CHROMYL COMPLEXES WITH ARYLOXY AND SILOXY LIGANDS

Interaction of CrO3 and 1 equiv of Ph3CCl in dichloromethane yields a mixture of CrO2Cl2, CrO2Cl(OCPh3) (1), and CrO2-(OCPh3)2 (2). Fractional crystallization givespure samples of red 1 and orange 2, which have been characterized by X-ray diffraction. Crystal data for 1: space group [formula omitted]; a = 9.913 (3), b = 10.173 (3), c = 9.019 (3) Å; a = 92.93 (2), μ = 92.74 (2), γ = 110.84 (3)°; Z = 2; R1, = 0.044, R2 = 0.059. Crystal data for 2: space group C2/c; a = 23.857 (6), b = 8.759 (3), c = 15.105 (5) Å; μ = 110.48 (3)°; Z = 4; R1 = 0.036, R2 = 0.057. A similar result was obtained on reaction of CrO3 and 1 equiv of Ph3SiCl, giving CrO2Cl2, CrO2Cl(OSiPh3) (3), and CrO2(OSiPh3)2 (4). These results are compared with the in situ systems CrO3/Me3SiCl and CrO3/Me3SiOSiMe3, which have been studied by 1H NMR spectroscopy and EI mass spectrometry. © 1990, American Chemical Society. All rights reserved.