Treatment of CrCl2(THF)(2) with (NaOSiBu3)-Bu-t afforded the tetrameric '' box '' [Cr(u-Cl)(u-(OSiBu3)-Bu-t)](4) (1, X-ray). THF cleaved 1 to provide trans-(silox)ClCr(THF)(2) (2), whereas degradation of 1 with 4-picoline caused disproportionation and the generation of trans-Cl2Cr(4-pic)(2) and trans-(silcox)(2)Cr(4-pic)(x) (n = 2, 3; 3, 3-4-pic). Chromous centers in 1 were antiferromagnetically coupled, and density functional calculations on the high-spin (multiplicity = 17) model [Cr(mu-Cl)(mu-OH)](4) (1') revealed that its singly occupied 3d orbitals spanned an energy range of similar to 2 eV. The addition of 8 equiv of Na(silox) to 1 yielded [((Bu3SiO)-Bu-t)Cr(u-(OSiBu3)-Bu-t)2](NaC6H6)-C-. (4, Y shaped, < OCrO(Na) = 91.28(7)degrees), and treatment of 4 with dibenzo-18-crown-6 produced [(Silox)(3)Cr][Na(dibenzo-18-crown-6)] (5, < OCrO = similar to 120 degrees, (120 + alpha)degrees, (120 - alpha)degrees). Calculations of [((Bu3SiO)-Bu-t)Cr(mu-(OSiBu3)-Bu-t)(2)]Na (4') and Cr(silox)(3)(-) (5') provided reasonable matches with the experimental geometries (X-ray). The trigonal chromic derivative (silox)(3)Cr (6) was synthesized from CrCl3(THF)(3) for structural and calculational comparisons to the chromous derivatives.