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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.


HRMS spectrum of complex 4: Observed and calculated pattern for [M–(PF6)4]4+.
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fig6: HRMS spectrum of complex 4: Observed and calculated pattern for [M–(PF6)4]4+.

Mentions: Reactions of 3,3′-bpy with [Pd(en)(H2O)2](NO3)2 and cis-[Pt(NH3)2(H2O)2](NO3)2 (1 : 1 ratio) give products of 1 : 1 stoichiometry [{Pd(en)(3,3′-bpy)}(NO3)2]n (3) and cis-[{Pt(NH3)2(3,3′-bpy)}(PF6)2]n (4) which, according to 1H NMR spectroscopy, are pure materials. Only single sets of 3,3′-bpy resonances are observed in both compounds, indicating that both compounds must be cyclic. Chemical shifts (δ, ppm; D2O, TMA as internal reference) are as follows: 3, 9.15, 8.84, 8.27, 7.69 ppm (3,3′-bpy) and 2.98 (en); 4, 8.99, 8.95, 8.23, 7.67 (3,3′-bpy). When TSP was used as a reference, shifts differed by 0.1 ppm (3) and 0.09 ppm (4), suggesting that the TSP anion interacts with the cations of 3 and 4 [29]. Although 4 was isolated in microcrystalline form, an X-ray structure determination proved impossible. The high resolution MS of a sample of 4 was carried out and confirmed a triangular structure (see (II) or (IV) in Figure 1). The mass spectrum displayed peaks due to [M–(PF6)]+: 1880.08114 (calcd. 1880.07904), (M–(PF6)2]2+: 867.55844 (calcd. 867.55828), and [M–(PF6)4]4+: 361.29666 (calcd. 361.29621). The HRMS spectrum of [M–(PF6)4]4+ is given in Figure 6 and compared with the simulated spectrum.


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)

HRMS spectrum of complex 4: Observed and calculated pattern for [M–(PF6)4]4+.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig6: HRMS spectrum of complex 4: Observed and calculated pattern for [M–(PF6)4]4+.
Mentions: Reactions of 3,3′-bpy with [Pd(en)(H2O)2](NO3)2 and cis-[Pt(NH3)2(H2O)2](NO3)2 (1 : 1 ratio) give products of 1 : 1 stoichiometry [{Pd(en)(3,3′-bpy)}(NO3)2]n (3) and cis-[{Pt(NH3)2(3,3′-bpy)}(PF6)2]n (4) which, according to 1H NMR spectroscopy, are pure materials. Only single sets of 3,3′-bpy resonances are observed in both compounds, indicating that both compounds must be cyclic. Chemical shifts (δ, ppm; D2O, TMA as internal reference) are as follows: 3, 9.15, 8.84, 8.27, 7.69 ppm (3,3′-bpy) and 2.98 (en); 4, 8.99, 8.95, 8.23, 7.67 (3,3′-bpy). When TSP was used as a reference, shifts differed by 0.1 ppm (3) and 0.09 ppm (4), suggesting that the TSP anion interacts with the cations of 3 and 4 [29]. Although 4 was isolated in microcrystalline form, an X-ray structure determination proved impossible. The high resolution MS of a sample of 4 was carried out and confirmed a triangular structure (see (II) or (IV) in Figure 1). The mass spectrum displayed peaks due to [M–(PF6)]+: 1880.08114 (calcd. 1880.07904), (M–(PF6)2]2+: 867.55844 (calcd. 867.55828), and [M–(PF6)4]4+: 361.29666 (calcd. 361.29621). The HRMS spectrum of [M–(PF6)4]4+ is given in Figure 6 and compared with the simulated spectrum.

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.