105335-17-9Relevant articles and documents
Syntheses of Isocyanides at the Metal, IX. - Radical Alkylation of Cyano Complexes, II. - O-Heterocyclic Isocyanides
Fehlhammer, Wolf Peter,Degel, Fritz,Beck, Gerhard
, p. 29 - 38 (2007/10/02)
Aryldiazonium pentacarbonyl(cyano)chromates decompose already below room temperature with evalution of N2 and formation of Cr(CO)5CNR, R being derived from the solvent (RH).Variation of the solvent (tetrahydrofuran, tetrahydropyran, 1,4-dioxane, trioxane, 1,3-dioxolane, tetrahydrothiophene, and diethyl ether) thus gives access to O(S)-heterocyclic isocyanide complexes , , , (traces only), (traces only), > and Cr(CO)5CN-CHMe-OEt, respectively, for the first time.Chemical, electro-chemical, and spectroscopic (EPR)findings are in support of an initial SET process between the diazonium cation and the cyanometalle anion leading to an aryl radical (which immediately reacts with the solvent by H abstraction) and the 17e- species CrI(CN)(CO)5 (which recombines with the remaining solvent radical to give the isocyanide complex).Epoxides (, ), contrary to the reaction scheme, experience ring opening, which results in the 2-hydroxyalkyl isocyanide complexes Cr(CO)5CN-CH2CMe2-OH and Cr(CO)5CN-CMe2CH2-OH (as mixture of isomers), and Cr(CO)5CN-CHMeCHMe-OH, respectively.The transferability of this novel synthesis of isocyanides to other (organometallic) cyano complexes is demonstrated by the "radical alkylation" in tetrahydrofuran of (1-) (M = Mo, W), (1-), and (1-) to give the corresponding coordination compounds of tetrahydro-2-isocyanofuran.
