Mercury(II) Cyanide

Kočovský, Pavel; Wang, Guijun; Sharma, Vibha

doi:10.1002/047084289x.rm034.pub2

Cited by 1 publication

(2 citation statements)

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“…Such boron compounds allow direct bond formation between the boron atom and an electrophilic reactant such as a metal cation. − Compounds containing a nucleophilic boron atom have coordinating properties similar to those of the carbenes. The latter are used often in the synthesis of catalytically active metal complexes. − Strong ligands such as carbenes, , cyanides, methyl, and ligands with a nucleophilic boron atom , form very stable complexes to mercury. Therefore, mercury complexes are good model compounds to study the properties of such ligands in comparison.…”

Section: Introductionmentioning

confidence: 99%

“…The latter are used often in the synthesis of catalytically active metal complexes. 16−18 Strong ligands such as carbenes, 19,20 cyanides, 21 methyl, 22 and ligands with a nucleophilic boron atom 15,23 form very stable complexes to mercury. Therefore, mercury complexes are good model compounds to study the properties of such ligands in comparison.…”

Section: Introductionmentioning

confidence: 99%

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Reaction of the Tricyanoborate Dianion [B(CN)₃]^2–with HgCl₂

Bernhardt

Bernhardt‐Pitchougina

Jenne

2017

Inorg. Chem.

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The very reactive [B(CN)] dianion has a strongly nucleophilic boron atom and can be used for the synthesis of tricyanoborates, which otherwise are difficult to access. Herein the reaction of this anion with HgCl is reported. The main product is the anionic mercury complex [Hg(B(CN))]. Heteronuclear NMR spectroscopic experiments shows that the reaction proceeds via the intermediate [ClHgB(CN)]. Even though [Hg(B(CN))] is the main product, it is difficult to obtain it in pure form, because it slowly decomposes in the presence of water and air to [(NC)HgB(CN)]. All three anions were fully characterized by hetereonuclear NMR spectroscopy (B, C, andHg). Single-crystal X-ray diffraction studies of the salts K[ClHgB(CN)], [PhP][Hg(B(CN))], K[(NC)HgB(CN)], and [PhP][(NC)HgB(CN)] revealed linear coordination environments around mercury for all anions. The Hg-B bonds range from 2.219(5) Å in [Hg(B(CN))] to 2.148(11) Å in [ClHgB(CN)], are in accord with the sum of the covalent radii of mercury and boron, and can be described as covalent single bonds. A comparison with related complexes indicates that the [B(CN)] dianion is a stronger ligand than chloride, cyanide, or carbenes. [Hg(B(CN))] hydrolyses in solution only in the presence of oxygen. It is suggested that cis-[Hg(OH)(B(CN))] is formed as a very unstable intermediate, which decomposes very fast to [(NC)HgB(CN)] and other products. The anion cis-[Hg(OH)(B(CN))] would contain mercury in the unusual oxidation state +IV. Quantum-chemical calculations were performed to support this assumption.

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