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Gas-phase core electron binding energies of organometallic nitrosyl complexes of chromium, molybdenum, and tungsten are reported. On going from Cr to W in the series CpM(NO)/sub 2/Cl (M = Cr, Mo, W), back-bonding to the NO groups increases and electron density is withdrawn from the Cl atoms. The data for CpM(NO)/sub 2/Cl and CpM(CO)/sub 2/NO (M = Cr, Mo, W) indicate that the back-bonding in the Mo and W compounds is significantly different from that in first-row transition-metal nitrosyls. Electron density is mainly transferred to the nitrosyl oxygen atom, whereas, in first-row nitrosyls, approximately equal amounts of electron density are transferred to the oxygen and nitrogen atoms.

X-ray photoelectron spectroscopic study of organometallic nitrosyl compounds of chromium, molybdenum, and tungsten