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Bebout, Deborah C.; Bush, James F.; Shumann, Elizabeth M.; Viehweg, Julie A.; Kastner, Margaret E.; Parrish, Damon A.; Baldwin, Steven M.

doi:10.1023/a:1024246501525

Cited by 11 publications

(9 citation statements)

References 16 publications

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“…The Hg−Hg#1 distance is 2.5358(8) Å and is much shorter than Hg−Hg distance of 3.00 Å in solid mercury and also shorter than the sum of the covalent radii, 2.88 Å. This distance is shorter than the Hg−Hg distance of 2.7362(6), 2.6881(4), and 2.5469(8) Å reported in [Pt 2 Hg 2 (P 2 phen) 3 ](PF 6 ) 2 , [Pd 2 Hg 2 (P 2 phen) 3 ](PF 6 ) 2 , and [Hg 2 (TLA) 2 ](CLO 4 ) 2 (TLA is abbreviation for tris[(2-(6-methylpyridyl))methyl]amine) complexes, respectively; , however, it is comparable to the Hg−Hg distance in Hg 2 Cl 2 , 2.53 Å . The Hg−Hg bond distance is near the higher end of the 2.49−2.56 Å range reported for the mercurous ion complexes .…”

Section: Resultsmentioning

confidence: 68%

“…Complex 5 is the first example of a structurally characterized mercurous cation complex of a monocycle where Hg 2 2+ is trapped inside the cavity of the monocycle. Catalano et al have explained why the formation of mercurous ion may be due to presence of HgO impurity with Hg(0) and the reaction of Hg(II) and Hg(0) strongly favors Hg 2 2+ . , Recently, Baldwin et al have reported the formation of mercurous dimer from the mercuric salt . They have also explained it as the disproportion of Hg(II) and Hg(0) to give Hg 2 2+ .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and Structure of Mercurous Ion and Dinuclear Lead(II) Complexes of the 28-Membered Selenaaza Macrocycle: Dominance of the Chelate Ring Size Effect and Conformational Requirement over Soft−Soft Interactions

2004

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The flexible and larger ring size macrocycle 4 (C(36)H(46)N(6)Se(2)) afforded stable complex 5 [Hg(2)(PF(6))(2)[C(36)H(46)N(6)Se(2)]] on treatment with 1 equiv of mercuric acetate followed by addition of NH(4)PF(6). The reaction of Pb(OCOCH(3))(2).4H(2)O with 4 followed by treatment with NH(4)PF(6) resulted in a dinuclear lead complex (6) [Pb(2)(PF(6))(2)(OCOCH(3))(2)[C(36)H(46)N(6)Se(2)]]. The crystal structures of complexes 5 and 6 are described: C(36)H(46)F(12)Hg(2)N(6)P(2)Se(2) a = 9.5106(5) A, b = 11.5222(6) A, c = 11.8161(6) A, alpha = 115.6110(10) degrees , beta = 96.5190(10) degrees , gamma = 106.2910(10) degrees , monoclinic, P, Z =1; C(44)H(57)F(12)N(8)O(4)P(2)Pb(2)Se(2) a = 9.4668(5) A, b = 11.9937(6) A, c = 25.2319(14) A, alpha = 102.4130(10) degrees , beta = 97.6130(10) degrees , gamma = 94.8540(10) degrees , monoclinic, P, Z = 2. The crystal structure of 5 revealed that Hg(2)(2+) is trapped inside the cavity of the macrocycle. The geometry around the mercurous ion is antiprismatic with Hg(2)(2+) coordinating to six nitrogen atoms forming four five-membered rings, and there is no interaction between the mercurous ion and the selenium donor atoms. The single crystal X-ray crystal structure of 6 indicates a distorted octahedral geometry around each lead atom in the cavity of the macrocycle due to presence of the sterochemically active lone pair on Pb(II). The octahedral geometry around each Pb(II) is satisfied by coordination to 3 nitrogen atoms, two oxygen atoms of the chelating acetate group, and bridging of one of the oxygen atoms of the nearby acetate.

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Section: Resultsmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Synthesis and Structure of Mercurous Ion and Dinuclear Lead(II) Complexes of the 28-Membered Selenaaza Macrocycle: Dominance of the Chelate Ring Size Effect and Conformational Requirement over Soft−Soft Interactions

2004

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“…The Baldwin group reported a Hg(I) complex of a tripodal nitrogen ligand isolated from the reaction with a Hg(II) salt via comproportionation of Hg(II) and Hg(0) to give Hg 2 2+ . In a range of studies, however, the serendipitous formation of Hg 2 2+ complexes from Hg(II) has been attributed to the role of the solvent or ligand as the possible reducing agent.…”

Section: Resultsmentioning

confidence: 99%

Group 12 Metal Complexes of an 18-Membered N₂O₂S₂ Macrocycle Incorporating Two Pyridines: First Examples of an Infinite Mercury(I) Complex and a Dumbbell-Shaped Heteronuclear Complex with a Macrocyclic Ligand

Seo

Kim

et al. 2016

Inorg. Chem.

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Homo- and heteronuclear group 12 metal (Zn, Cd, and Hg) complexes 1-6 containing a newly designed 18-membered NOS macrocycle incorporating two pyridine subunits (L) were prepared and structurally characterized. The individual complexes isolated exhibit unusual stoichiometries, geometries, oxidation states, and structural topologies and include an infinite mercurous complex and a heteronuclear dumbbell-shaped complex. Both the Zn(II) complex [Zn(L)][ZnBr] (1) and the Cd(II) complex [Cd(L)Br] (2) are mononuclear, with the metal ion located inside the macrocyclic cavity. The six-coordinated Zn(II) center in 1 adopts an octahedral geometry and is shielded from the anion and solvent by the strongly bound macrocycle. The Cd(II) center in 2 is seven-coordinate, being bound equatorially to two N donors, two O donors, and a S donor from the macrocycle and axially to two bromide ions on opposite sides of the macrocyclic plane, adopting a pentagonal-bipyramidal geometry. In the Hg(II) complexations, the configuration adopted by the macrocycle L shows a dependence of the nuclearity on the anion used. When mercury(II) bromide was used, the dinuclear complex [Hg(L)Br] (3) was obtained, while the reaction with mercury(II) nitrate afforded the unexpected Hg(I) complex {[Hg(L)](NO)} (4) with a one-dimensional polymeric structure. In heterometallic complexation experiments, one-pot reaction of L with a mixture of ZnBr and CdBr·4HO resulted in the stepwise isolation of two pure solubility-dependent Cd(II) complexes (2 and 5), including the half-dumbbell-type complex [Cd(L)(μ-Br)(CdBr)] (5), while a mixture of CdBr·4HO and HgBr yielded the heterometallic bis(macrocycle) product [(CdL)(μ-HgBr)](HgBr) (6). This is the first example of a heteronuclear dumbbell-shaped complex in which two terminal macrocyclic Cd(II) complexes are linked by a hexabromodimercury(II) cluster via Cd-Br-Hg bonds. The heterometallic dumbbell 6 can be considered as a good example of competition and collaboration between Cd(II) and Hg(II) ions because its formation is associated with the higher coordination affinity of Cd(II) toward the macrocycle and the formation of the (HgBr) cluster, which links the two endocyclic Cd(II) complexes directly. Both NMR titration and comparative NMR data indicate a relatively higher coordination affinity of Cd(II) toward the macrocycle than occurs for Hg(II), in parallel to the situation observed in the solid state.

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“…The deep blue colour results from intraligand transitions, a similar colour being observed for the Cd analogue. In another study producing a bimetallic complex, Bebout et al 52 encapsulated a dimeric mercurous [Hg 2 ] 21 ion within a pair of tetradentate tripodal nitrogen ligands, tris[(2-(6-methylpyridyl)) methyl]amine. In this instance the Hg … Hg bond distance is very short at ca.…”

Section: Mercurymentioning

confidence: 99%

10 Zinc, cadmium and mercury

Shannon

2004

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This Chapter seeks to highlight advances in chemistry involving the Group 12 elements zinc, cadmium and mercury published during the year 2003. Given the burgeoning quantity of literature published in this area, the purpose of this review is not to provide a comprehensive list of all papers published involving zinc, cadmium and mercury, but rather to draw attention to some of the more important discoveries in this field. Hence, this review has been focused on the synthesis of new liganded complexes and discusses potential applications for these species. Literature highlightsAmongst the literature for 2003, a large number of papers have been published on the development of coordination polymers and networks which transcend the use of Zn, Cd and Hg as the templating metal. One interesting paper in this area describes the synthesis of a zinc coordination polymer containing 4-sulfanylmethyl-4A-phenylcarboxylate pyridine (spcp), Zn(spcp)(OH), in which helical structure is found with the compound exhibiting SHG properties. 1 Another is the development of a variety of zinc terpyridyl polymers that exhibit emission colours right across the spectrum from violet to yellow. 2 The high photoluminescence quantum yields mean that these materials have great potential for use in light-emitting materials for electroluminescent devices.In more traditional coordination chemistry, an unusual Cd 4 (m-O) motif was found to be the core structure forming unit in a cadmium coordination complex containing both 2,2'-dihydroxy-[1,1']-binaphthalene-3,3'-dicarboxylate acid and pyridine-2-one, ligands; 3 this configuration gives rise to a strong ligand-to-metal-charge-transfer emission in the green-blue region.In the area of mercury chemistry, one of the more unusual papers of 2003 describes the synthesis of mercury-xenon complexes 4 in which the noble gas is directly coordinated to the mercury cation, and crystallised out as mixed antimony fluoride salts of composition [HgXe] 21 [SbF 6 ] 2 [Sb 2 F 11 ] 2 .

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Untitled

Cited by 11 publications

References 16 publications

Synthesis and Structure of Mercurous Ion and Dinuclear Lead(II) Complexes of the 28-Membered Selenaaza Macrocycle: Dominance of the Chelate Ring Size Effect and Conformational Requirement over Soft−Soft Interactions

Synthesis and Structure of Mercurous Ion and Dinuclear Lead(II) Complexes of the 28-Membered Selenaaza Macrocycle: Dominance of the Chelate Ring Size Effect and Conformational Requirement over Soft−Soft Interactions

Group 12 Metal Complexes of an 18-Membered N₂O₂S₂ Macrocycle Incorporating Two Pyridines: First Examples of an Infinite Mercury(I) Complex and a Dumbbell-Shaped Heteronuclear Complex with a Macrocyclic Ligand

10 Zinc, cadmium and mercury

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Untitled

Cited by 11 publications

References 16 publications

Synthesis and Structure of Mercurous Ion and Dinuclear Lead(II) Complexes of the 28-Membered Selenaaza Macrocycle: Dominance of the Chelate Ring Size Effect and Conformational Requirement over Soft−Soft Interactions

Synthesis and Structure of Mercurous Ion and Dinuclear Lead(II) Complexes of the 28-Membered Selenaaza Macrocycle: Dominance of the Chelate Ring Size Effect and Conformational Requirement over Soft−Soft Interactions

Group 12 Metal Complexes of an 18-Membered N2O2S2 Macrocycle Incorporating Two Pyridines: First Examples of an Infinite Mercury(I) Complex and a Dumbbell-Shaped Heteronuclear Complex with a Macrocyclic Ligand

10 Zinc, cadmium and mercury

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Group 12 Metal Complexes of an 18-Membered N₂O₂S₂ Macrocycle Incorporating Two Pyridines: First Examples of an Infinite Mercury(I) Complex and a Dumbbell-Shaped Heteronuclear Complex with a Macrocyclic Ligand