71895-18-6

Upstream product

• 63866-73-9 Fe(CO)4(CNC₆H₃(CH₃)2) 
• 119072-54-7 2,6-dimethylphenyl isonitrile 
• 75517-52-1 Fe(CO)(CNC₆H₃(CH₃)2)4 

Relevant academic research and scientific papers

SUPPORTED TRANSITION METALS AND METAL OXIDES AS CATALYSTS FOR THE METAL CARBONYL SUBSTITUTION REACTION

A range of supported transition metals and metal oxides have been investigated as catalysts for the metal carbonyl substitution reaction M-CO+L->M-L+CO (L=isocyanide (RNC), Group V donor ligand).The use of model substitution reactions reveals the metals Pd, Pt, Ru and Rh and the oxides PdO and PtO2 to be efficient catalysts for substitution reactions of mono-, di- and polynuclear metal carbonyl complexes, and, while there are observable effects which relate to the nature of the catalyst support, catalyst dispersion, catalyst activation and catalyst poisoning, the generally observed orders of activity are Pd>Pt>Ru>Rh and PdO>PtO2.The radical traps hydroquinone and galvinoxyl have an inhibiting effect on catalyst, while light has a mild promotional effect.These observations are consistent with a catalytic mechanism similar to that observed for 5-C5H5)Fe(CO)2>2>, namely a radical non-chain process.The metal and metal oxides display considerable potential for the synthesis of substituted metal carbonyl complexes including 5-n(CNR)n> (n=1-5), 6-n(CNR)n> (M=Cr, Mo, W; n=1-3), (M3(C)12-n(CNR)n> (M=Ru,(n=1-3; M=Os, n=1-4), and (L=Group V donor ligand).Certain catalyst supports (zeolites, activated carbon) have themselves been found to possess mild activity for the catalytic carbonyl substitution reaction.

Catalysed and Non-catalysed Reaction Between and Isonitriles

The reaction between and isonitrile, RNC, is catalysed by CoCl2*H2O and readily yields the complexes (n = 1-3, R = Me, C6H11, tBu, PhCH2, Ph, 2,6-Me2C6H3, or 2,4,6-Me3C6H2; n = 4, R = tBu; n = 4 or 5, R = Ph, 2,6-Me2C6H3, or 2,4,6-Me3C6H2).The high-yield synthesis of from and RNC in the absence of catalyst is also reported.Trimethylamine N-oxide has been used to synthesize from and RCN and results are compared with the CoCl2 catalysed reaction.All products were characterized by i.r. and n.m.r. spectroscopy.The higher substituted derivatives were further characterized by reaction with I2 and tetracyanoethylene (tcne) and gave (n = 2, R = tBu, PhCH2, or 2,6-Me2C6H3; n = 3, R = tBu or 2,6-Me2C6H3; n = 4, R = 2,6-Me2C6H3) and cis- and trans- from appropriate starting materials.Mechanistic data suggest that the reaction occurs via attack of catalyst at a co-ordinated CO ligand.Subsequent attack by unco-ordinated RNC in an intermolecular, non-bridging mechanism leads to the required isonitrile derivatives.

Metal Carbonyl Substitution Reactions catalysed by Transition Metal Complexes

The reaction of Fe(CO)5 with isonitriles RNC in the presence of CoCl2*2H2O as catalyst to give Fe(CO)5-n(RNC)n (n = 1-5) is reported.