] with LiC 6 Cl 5 in the presence of [NBu 4 ]Br gave the organochromium(II) salt [NBu 4 ] 2 [Cr II (C 6 Cl 5 ) 4 ] (3) instead, as the result of a reduction process. The salt [NBu 4 ][Cr III (C 6 Cl 5 ) 4 ] (4) was cleanly prepared by comproportionation of 3 and [Cr IV (C 6 Cl 5 ) 4 ]. The reaction of [MoCl 4 (dme)] with LiC 6 Cl 5 in Et 2 O solution proceeded with oxidation of the metal center to give the paramagnetic (S=1/2), five-coordinate salt [Li(thf) 4 ][Mo V O(C 6 Cl 5 ) 4 ] (5). The crystal and molecular structures of 1 and 2 have been established by X-ray diffraction methods. The magnetic properties of 1 and 4 (S=3/2) as well as those of 2 (S=1) have been established by EPR spectroscopy as well as by ac and dc magnetization measurements.