Multinuclear magnetic resonance (phosphorus-31, selenium-77, mercury-199) and electrochemical studies of nonlabile mercury(II) complexes with group 15/group 16 donor ligands

Bond, Alan M.; Colton, R.; Ebner, J.

doi:10.1021/ic00283a008

Cited by 30 publications

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“…Due to the low solubility of the mercury compound 9b , only a weak, broad singlet is observed in the 199 Hg NMR spectrum instead of the expected quintet arising from the coupling to four equivalent phosphorus atoms. The chemical shift of −793 ppm is, however, comparable with that of the quintet observed at −785 ppm for a related cationic Hg(II) complex of the neutral ligand, {Hg[H 2 C(PPh 2 Se) 2 ] 2 [ClO 4 ] 2 } . In addition, doublets are visible at −124 and −82 ppm in the 77 Se NMR spectra of 9a and 9b , respectively, both at somewhat lower field than the corresponding signal for Li 8a .…”

Section: Resultssupporting

confidence: 54%

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Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ⁱPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻

2009

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Section: Resultssupporting

confidence: 54%

“…. 31 In addition, a doublet is visible at -124 and -82 ppm in the 77 Se NMR spectra of 9a and 9b, respectively, both at somewhat lower field than the corresponding signal for Li8a.…”

Section: Synthesis Of {Hg[hc(pph2se)2]2} (9b)mentioning

confidence: 91%

Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ⁱPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻

2009

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Mercury: Inorganic & Coordination ChemistryBased in part on the article Mercury: Inorganic & Coordination Chemistry by Gregory J. Grant which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Bebout

2005

Encyclopedia of Inorganic Chemistry

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Mercury is one of the oldest known elements. The element exhibits surprisingly different chemistry from its congeners zinc and cadmium, and it is the only group 12 member without a known beneficial biological role. Unique properties associated with the element and its compounds have led to diverse applications. However, many of these are being phased out to minimize further increases in the environmental and atmospheric burden with this toxic heavy metal. Motivations to study the compounds and complexes of mercury include potential for discovery of novel properties such as high‐temperature superconductivity and improved understanding of its interactions in physiological systems. Valuable characterization of mercury‐containing compounds is possible with 199 Hg NMR techniques. Mercury is the only group 12 member to have a stable monovalent state. Observed primarily in the oldest known and most common of all metal polycations, Hg 2 2+ , this metal–metal bonded species readily disproportionates into Hg 2+ and Hg 0 . Mercury(I) compounds, typically, have a linear structure of type XHgHgX. Halides, oxy salts, oxides, and coordination compounds with oxygen and weakly basic nitrogen‐donor ligands are best known for Hg 2 2+ . The most prevalent ionization state of mercury, Hg 2+ , is a d 10 metal ion, which lacks strong coordination number and geometry preferences. As a result, structural characterization of its compounds by X‐ray crystallography is particularly critical. A wide range of halides, pseudohalides, and chalcogenides of Hg 2+ are known. The softness of Hg 2+ has led to an investigation of coordination, with a wide variety of sulfur ligands and physiological sulfur donors being assumed to be the most important. Mercury(II) typically has a stronger affinity for S‐, N‐, and P‐donors than any other divalent metal ion. However, Hg 2+ also has a tendency to undergo incredibly rapid ligand exchange. Recent studies have shown that sterically demanding multidentate ligand systems can suppress ligand exchange processes.

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Chemistry at the Sterically Shielded Mercury Centre of the [(η4-pp3)PtHg] Fragment

Schuh¹,

Kopacka²,

Wurst³

et al. 2001

Eur. J. Inorg. Chem.

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Treatment of [(η 4 -pp3)PtH]OTf (pp3 = tris[2-(diphenylphosphanyl)ethyl]phosphane) with PhHgCl gave [(η 4 -pp3)-PtHgCl]OTf (1a) in good yield. The reaction of 1a with the carbonylmetallates [Mn(CO) 5 ] − or [Co(CO) 4 ] − and TlOTf produced the linear trinuclear clusters [(η 4 -pp3)-PtHgMn(CO) 5 ]OTf (2) or [(η 4 -pp3)PtHgCo(CO) 4 ]OTf (3), respectively. The reaction of 1a with PR 3 and TlOTf gave [(η 4 -pp3)PtHg(PR 3 )](OTf) 2 (4: R = nBu; 5: R = Ph), with Ph 2 P(CH 2 ) n PPh 2 (n = 1, 2) or dppmSe [dppmSe = bis(diphenylphosphanyl)methane monoselenide] adducts in which the diphosphane/diphosphane monoselenide adopts a mono-

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Multinuclear magnetic resonance (phosphorus-31, selenium-77, mercury-199) and electrochemical studies of nonlabile mercury(II) complexes with group 15/group 16 donor ligands

Cited by 30 publications

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Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ⁱPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻

Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ⁱPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻

Mercury: Inorganic & Coordination ChemistryBased in part on the article Mercury: Inorganic & Coordination Chemistry by Gregory J. Grant which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Chemistry at the Sterically Shielded Mercury Centre of the [(η4-pp3)PtHg] Fragment

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Multinuclear magnetic resonance (phosphorus-31, selenium-77, mercury-199) and electrochemical studies of nonlabile mercury(II) complexes with group 15/group 16 donor ligands

Cited by 30 publications

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Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh2E)(PPh2)]− (E = Se, Te) and [HC(PR2E)2]− (E = Se, Te, R = Ph; E = Se, R = iPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR2Se)2]−

Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh2E)(PPh2)]− (E = Se, Te) and [HC(PR2E)2]− (E = Se, Te, R = Ph; E = Se, R = iPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR2Se)2]−

Mercury: Inorganic & Coordination ChemistryBased in part on the article Mercury: Inorganic & Coordination Chemistry by Gregory J. Grant which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Chemistry at the Sterically Shielded Mercury Centre of the [(η4-pp3)PtHg] Fragment

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Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ⁱPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻

Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ⁱPr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻