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Molecular Architectures Derived from Metal Ions and the Flexible 3,3'-Bipyridine Ligand: Unexpected Dimer with Hg(II).

Khutia A, Sanz Miguel PJ, Lippert B - Bioinorg Chem Appl (2010)

Bottom Line: H(2)O}(n) (1), with all other metal entities cyclic structures were formed.Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities.With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer.

View Article: PubMed Central - PubMed

Affiliation: Fakultät Chemie, Technische Universität Dortmund, 44221 Dortmund, Germany.

ABSTRACT
The flexible ditopic ligand 3,3'-bipyridine (3,3'-bpy) has been reacted with a series of transition metal species (Ag(+), Hg(2+), cis-a(2)M(2+) (a = NH(3) or a(2) = en; M = Pt, Pd), trans-a(2)Pt(2+) (a = NH(3))) in an attempt to produce discrete cyclic constructs. While Ag(+) gave a polymeric structure {[Ag(3,3'-bpy)](ClO(4)) . H(2)O}(n) (1), with all other metal entities cyclic structures were formed. Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities. With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer. With trans-(NH(3))(2)Pt(2+), different species are formed according to (1)H NMR spectroscopy, the nature of which was not established.

No MeSH data available.


(a) View of 2 with atom numbering scheme. (b) Side view of 2, evidencing a boat conformation of the mercury atoms with respect to the 3,3′-bpy ligands.
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fig5: (a) View of 2 with atom numbering scheme. (b) Side view of 2, evidencing a boat conformation of the mercury atoms with respect to the 3,3′-bpy ligands.

Mentions: The crystal structure of the dinuclear species [Hg(3,3'-bpy)(CH3COO)2]2· 3H2O (2) is given in Figure 5. Unlike in 1, in 2 the 3,3′-bpy ligands adopt a cis-conformation of the two pyridyl rings, with a twist angle of 30.4(2)°, and act as bridges between two mercury centers. The coordination geometry of the Hg ion (Table 3) is distorted tetrahedral, enclosing two 3,3′-bpy entities (Hg1-N1a, 2.274(3) Å; Hg1-N1b, 2.263(3) Å), and two chelating/semichelating acetates (Hg1-O11, 2.490(3) Å; Hg1-O12, 2.392(3) Å; and Hg1-O21, 2.286(3) Å; Hg1-O22, 2.762(3) Å). Selected distances and angles around mercury are listed in Table 3. Both 3,3′-bpy ligands and their bonded mercury atoms are almost coplanar with a tendency towards a boat conformation (distance from Hg1 to the plane defined by N1a, N1b, N1a′, N1b′ is 0.58 Å).


Molecular Architectures Derived from Metal Ions and the Flexible 3,3'-Bipyridine Ligand: Unexpected Dimer with Hg(II).

Khutia A, Sanz Miguel PJ, Lippert B - Bioinorg Chem Appl (2010)

(a) View of 2 with atom numbering scheme. (b) Side view of 2, evidencing a boat conformation of the mercury atoms with respect to the 3,3′-bpy ligands.
© Copyright Policy - open-access
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC2901620&req=5

fig5: (a) View of 2 with atom numbering scheme. (b) Side view of 2, evidencing a boat conformation of the mercury atoms with respect to the 3,3′-bpy ligands.
Mentions: The crystal structure of the dinuclear species [Hg(3,3'-bpy)(CH3COO)2]2· 3H2O (2) is given in Figure 5. Unlike in 1, in 2 the 3,3′-bpy ligands adopt a cis-conformation of the two pyridyl rings, with a twist angle of 30.4(2)°, and act as bridges between two mercury centers. The coordination geometry of the Hg ion (Table 3) is distorted tetrahedral, enclosing two 3,3′-bpy entities (Hg1-N1a, 2.274(3) Å; Hg1-N1b, 2.263(3) Å), and two chelating/semichelating acetates (Hg1-O11, 2.490(3) Å; Hg1-O12, 2.392(3) Å; and Hg1-O21, 2.286(3) Å; Hg1-O22, 2.762(3) Å). Selected distances and angles around mercury are listed in Table 3. Both 3,3′-bpy ligands and their bonded mercury atoms are almost coplanar with a tendency towards a boat conformation (distance from Hg1 to the plane defined by N1a, N1b, N1a′, N1b′ is 0.58 Å).

Bottom Line: H(2)O}(n) (1), with all other metal entities cyclic structures were formed.Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities.With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer.

View Article: PubMed Central - PubMed

Affiliation: Fakultät Chemie, Technische Universität Dortmund, 44221 Dortmund, Germany.

ABSTRACT
The flexible ditopic ligand 3,3'-bipyridine (3,3'-bpy) has been reacted with a series of transition metal species (Ag(+), Hg(2+), cis-a(2)M(2+) (a = NH(3) or a(2) = en; M = Pt, Pd), trans-a(2)Pt(2+) (a = NH(3))) in an attempt to produce discrete cyclic constructs. While Ag(+) gave a polymeric structure {[Ag(3,3'-bpy)](ClO(4)) . H(2)O}(n) (1), with all other metal entities cyclic structures were formed. Interestingly, Hg(CH(3)COO)(2) produced a dinuclear complex [Hg(3,3'-bpy)(CH(3)COO)(2)](2) . 3H(2)O (2), in which the two 3,3'-bpy ligands adopt a cis-orientation of the coordinating pyridyl entities. With cis-(NH(3))(2)Pt(2+), a cyclic complex 4 was isolated in crystalline form which, according to HRMS, is a trimer. With trans-(NH(3))(2)Pt(2+), different species are formed according to (1)H NMR spectroscopy, the nature of which was not established.

No MeSH data available.