Characterization of the First N2S(alkylthiolate)lead Compound: A Model for Three-Coordinate Lead in Biological Systems

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• 作者：Ryan J. Andersen ; Robert C. diTargiani ; Robert D. Hancock ; Charlotte L. Stern ; David P. Goldberg ; Hilary A. Godwin
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：August 21, 2006
• 年：2006
• 卷：45
• 期：17
• 页码：6574 - 6576
• 全文大小：55K
• 年卷期：v.45,no.17(August 21, 2006)
• ISSN：1520-510X

文摘

A new N₂S(alkylthiolate)-coordinated Pb²⁺ compound {2-methyl-1-[methyl(2-pyridin-2-ylethyl)amino]propane-2-thiolatolead perchlorate, [PATH-Pb][ClO₄]} has been synthesized and characterizedby X-ray diffraction and by ²⁰⁷Pb NMR. [PATH-Pb]⁺ is the firstreported three-coordinate Pb complex with an alkanethiolate ligandand, hence, is a good model for Pb-cysteine interactions inproteins. The Pb center displays distorted trigonal-planar geometry.The Pb-S bond lengths are extremely short (2.590(10) and2.597(10) Å for two distinct monomers in the unit cell). ²⁰⁷Pb NMRrevealed a Pb resonance at 5318 ppm, much further downfieldthan Pb complexes with N and O ligation. Given recent evidenceof three-coordinate Pb-binding in proteins with cysteine-rich metal-binding sites, [PATH-Pb]⁺ is an important model for Pb sites inbiological systems. Crystal data: C₁₂H₁₉N₂SPbClO₄, M_r = 529.99,monoclinic, P2₁/n, a = 16.8297(9) Å, b = 11.9719(6) Å, c =17.0868(9) Å, V = 3237.7(3) ų, and Z = 8.