CHEMICAL AND X-RAY STRUCTURAL STUDIES ON THE (ACETATO)PENTACARBONYLMETALATES AND (TRIFLUOROACETATO)PENTACARBONYLMETALATES OF CHROMIUM AND MOLYBDENUM
Academic Article
Overview
Identity
Additional Document Info
Other
View All
Overview
abstract
The reaction of [PNP] [Mo(CO)sCl], PNP = [Ph3PNPPh3]+, with Ag02CCH3 and Ag02CCF3 in dichloromethane readily affords the complexes [PNP] [Mo(CO)5(02CCH3)] (1) and [PNP] [Mo(CO)5(02CCF3)] (2a) in good yield. The trifluoroacetate derivative of chromium (2b) is conveniently prepared in a similar manner. All three compounds crystallize in the triclinic space group P7 with cell dimensions a = 10.563 (1), b = 12.154 (2), c = 17.047 (2), a = 104.01 (1), = 106.86 (1), and = 91.79 (1) for 1, a = 10.766 (2), b = 12.210 (1) A, c = 17.115 (2), a = 104.10 (1), = 106.59 (1), and y = 92.77 (1) for 2a, and a = 10.715 (2) A, b = 12.141 (2) A, c = 17.070 (2) A, a = 104.21 (1), = 106.57 (1), and y = 92.56 (2) for 2b. The structure of i was refined to values of R1 = 0.069 and R2 = 0.083 for 54 atoms (18 anisotropic) and 2860 reflections with I > 3 (I), while 2b was refined to values of = 0.073 and R2 = 0.089 for 57 atoms (21 anisotropic) and 3470 reflections with I > 3 (I). The structure of 2a converged with Rl = 0.050 and R2 = 0.070 for 5338 reflections with I > 3(I) and 57 anisotropic atoms. The most significant structural aspects are essentially equivalent (M)O-C and C=0 bond lengths and short trans M-C(O) bond distances. Ligand substitutional processes involving displacement of either the acetate or carbonyl ligands in [PNP] [Mo(CO)5(02CCH3)] are very facile, thus making them interesting and useful for preparing other compounds. 1981, American Chemical Society. All rights reserved.
