ORGANOMETALLIC NITROSYL CHEMISTRY .8. PREPARATION AND CHARACTERISTIC CHEMISTRY OF (ETA5-C5H5)W(NO)2H AND ITS GROUP 6B CONGENERS

The chloro compounds (η5-C5H5)M(NO)2Cl (M=Mo, W. o. Cr) react with Na[AlH2(OCH2CH2OCH3)2] in toluene to form either the new hydrido complexes (η5-C5H5)M(NO)2H (M=Mo or W) or the known [(η5-C5H5)Cr(NO)2]2 complex. The hydridomolybdenum complex slowly decomposes at ambient temperature, but the thermally stable tungsten analogue can be isolated and fully characterized. (η5-C5H5)W(NO)2H exhibits a VMH at 1900 cm-1 in its infrared spectrum and a low-field hydride resonance at δ 2.27 in its 1H NMR spectrum. Its characteristic chemistry is dominated by its tendency to function as a source of H-. Hence, (η5-C5H5)W(NO)2H is inert to CHCl3, CCl4, and (C2H5)3N, but it reacts readily with anhydrous p-toluenesulfonic acid and trityl tetrafluoroborate (in CH3CN) to yield (η5-C5H5)W(NO)2OSO2C6H4CH3 and [(η5-C5H5)W(NO)2(CH3CN)]BF4, respectively. However, the hydridotungsten complex is not sufficiently hydridic to attack Fe(CO)5, and it reacts with acidic hydridocarbonyls such as HCo(CO)4 or (η5-C5H5)W(CO)3H to afford products resulting from the scrambling of CO and NO ligands rather than bimetallic carbonyl nitrosyls. © 1979, American Chemical Society. All rights reserved.