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Terminal Iron Carbyne Complexes Derived from Arrested CO 2 Reductive Disproportionation
Author(s) -
Mokhtarzadeh Charles C.,
Moore Curtis E.,
Rheingold Arnold L.,
Figueroa Joshua S.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201705877
Subject(s) - carbyne , disproportionation , chemistry , isocyanide , adduct , reductive elimination , substituent , trimethylphosphine , aryl , molecule , medicinal chemistry , photochemistry , crystallography , stereochemistry , crystal structure , catalysis , organic chemistry , alkyl , carbene
Abstract The encumbered tetraisocyanide dianion Na 2 [Fe(CNArMes2) 4 ] reacts with two molecules of CO 2 to effect reductive disproportionation to CO and carbonate ([CO 3 ] 2− ). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested by silylative esterification of a mono‐CO 2 adduct. This results in the formation of four‐coordinate terminal iron carbynes possessing an aryl carbamate substituent owing to the direct attachment of an C(O)OSiR 3 group to an isocyanide nitrogen atom. Crystallographic, spectroscopic, and computational analyses of these iron–carbon multiply bonded species reveal electronic structure properties indicative of a conformationally locked iron carbyne unit.