25792-38-5

Upstream product

• 931-53-3 Cyclohexyl isocyanide 
• 19706-02-6 [Fe(CO)4(CNC₆H₁₁)] 
• 538-75-0 dicyclohexyl-carbodiimide 
• 100447-70-9 triiron dodecacarbonyl 
• 19706-02-6 Fe(CO)4(CNC₆H₁₁) 

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.

Reaction of [Fe3(CO)12] with dicyclohexylcarbodiimide. Formation and structure of [Fe2(CO)6{μ,μ′-(C6H 11N)2CFe(CO)4}]

The reaction of the carbodiimide C6H11NCNC6H11 (C6H11 = cyclohexyl) with [Fe2(CO)9] in boiling hexane gives the same products as it does with [Fe(CO)5], i.e., [Fe(CO)4(CNC6H11)] (I) and [Fe2(CO)6{μ,μ′-(C6H 11N)2CNC6H11}] (II), but with [Fe3(CO)12] in boiling heptane it also gives the previously unknown derivative [Fe2(CO)6{μ,μ′-(C6H 11N)2CFe(CO)4}] (III). The molecular structure of III has been determined by a single-crystal X-ray diffraction study. This shows that the Fe2(CO)6 fragment has the familiar saw horse structure with each of the two N atoms of the coordinated carbodiimide molecule bridging its two iron atoms and the carbodiimide carbon atom acting as an axial carbene ligand to a distorted trigonal-bipyramidal Fe(CO)4 moiety. The structure was solved by the heavy-atom method and refined by least squares to R = 0.074 for 1559 nonzero unique photographic reflections. Crystals of the compound are monoclinic, space group P21/n, with a = 10.876 (4) A?, b = 16.609 (7) A?, c = 14.982 (5) A?, and β = 90.7 (1)° for Z = 4. The IR spectrum of III is consistent with the presence of two isomers in solution arising from restricted rotation of the Fe(CO)4 moiety about the Fe-C(carbene) bond. The X-ray structure determination shows that this behavior is probably due to steric interactions between the Fe(CO)4 carbonyl ligands and the cyclohexyl groups. Although i-PrNCN-i-Pr reacts similarly with [Fe3(CO)12] to give products analogous to I, II, and III, with the last again exhibiting rotational isomerism, p-MeC6H4NCN-p-MeC6H4 forms counterparts of I and II but not III.