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Studies on transition metal nitrosyl chemistry Malito, John T.


The reactions of nitrosyl chloride with a variety of anionic and neutral metal carbonyl and η⁵-cyclopentadienylmetal carbonyl compounds of Cr, Mo, W, Mn, Re, Fe and Co are described. In most cases nitrosyl-containing complexes are formed in reasonable yields. The advantages and limitations of nitrosyl chloride as a general synthetic reagent for the preparation of transition metal nitrosyl complexes are discussed. The high yield syntheses of CpM(CO)₂(NO) (M = Cr, Mo or W) from Na[CpM(CO)₃] and Diazald are detailed. Subsequent reaction of the dicarbonylnitrosyl species with nitrosyl chloride affords the corresponding CpM(NO)₂Cl complexes in excellent yields. The CpM(NO)₂R (M = Cr or Mo; R = Me, Et, i-Bu or Ph: M = W; R = Me or Ph) complexes are obtained in the reactions of CpM(NO)₂Cl with alkyl- or arylaluminum reagents. Some further derivatives of the CpM(NO)₂Cl complexes and the high yield preparation of [CpCr(NO)₂]₂ are also described. Previously unreported compounds are characterized by infrared and nuclear magnetic resonance spectroscopy and by mass spectrometry.

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