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Mercury Cyanides and Isocyanides: NCHgCN and CNHgNC as well as NCHgHgCN and CNHgHgNC: Simple Molecules with Short, Strong Hg−Hg Bonds
Author(s) -
Andrews Lester,
Cho HanGook
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904727
Subject(s) - mercury (programming language) , molecule , chemistry , simple (philosophy) , environmental chemistry , computational chemistry , inorganic chemistry , organic chemistry , computer science , philosophy , epistemology , programming language
Mercury atoms, laser‐ablated from an amalgam dental filling target, react with cyanogen in excess argon during condensation at 4 K to form two major products in the 2200 cyanide M−C−N stretching region of the IR spectrum, which were assigned to NCHgCN and NCHgHgCN from their antisymmetric C−N stretching mode absorptions at 2213.8 and 2180.1 cm −1 . Two broader bands in the isocyanide region at 2098.2 and 2089.6 cm −1 were assigned to CNHgNC and CNHgHgNC. The N‐bonded isomers were computed to be 603/33 and 823/69 times more intense IR absorbers than the C‐bonded isomers at the CCSD level of theory. The dissociation energy for the NCHg−HgCN molecule into two HgCN molecules was calculated to be 296 kJ mol −1 and that for CNHg−HgNC into two HgNC molecules is 304 kJ mol −1 . These simple molecules with two cyanide or two isocyanide ligands have two of the shortest and strongest known Hg−Hg single bonds as the two electronegative CN ligands withdraw antibonding electron density from the bonding region.