The heteroscorpionate ligand bis(3,5-di-tert-butylpyrazol-1-yl)dithioacetate (bdtbpzdta) has been synthesized by reacting bis(3,5-di-tert-butylpyrazol-1-yl)methane with n-BuLi and CS2. The ligand was isolated as [bis(3,5-di-tert-butylpyrazol-1-yl)dithioacetato](tetrahydrofuran)lithium(I) tetrahydrofuran monosolvate, [Li(C24H39N4S2)(C4H8O)]·C4H8O or [Li(bdtbpzdta)(THF)]·THF, in which the lithium cation is bound by the κ(3)N,N',S-coordinated heteroscorpionate ligand. A similar coordination mode is observed for a zinc chloride complex bearing the bdtbpzdta ligand, namely [bis(3,5-di-tert-butylpyrazol-1-yl)dithioacetato]chloridozinc(II), [Zn(C24H39N4S2)Cl] or [Zn(bdtbpzdta)Cl], which exhibits κ(3)N,N',S-coordination and resembles the active site of zinc-containing peptide deformylases (PDFs).
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http://dx.doi.org/10.1107/S0108270113021148 | DOI Listing |
RSC Adv
October 2024
Department of Chemistry, Marquette University Milwaukee Wisconsin 53201-1881 USA
A series of rhenium and manganese carbonyl complexes of a heteroscorpionate ligand with an atypical NP-donor set has been prepared to better understand their electronic and CO releasing properties. Thus, the ligand, pzTTP, with an ,-bis(pyrazol-1-yl)tolyl group decorated with an -situated di(-tolyl)phosphanyl reacts with carbonyl group 17 reagents to give [-(κNP-pzTTP)Re(CO)Br], 1, and [-(κNP-pzTTP)M(CO)](OTf = OSCF), 2-M (M = Re, Mn), if care is taken during the preparation of the manganeses derivative. When heated in CHCN, 2-Mn slowly transforms to [,-(κNP-pzTTP)Mn(CO)(NCCH)](OTf), 3-Mn.
View Article and Find Full Text PDFDalton Trans
October 2024
LCC, CNRS and Université de Toulouse (UPS, INP), 205 Route de Narbonne, F-31077 Toulouse, France.
In this paper, we report the synthesis of six novel triazole-based heteroscorpionate ligands based on heterocycle metathesis reactions and their iron(II) complexes. Single crystal structure analyses were performed, the spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships were compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post-synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior at room temperature.
View Article and Find Full Text PDFInorg Chem
August 2024
Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States.
Locally high-spin iron hydrides are proposed to play a critical role as intermediates in iron-molybdenum cofactor (FeMoco)-catalyzed N fixation. Inspired by these biological systems, we report herein our initial investigations into low-coordinate iron hydride chemistry supported by our N,N,C-heteroscorpionate ligands. Those ligands with smaller steric profiles are unable to completely suppress the formation of a binuclear [Fe(μ-H)] complex; however, the incorporation of more substantial steric bulk allows for the isolation of a rare example of a terminal, high-spin ( = 2) Fe hydride.
View Article and Find Full Text PDFInorg Chem
July 2024
Universidad de Castilla-La Mancha, Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas, Instituto Regional de Investigación Científica Aplicada-IRICA, Ciudad Real 13071, Spain.
Inorg Chem
May 2024
Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049 001 Lisboa, Portugal.
The borane-functionalized (BR) bis(3,5-dimethylpyrazolyl)methane () ligands (BR: 9-borabicyclo[3.3.1]nonane or 9-BBN), (BR: BCy), and (BR: B(CF)) were synthesized by the allylation-hydroboration of .
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