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Draper ND, Batchelor RJ, Aguiar PM, et al. Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries. Inorg Chem. 2004;43(21):6557-67doi: 10.1021/ic049792e.
Draper, N. D., Batchelor, R. J., Aguiar, P. M., Kroeker, S., & Leznoff, D. B. (2004). Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries. Inorganic chemistry, 43(21), 6557-67. https://doi.org/10.1021/ic049792e
Draper, Neil D, et al. "Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries." Inorganic chemistry vol. 43,21 (2004): 6557-67. doi: https://doi.org/10.1021/ic049792e
Draper ND, Batchelor RJ, Aguiar PM, Kroeker S, Leznoff DB. Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries. Inorg Chem. 2004 Oct 18;43(21):6557-67. doi: 10.1021/ic049792e. PMID: 15476352.
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Inorg Chem. 2004 Oct 18;43(21):6557-67. doi: 10.1021/ic049792e.

Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries.

Inorganic chemistry

Neil D Draper, Raymond J Batchelor, Pedro M Aguiar, Scott Kroeker, Daniel B Leznoff

Affiliations

  1. Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, British Columbia V5A 1S6, Canada.

PMID: 15476352 DOI: 10.1021/ic049792e

Abstract

In the reaction of organic monocationic chlorides or coordinatively saturated metal-ligand complex chlorides with linear, neutral Hg(CN)(2) building blocks, the Lewis-acidic Hg(CN)(2) moieties accept the chloride ligands to form mercury cyanide/chloride double salt anions that in several cases form infinite 1-D and 2-D arrays. Thus, [PPN][Hg(CN)(2)Cl].H(2)O (1), [(n)Bu(4)N][Hg(CN)(2)Cl].0.5 H(2)O (2), and [Ni(terpy)(2)][Hg(CN)(2)Cl](2) (4) contain [Hg(CN)(2)Cl](2)(2-) anionic dimers ([PPN]Cl = bis(triphenylphosphoranylidene)ammonium chloride, [(n)Bu(4)N]Cl = tetrabutylammonium chloride, terpy = 2,2':6',6' '-terpyridine). [Cu(en)(2)][Hg(CN)(2)Cl](2) (5) is composed of alternating 1-D chloride-bridged [Hg(CN)(2)Cl](n)(n-) ladders and cationic columns of [Cu(en)(2)](2+) (en = ethylenediamine). When [Co(en)(3)]Cl(3) is reacted with 3 equiv of Hg(CN)(2), 1-D [[Hg(CN)(2)](2)Cl](n)(n-) ribbons and [Hg(CN)(2)Cl(2)](2-) moieties are formed; both form hydrogen bonds to [Co(en)(3)](3+) cations, yielding [Co(en)(3)][Hg(CN)(2)Cl(2)][[Hg(CN)(2)](2)Cl] (6). In [Co(NH(3))(6)](2)[Hg(CN)(2)](5)Cl(6).2H(2)O (7), [Co(NH(3))(6)](3+) cations and water molecules are sandwiched between chloride-bridged 2-D anionic [[Hg(CN)(2)](5)Cl(6)](n)(6n-) layers, which contain square cavities. The presence (or absence), number, and profile of hydrogen bond donor sites of the transition metal amine ligands were observed to strongly influence the structural motif and dimensionality adopted by the anionic double salt complex anions, while cation shape and cation charge had little effect. (199)Hg chemical shift tensors and (1)J((13)C,(199)Hg) values measured in selected compounds reveal that the NMR properties are dominated by the Hg(CN)(2) moiety, with little influence from the chloride bonding characteristics. delta(iso)((13)CN) values in the isolated dimers are remarkably sensitive to the local geometry.

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