Mercury(II)halide complexes of tertiary phosphines. Part VI. The crystal structure of HgCl2(PPh32 and a comparison with related compounds

Bell, Norman A.; Dee, Terence D.; Goldstein, Michael; McKenna, Paul; Nowell, Ian W.

doi:10.1016/s0020-1693(00)83650-6

Cited by 56 publications

(7 citation statements)

References 3 publications

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“…The M–P distances are the longest for the Cd compound 9 (M = Zn, 2.463(av) Å; M = Cd, 2.587(av) Å; M = Hg, 2.495(av) Å). They are comparable to those of metal–phosphine complexes such as MCl 2 ·2PPh 3 . Those complexes seem to be less soluble than 7 – 10 and were usually handled in water/alcohol, acetonitrile, glacial acetic acid, or chloroform.…”

Section: Results and Discussionsupporting

confidence: 51%

MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

2020

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Two equivalents of the phosphinylvinyl Grignard reagent Mes2PC[MgCl(THF)2]CHPh (2) reacted with MeGaCl2, EtGaCl2, or MeInCl2 by salt elimination and formation of the frustrated Lewis pairs 4–6, which have two Lewis basic P atoms in their molecular backbones. These FLPs coordinated and solubilized MCl2 compounds (M = Zn, Cd, Hg) by the chelating coordination of the Zn, Cd, or Hg atoms with phosphorus. The interaction of one Cl atom with the Lewis acidic Ga or In atoms resulted in the formation of norbornane type molecular structures with M–Cl–E bridges (E = Ga, In) and relatively weak M–Cl bonds. The products showed a fascinating dynamic behavior in solution, which gave rise to highly complex NMR spectra. The reaction of 4 with AuCl resulted in cleavage of the Au–Cl bond and the transfer of the Cl atom to the Lewis acidic Ga atom.

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Section: Results and Discussionsupporting

confidence: 51%

MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

2020

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“…The geometry around mercury is distorted tetrahedral. The Hg-P distances of 2.453(2) and 2.456(2) Å in 4 and 5, respectively, are in the range of 2.39(1)-2.574(3) Å reported previously for 1:2 mercuric halide-phosphine complexes [24,25]. The P-Hg-P angles 143.93 (8) [26], where the P-Hg-P angles are 134°and 158°, respectively.…”

Section: Molecular Structures Of the 1:1 Complexes 2 Andsupporting

confidence: 56%

Synthesis, crystal structures and spectra of Hg(II)-1,2-bis(diphenylphosphino)ethane monoxide complexes: Monomer and polymer formation

Mothi¹,

Neels²,

Stœckli-Evans³

et al. 2007

Polyhedron

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The reaction of mercury(II) halides with 1,2-bis(diphenylphosphino)ethane monoxide (dppeO) in 1:1 molar ratio yielded P,Ocoordinated polymers having the empirical formula [HgX 2 (dppeO)] n [X = Cl (1), Br (2), I (3)]. In contrast, the reaction between the same reactants in a 1:2 molar ratio yielded the P, P-coordinated monomeric complexes, HgX 2 (dppeO) 2 [X = Cl (4), Br (5), I (6)]. The structures of 2, 3, 4 and 5 have been characterized crystallographically. The results indicate that the geometry around the mercury atom in each of these molecules is tetrahedral with considerable distortion. The 31 P NMR spectra of the 1:1 complexes indicate the dissociation of the Hg-O bond in solution.

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“…IR and Raman Spectroscopy. Vibrational spectroscopy is well established as a tool for characterizing metal geometries in phosphine complexes of mercury halides and pseudohalides. , Mercury halide ν(Hg−X) stretching modes for X = Cl, Br, I, SCN have been assigned on the basis of far-IR and Raman studies on dppe complexes; both terminal and bridging species were identified.…”

Section: Resultsmentioning

confidence: 99%

Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of a Series of Mercury(II) Complexes Containing the Bidentate Phosphine Ligand Ph₂PCH₂Si(CH₃)₂CH₂PPh₂ (L²)

et al. 1997

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The bidentate phosphine ligand Ph(2)PCH(2)Si(CH(3))(2)CH(2)PPh(2) (L(2)), an analogue of 1,3-bis(diphenylphosphino)propane (dppp), coordinates to mercury(II) salts to form complexes of the general formula [HgX(2).L(2)] (X = Cl, Br, I, NCS). Infrared, Raman, and multinuclear ((1)H, (13)C, (31)P, (199)Hg) NMR spectroscopic studies show that the complexes exhibit four-coordinate pseudotetrahedral metal geometry. [HgI(2)(Ph(2)PCH(2)Si(CH(3))(2)CH(2)PPh(2))] (1) crystallizes in the monoclinic space group P2(1)/n with a = 13.028(2) Å, b = 17.402(5) Å, c = 13.849(2) Å, beta = 90.635(14) degrees, V = 3139.5(11) Å(3), and Z = 4. The structure contains a tetrahedral mercury center with the phosphine ligand bound in a bidentate fashion: Hg-P 2.511(2), 2.515(2) Å; P-Hg-P 105.28(6) degrees. The complex [HgCl(2)](2).L(2) has also been generated via a 2:1 metal:phosphine stoichiometry.

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Mercury(II)halide complexes of tertiary phosphines. Part VI. The crystal structure of HgCl2(PPh32 and a comparison with related compounds

Cited by 56 publications

References 3 publications

MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

Synthesis, crystal structures and spectra of Hg(II)-1,2-bis(diphenylphosphino)ethane monoxide complexes: Monomer and polymer formation

Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of a Series of Mercury(II) Complexes Containing the Bidentate Phosphine Ligand Ph₂PCH₂Si(CH₃)₂CH₂PPh₂ (L²)

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Mercury(II)halide complexes of tertiary phosphines. Part VI. The crystal structure of HgCl2(PPh32 and a comparison with related compounds

Cited by 56 publications

References 3 publications

MCl2Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P2-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

MCl2Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P2-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

Synthesis, crystal structures and spectra of Hg(II)-1,2-bis(diphenylphosphino)ethane monoxide complexes: Monomer and polymer formation

Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of a Series of Mercury(II) Complexes Containing the Bidentate Phosphine Ligand Ph2PCH2Si(CH3)2CH2PPh2 (L2)

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MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

MCl₂Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P₂-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of a Series of Mercury(II) Complexes Containing the Bidentate Phosphine Ligand Ph₂PCH₂Si(CH₃)₂CH₂PPh₂ (L²)