title: Relation between intramolecular NH...S hydrogen bonds and coordination number in mercury(II) complexes with carbamoylbenzenethiol derivatives.
abstract: A novel series of bis(carbamoylthiophenolato)mercury(II) complexes, [Hg(S-RNHCOC6H4)2] (1, R = 2-t-Bu; 2, R = 2-CH3; 3, R = 2-C6H5CH2; 4, R = 4-t-Bu), and a tetrakis(carbamoylthiophenolato)mercury(II) complex, (NEt4)2[Hg-(S-2-CH3NHCOC6H4)4] (5), were synthesized and characterized by 1H NMR, IR, 199Hg NMR, and crystallographic analyses. The bis(carbamoylthiophenolato)mercury complexes 1-3 do not have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom coordinated to mercury, whereas the tetrakis(thiophenolato)mercury complex 5 does have an intramolecular NH...S hydrogen bond. A relatively weak NH...S hydrogen bond in 5 can be seen in the 1H NMR spectra and the IR spectra in chloroform and in the solid state. The 199Hg NMR spectra in bis(carbamoylthiophenolato)mercury complexes 1-4 show a downfield shift, with an increase in the flow of electrons to mercury(II) from the oxygen atom due to the intramolecular Hg...O bonding interaction. Conversely, the 199Hg NMR spectra in 5 show a high-field shift with a decrease in the flow of electrons to mercury(II) from the sulfur atom due to the intramolecular NH...S hydrogen bond.
authors.affiliation: Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Kato
authors.forename: Kazunori
authors.initials: K
authors.lastname: Kojima
authors.forename: Taka-aki
authors.initials: TA
authors.lastname: Okamura
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Yamamoto
authors.forename: Takeshi
authors.initials: T
authors.lastname: Yamamura
authors.forename: Norikazu
authors.initials: N
authors.lastname: Ueyama