Preparation of Mercury(II) Complexes of Tris[(2-pyridyl)methyl]amine and Characterization by X-ray Crystallography and NMR Spectroscopy
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- 作者：Deborah C. Bebout ; David E. Ehmann ; Jonathan C. Trinidad ; Kathleen K. Crahan ; Margaret E. Kastner ; and Damon A. Parrish
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：September 10, 1997
- 年：1997
- 卷：36
- 期：19
- 页码：4257 - 4264
- 全文大小：217K
- 年卷期：v.36,no.19(September 10, 1997)
- ISSN：1520-510X
文摘
The complexation of Hg(II) by the tripodal ligandtris[(2-pyridyl)methyl]amine (TMPA) was investigatedbysolution state NMR and X-ray crystallography. Mercury coordinationcompounds exhibiting rarely observedroom-temperature solution state NMR1H199Hg and13C199Hg satellites were characterized.Solvent, counterion,temperature, and concentration effects on solution state NMR propertieswere investigated. The solution stateNMR were correlated with two solid state structures. Theeight-coordinate complex[Hg(TMPA)2](ClO4)2(1)crystallizes in the monoclinic space groupP21/n with a =9.735(10) Å, b = 10.963(2) Å, c =18.553(34) Å, 
chars/beta2.gif" BORDER=0 ALIGN="middle">= 103.81(12)
, and Z = 2. The mercury is atthe inversion center of a bicapped trigonal antiprism. TheHg-Namine distance is 2.560(3) Å, and the averageHg-Npyridyl distance is 2.58(2) Å. Thefive-coordinate complex[Hg(TMPA)Cl]2(HgCl4)(2) crystallizes in the triclinic space groupP
cr.gif"> with a = 11.887(2) Å,b = 13.260(2) Å,c = 15.278(4) Å, chars/alpha.gif" BORDER=0> = 112.27(2), chars/beta2.gif" BORDER=0 ALIGN="middle"> =109.39(2), chars/gamma.gif" BORDER=0 > = 90.670(10), and Z = 2.The two crystallographicallyunique cations are distorted trigonal bipyramids. The averageHg-Cl distance is 2.355(12) Å, the average Hg-Namine distance is 2.43(2) Å, and the averageHg-Npyridyl distance is 2.40(5) Å.
chars/beta2.gif" BORDER=0 ALIGN="middle">= 103.81(12), and Z = 2. The mercury is atthe inversion center of a bicapped trigonal antiprism. TheHg-Namine distance is 2.560(3) Å, and the averageHg-Npyridyl distance is 2.58(2) Å. Thefive-coordinate complex[Hg(TMPA)Cl]2(HgCl4)(2) crystallizes in the triclinic space groupPcr.gif"> with a = 11.887(2) Å,b = 13.260(2) Å,c = 15.278(4) Å, chars/alpha.gif" BORDER=0> = 112.27(2), chars/beta2.gif" BORDER=0 ALIGN="middle"> =109.39(2), chars/gamma.gif" BORDER=0 > = 90.670(10), and Z = 2.The two crystallographicallyunique cations are distorted trigonal bipyramids. The averageHg-Cl distance is 2.355(12) Å, the average Hg-Namine distance is 2.43(2) Å, and the averageHg-Npyridyl distance is 2.40(5) Å.