The rotational orientation of cyclopentadienyl rings usually has no effect on d-orbital energy levels and splitting in transition metal complexes. With related but less symmetrical carbocyclic ligands, however, the magnetic properties of the associated complexes can be altered by the alignment of the ligands. Examples of this effect are found in substituted organochromium(II) bis(indenyl) complexes. The monosubstituted compounds (1-RC9H6)(2)Cr (R = t-Bu, SiMe3) are prepared from the substituted lithium indenides and CrCl2 in THF; they are high-spin species with four unpaired electrons. Their spin state likely reflects that in the unknown monomeric (C9H7)(2)Cr, which is calculated to have a high-spin (S = 2) ground state in the staggered configuration (180 rotation angle). However, the analogous bis(indenyl) complexes containing t-Bu or SiMe3 groups in both the 1 and 3 positions on the indenyl ligands ((1,3-R2C9H5)(2)Cr) are low-spin compounds with two unpaired electrons. X-ray diffraction results indicate that [1-(t-Bu)C9H6](2)Cr exists in a staggered conformation, with Cr-C (av) = 2.32(4) Angstrom. In contrast, the average Cr-C distances in [1,3-(t-Bu or SiMe3)(2)C9H5](2)Cr are 2.22(2) and 2.20(2) Angstrom, respectively, and the rings are in a gauche configuration, with rotation angles of 87degrees. The indenyl conformations are sterically imposed by the bulk of the t-Bu and SiMe3 substituents. The change from a staggered to a gauche indenyl orientation lowers the symmetry of a (C9H7)(2)M complex and allows greater mixing of metal and ligand orbitals. Calculations indicate that previously nonbonding pi orbitals of the indenyl anion are able to interact with the chromium d orbitals, producing bonding and antibonding combinations. The latter remain unpopulated, and the resulting increase in the HOMO-LUMO gap forces the complexes to adopt a low-spin configuration. The possibility of using sterically imposed ligand rotation as a means of spin-state manipulation makes indenyl compounds a potentially rich source of magnetically adjustable molecules.