Iron carbonyl nitrosyl

Wang X, Zhou M, Andrews L (2000) Reactions of iron atoms with nitric oxide and carbon monoxide in excess argon infrared spectra and density functional calculations of iron carbonyl nitrosyl complexes. J Phys Chem A 104 10104-10111... 

I remember with great satisfaction my collaboration with J. S. Anderson in the Heidelberg Institute. In 1932 he made the volatile, previously unrecognized as such, dinitrosyldicarbonyliron by the action of pure nitric oxide on a solution of Fe3(CO)12 in iron pentacarbonyl (98). The complex Fe(CO)2(NO)2 was a deep red liquid at room temperature. With this compound the isoelectronic series Ni(CO)4, Co(CO)3NO, Fe(CO)2(NO)2 arose, and in this manner the field of carbonyl nitrosyls was opened up. The next member of this isoelectronic series, Mn(CO)(NO)3, predicted by us in 1932, was discovered recently (99). A study of the chemical behavior of the carbonyl nitrosyls, namely the ready substitution of the CO but not of the NO groups, was essentially established by Anderson (100), with the isolation of the derivatives Fe(NO)2py2, Fe(NO)2(o-phen), Co(NO)(CO)(o-phen), and Co(NO)(CO)(PR3)2, etc. 

Unstable metal nitrosyls are formed by Fe, Ru and Ni. Black Fe(NO)4, made by heating iron carbonyl with NO under pressure at 50°, is the most stable. The structure is unknown, but the ionic formula NO+[Fe(NO)3] has been suggested to explain its low volatility. Ruthenium tetranitrosyl, Ru(NO)4, is made as cubic, red crystals when NO is passed into Ru2(CO)g. A compound of empirical formula Ni(NO)2 is obtained as a blue powder when NO is passed into Ni(CO)4 dissolved in CHCI3. 

Iron Chemistry of NS3-Carbonyl, Nitrosyl and Isocyanide Complexes... 

Iron Carbonyl Derivatives.—The first binary metal nitrosyl cation, [Fe2(NO) ] +, stable only below - 20 °C, has been isolated as its [PF g] salt from the reaction of [Fe(CO)2(NO)2] with [NO][PFe]. It probably possesses a symmetrical structure with terminal NO ligands and an Fe=Fe double bond. ... 

Very interesting features emerge from the comparison of the carbonyl, dioxygen, and nitrosyl iron porphyrins in Series a, d, and e. (Note that for the tetraarylporphy-rins the 0-bands are given.)... 

With respect to the derivatives of metal carbonyls, the substituted metal carbonyls of the VIB Group (e.g., Mo(CO)apya), the halogenocar-bonyls of iron, ruthenium, iridium, and platinum, the hydridocarbonyls H2Fe(CO)4 and HCo(CO)4 discovered in 1931 and 1934, and the nitrosyl carbonyls FelCOj NOjg and Co(CO)3NO were the most important (/). The known anionic CO complexes were limited to [HFe(CO)J and [Co(CO)J-. For studies of substitution reactions of metal carbonyls at this time, work was almost totally limited to reactions involving the classical N ligands such as NH3, en, py, bipy, and phen. 

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