Correlation of a Solution-State Conformational Change between Mercuric Chloride Complexes of Tris[(2-(6-methylpyridyl))methyl]amine with X-ray Crystallographic Structures
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- 作者：Deborah C. Bebout ; James F. Bush II ; Kathleen K. Crahan ; Margaret E. Kastner ; and Damon A. Parrish
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：September 7, 1998
- 年：1998
- 卷：37
- 期：18
- 页码：4641 - 4646
- 全文大小：142K
- 年卷期：v.37,no.18(September 7, 1998)
- ISSN：1520-510X
文摘
Solution-state NMR and X-ray crystallography were used to investigate the complexation of HgCl2 by the potentiallytetradentate ligand tris[(6-methyl-2-pyridyl)methyl]amine (TLA) in acetonitrile. A change in the ligandconformation as a function of the metal-to-ligand ratio could be indirectly monitored through large changes in3J(1H199Hg) to the methylene protons at -40 
C. The solution-state NMR were correlated with two solid-statestructures. The five-coordinate complex [Hg(TLA)Cl2] (1) crystallizes in the triclinic space group P
with a =8.663(3) Å, b = 11.539(4) Å, c = 13.739(3) Å, 
= 80.81(2), 
= 75.84(2), 
= 80.97(3), and Z = 2. TheHg-Namine distance of 2.505(7) Å for the tridentate ligand is the same as the average Hg-Nlutidyl distance of2.50(3) Å for the two bound lutidyl nitrogens. [Hg(TLA)Cl]2(Hg2Cl6) (2) also crystallizes in P with a = 10.606(2) Å, b = 15.104(3) Å, c = 17.785(4) Å, = 67.46(3), = 83.52(3), = 80.29(3), and Z = 2. The ligandis tetradentate in the two crystallographically unique cations which are arranged in a dimer-like orientation. Theaverage Hg-Cl distance is 2.37 (1) Å, and the average interionic Hg-Cl distance is 3.51(1) Å. The Hg- Nlutidyldistances are of two types: two have an average distance of 2.36(3) Å, nearly the same as the Hg-Namine distanceof 2.35(2) Å. The remaining four Nlutidyl distances have an average distance of 2.56(5) Å.
C. The solution-state NMR were correlated with two solid-statestructures. The five-coordinate complex [Hg(TLA)Cl2] (1) crystallizes in the triclinic space group P with a =8.663(3) Å, b = 11.539(4) Å, c = 13.739(3) Å, = 80.81(2), = 75.84(2), = 80.97(3), and Z = 2. TheHg-Namine distance of 2.505(7) Å for the tridentate ligand is the same as the average Hg-Nlutidyl distance of2.50(3) Å for the two bound lutidyl nitrogens. [Hg(TLA)Cl]2(Hg2Cl6) (2) also crystallizes in P with a = 10.606(2) Å, b = 15.104(3) Å, c = 17.785(4) Å, = 67.46(3), = 83.52(3), = 80.29(3), and Z = 2. The ligandis tetradentate in the two crystallographically unique cations which are arranged in a dimer-like orientation. Theaverage Hg-Cl distance is 2.37 (1) Å, and the average interionic Hg-Cl distance is 3.51(1) Å. The Hg- Nlutidyldistances are of two types: two have an average distance of 2.36(3) Å, nearly the same as the Hg-Namine distanceof 2.35(2) Å. The remaining four Nlutidyl distances have an average distance of 2.56(5) Å.