77826-99-4

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• 88333-03-3 Benzyl isocyanide 
• 14040-11-0 tungsten hexacarbonyl 
• 622-79-7 benzyl azide 
• 100-46-9 benzylamine 

Relevant academic research and scientific papers

Synthesis of Isonitrile Complexes of Group-VI Metal Carbonyls and Their Use as Mediator in the [2+2+2]-Cyclization of Alkynes

A method for selective synthesis of metal carbonyl complexes with certain number of isonitriles has been introduced. The use of these complexes as a mediator in the partially intermolecular [2+2+2]-cyclic cotrimerization of alkynes has also been demonstrated.

Organic Syntheses via Transition Metal Complexes, 31. - N-Benzylketenimine Complexes - Metal Influence on Rearrangement and Addition Reactions

N-Benzylketenimine complexes, LnM 3 are obtained on addition of benzyl isocyanide to metal carbene complexes 1.They can be easily isomerized by a 1,3-N/C migration of the benzyl group to give 3-phenylpropanenitrile complexes 5.The tendency for this rearrangement is strongly influenced by the nature of the metal and follows the sequence Mo > Cr > W >> Mn, Fe.This is demonstrated by competition experiments involving the addition of methanol to give aminocarbene complexes 6 and the addition of a further equivalent of benzyl isocyanide to give di(imino)indane complexes and/or azetidinylidene complexes (11 and/or 12 and 13, respectively).One observes the formation of di(imino)indanes with chromium and molybdenum complexes, but with manganese and iron complexes azetidines are formed.Tungsten complexes play an intermediate role in so far as both systems are obtained.

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.

Preparation of some dithiocarbene complexes, W(CO)5[C(SR)2], and their reactions with nucleophiles

The reaction of W(CO)5CS with -SR (R = CH3, C2H5, i-C3H7, n-C4H9, or t-C4H9) followed by alkylation of the resulting dithioester anion, W(CO)5[C(=S)SR]-, by R′I (R′ = CH3 or C2H5) produces [bis(alkylthio)carbene] tungsten complexes, W(CO)5[C(SR)(SR′)], in good yield. The substituted tetracarbonyl[bis(methylthio)carbene]tungsten complexes cis-W-(CO)4[P(OCH3)3][C(SCH3) 2] and cis-W(CO)4[P(OPh)3][C(SCH3)2] are prepared by an analogous route using cis-W-(CO)4L(CS), where L = P(OCH3)3 or P(OPh)3. (Cyclic dithiocarbene)tungsten complexes may be prepared in a similar manner from W(CO)5CS, NaS(CH2)nSH (n = 2, 3, 4), and CH3I to give W(CO)5CS(CH2)nS. The carbene complex W(CO)5{C(SCH3)[SFe(CO)2Cp]} (Cp = η5C5H5) is prepared by the reaction of W(CO)5[C(=S)(SCH3)]- with CpFe-(CO)2(THF)+. Isocyanide complexes, W(CO)5CN-R, are formed when W(CO)5[C(SCH3)2] reacts with primary amines, RNH2, where R = CH3, (CH2)2CH3, CH2Ph, C6H11, and (CH2)2N(CH3)2, or the diamine NH2(CH2)3NH2. When cis-W(CO)4[P(OPh)3][C(SCH3)2] is reacted with NH2CH2Ph and NH2(CH2)3NH2, isocyanide complexes are also formed. The reaction of W(CO)5[C(SCH3)2] with secondary amines NH(CH3)2, HN(CH2)2OCH2CH2, or HN(CH2)4CH2 yields (aminothiocarbene)tungsten complexes, W(CO)5[C(SCH3)NR2]. The compound [N(C2H5)4+][W(CO)5CN -] was formed from the reaction of W(CO)5[C(SCH3)2] with [N(C2H5)4+][N3 -].