Reactivity of the hydride [coH{P(OEt)2Ph}4] with RN2+ (R = aryl), NO+, and H+ cations: Preparation and properties of new cobalt complexes. Measurements of T1 for [coH{P(OEt)2Ph}4] and [coH2{P(OEt)2Ph}4]BPh4

The reaction of [CoH{P(OEt)2Ph}4] with RN2+ (R = 4-CH3C6H4) affords the paramagnetic cationic hydride [CoH{P(OEt)2Ph}4]+, with NO+ the dinitrosyl cation [Co(NO)2{P(OEt)2Ph}2]+, and with HBF4·Et2O the cationic dihydride [CoH2{P(OEt)2Ph}4]+. Characterization of the complexes by i.r., e.s.r., and variable-temperature 1H and 31P-{1H} n.m.r. spectra is described. Variable-temperature 1H n.m.r. T1 measurements at 80, 200, and 400 MHz for both [CoH{P(OEt)2Ph}4] and [CoH2{P(OEt)2Ph}4]BPh4 are also reported. The reactivity of the cationic hydrides with CO, RNC, NO, I2, and RN2+ was investigated and the new cations [Co(CNR)2{P(OEt)2Ph}3]+ (R = 4-CH3C6H4, 4-CH3OC6H4, or 4-ClC6H4) and [CoH(I){P(OEt)2Ph}4]+ synthesized. The unstable intermediate [CoH(NO){P(OEt)2Ph}4]+ [ν(NO) at 1 680 cm-1] was also detected.