Three chromium(III) 1,2,4-diazaphospholide complexes were prepared: 3,5-di- tert-butyl-1,2,4-diazaphospholide chromium(III) dichloride [( η2-3,5- tBu2dp)Cr(THF)2Cl2] ( 1), 3,5-di-phenyl-1,2,4-diazaphospholide chromium(III) dichloride [( η2-3,5-Ph2dp)Cr(THF)2Cl2] ( 2), and 2,6-bis( N-1,2,4-diazaphosphol-1-yl)pyridine chromium(III) trichloride {[2,6-bis( N-1,2,4-diazaphosphol-1-yl)pyridine]CrCl3} ( 3). X-ray diffraction analysis has shown that these six-coordinate complexes each have a pseudo-octahedral configuration. Electron paramagnetic resonance (EPR) spectroscopy data for complex 1 for the paramagnetic S = 3/2 system ( d3 electron configuration) confirm a Cr(III) center in the octahedral coordination environment. The magnetic susceptibility of complex 1 followed the Curie-Weiss law well between 25 and 300 K. The magnetic moment of 1 was found to be close to the spin-only magnetic moment expected for three unpaired electrons (3.87 μB). [ABSTRACT FROM AUTHOR]