Characterization of Mercury(II) Complexes of Bis[(2-pyridyl)methyl]amine by X-ray Crystallography and NMR Spectroscopy
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- 作者：Deborah C. Bebout ; Anne E. DeLanoy ; David E. Ehmann ; Margaret E. Kastner ; Damon A. Parrish ; and Raymond J. Butcher
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：June 15, 1998
- 年：1998
- 卷：37
- 期：12
- 页码：2952 - 2959
- 全文大小：112K
- 年卷期：v.37,no.12(June 15, 1998)
- ISSN：1520-510X
文摘
Solution-state NMR and X-ray crystallography were used toinvestigate the complexation of Hg(II) by thetridentateligand bis[(2-pyridyl)methyl]amine (BMPA).Mercury coordination compounds exhibiting rarely observedsolution-state NMR 1H199Hg satellites werecharacterized. Temperature and concentration effects onsolution-state NMRproperties were investigated. The solution-state NMR werecorrelated with two solid-state structures. Thedistortedtrigonal prismatic complex[Hg(BMPA)2](ClO4)2·0.5toluene(1) crystallizes in the triclinic space groupP
cr.gif"> witha = 10.953(5) Å, b = 12.812(5) Å,c = 13.006(5) Å, 
chars/alpha.gif" BORDER=0> = 67.50(3)
, chars/beta2.gif" BORDER=0 ALIGN="middle"> =82.74(3), chars/gamma.gif" BORDER=0 > = 67.88(3), and Z =2.The Hg-Namine bonds are 2.404(4) and2.350(4) Å and the Hg-Npyridyl bond lengths aresimilar, ranging from2.352(4) to 2.557(5) Å. Solution NMR studies areconsistent with rapid equilibrium between isomerictrigonalprismatic and facial octahedral forms of this complex. A twistingmechanism is proposed to mediateinterconversion. The distorted square planar complex[Hg(BMPA)NCCH3](ClO4)2(7) crystallizes in the monoclinicspace group P21/c with a= 12.987(2) Å, b = 17.469(4) Å, c= 8.886(2) Å, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 95.200(12), and Z =4. TheHg-Namine distance is 2.403 Å, the averageHg-Npyridyl distance is 2.23 Å, and theHg-Nnitrile distance is 2.229Å. The BMPA ligand is bound to Hg(II) in a meridionalfashion with a solvent molecule in the same plane andclose associations to two axial perchlorates with Hg-O distances of2.707(7) and 2.90(2) Å. Solution NMRstudies support limited dynamics for a cation with similar interactionsbetween BMPA and Hg(II).
cr.gif"> witha = 10.953(5) Å, b = 12.812(5) Å,c = 13.006(5) Å, chars/alpha.gif" BORDER=0> = 67.50(3), chars/beta2.gif" BORDER=0 ALIGN="middle"> =82.74(3), chars/gamma.gif" BORDER=0 > = 67.88(3), and Z =2.The Hg-Namine bonds are 2.404(4) and2.350(4) Å and the Hg-Npyridyl bond lengths aresimilar, ranging from2.352(4) to 2.557(5) Å. Solution NMR studies areconsistent with rapid equilibrium between isomerictrigonalprismatic and facial octahedral forms of this complex. A twistingmechanism is proposed to mediateinterconversion. The distorted square planar complex[Hg(BMPA)NCCH3](ClO4)2(7) crystallizes in the monoclinicspace group P21/c with a= 12.987(2) Å, b = 17.469(4) Å, c= 8.886(2) Å, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 95.200(12), and Z =4. TheHg-Namine distance is 2.403 Å, the averageHg-Npyridyl distance is 2.23 Å, and theHg-Nnitrile distance is 2.229Å. The BMPA ligand is bound to Hg(II) in a meridionalfashion with a solvent molecule in the same plane andclose associations to two axial perchlorates with Hg-O distances of2.707(7) and 2.90(2) Å. Solution NMRstudies support limited dynamics for a cation with similar interactionsbetween BMPA and Hg(II).