Iron carbonyl derivatives field

A novel field was opened by Albine and Kisch and by Volpin and co-workersby allowing diazirines to react with metal carbonyls. 3,3-Dimethyl and 3,3-pentamethylenediazirine react with FejlCOjg to form the iron tetracarbonyl derivatives 160 and 161. In acid solution 161 is slowly converted into 162 and 163. 

Synthesis o-f transition metal derivative s. In view o-f the -final goal o-f this survey, that is the catalytic deoxygenation o-f nitro compounds by carbon monoxyde, o-f particular interest are the stoichiometric reactions o-f these compounds with metal carbonyls. Carbonyl ligands coordinated to metal atoms in a high oxydation state should be more susceptible to attack by nucleophiles, than those bound to metal in a low oxydation state. However, the reactivity o-f nitro compounds has been studied in practice only with carbonyl complexes o-f metals in zero or less oxydation states. The -first report in this -field is concernded with the reactions o-f Fe(C0>5 with a series o-f aromatic nitro compounds] 56], leading to dimeric iron-nitroso derivatives[23j ... 

The formation of a nitroso complex from the reaction of an organic nitro compound and a metal carbonyl complex was the topic of the first report in this field. It has been reported that by reaction of Fe(CO)5 with a series of aromatic nitro compounds, dimeric iron-nitroso derivatives can be obtained (eq. 15) [50-52] ... 

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. 

The first mononuclear carbonyl compound of cobalt, iron or manganese known was the pentacarbonyl complex [Fe(CO)5] " with a trigonal-bipyramidal ligand field (see Fig. 2). Though related electroneutral species of cobalt and manganese are not known due to a strict observance of the 18-electron-rule in these cases, the monoanionic manganese derivative fMn(CO)5] has also been described as a trigonal-bipyramidal species. ... 

The 3c-nmR spectrum of the thermal reaction product between 1,7-octadiene and FeCCO) (Fig. M) is complex and consists of 24 principal peaks which can only be accounted for in terms of the formation of a minimum of the six isomeric octadienyl iron tricarbonyl compounds shown in Fig. 2. While we have not unequivocally assigned each of these peaks, the eleven peaks at high field (14-40 ppm) are due to -CH and -CH2 carbons. The six peaks at (53-66 ppm) are mainly derived from the 1,4 carbons of the diene and the six peaks at 81-93 Ppm may be attributed to the 2,3 carbons of the diene. The low field doublet at 212 and 213 ppm derives from the carbonyl carbons and is indicative of two distinct carbonyl environments. 

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