Characterization of the first N2S(alkylthiolate)lead compound: a model for three-coordinate lead in biological systems.
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 characterized by X-ray diffraction and by 207Pb NMR. [PATH-Pb]+ is the first reported three-coordinate Pb complex with an alkanethiolate ligand and, hence, is a good model for Pb-cysteine interactions in proteins. The Pb center displays distorted trigonal-planar geometry. The Pb-S bond lengths are extremely short (2.590(10) and 2.597(10) A for two distinct monomers in the unit cell). 207Pb NMR revealed a Pb resonance at 5318 ppm, much further downfield than Pb complexes with N and O ligation. Given recent evidence of three-coordinate Pb-binding in proteins with cysteine-rich metal-binding sites, [PATH-Pb]+ is an important model for Pb sites in biological systems. Crystal data: C12H19N2SPbClO4, Mr = 529.99, monoclinic, P2(1)/n, a = 16.8297(9) A, b = 11.9719(6) A, c = 17.0868(9) A, V = 3237.7(3) A3, and Z = 8.
Andersen
Ryan J
RJ
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA.
diTargiani
Robert C
RC
Hancock
Robert D
RD
Stern
Charlotte L
CL
Goldberg
David P
DP
Godwin
Hilary A
HA
D000478:Alkylation; D007854:Lead / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008954:Models, Biological; D008958:Models, Molecular; D008968:Molecular Conformation; D011336:Probability; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013696:Temperature
D013438:Sulfhydryl Compounds; D007854:Lead