The structures of two polymorphs, one triclinic and one monoclinic, of cis-dichlorobis(dibenzyl sulfido-kappaS)platinum(II), cis-PtCl(2)(Bz(2)S)(2), have been determined at 295, 250, 200, 150 and 100 K. In both polymorphs the complex has a structure where platinum(II) coordinates two dibenzyl sulfide molecules and two chloro ligands, forming a complex with pseudo-square-planar coordination geometry. The triclinic polymorph shows disorder at all temperatures. Both polymorphs have a packing arrangement involving centrosymmetric structural dimers. cis-PtCl(2)(Bz(2)S)(2) belongs to a group of complexes with the general formula PtX(2)L(2), where X is a halogen and L is a ligand with a donor atom from groups 14, 15 or 16. The distribution of structural classes among 173 cis-PtX(2)L(2) compounds found in the Cambridge Structural Database (CSD, Version 5.28, November 2006) has been investigated. The predominant structural class [notation according to Belsky & Zorkii (1977). Acta Cryst. A33, 1004-1006] among the cis compounds is P2(1)/c, Z = 4 (1) (73 structures, 42%), followed by P\bar 1, Z = 2 (1) (33 structures, 19%). Inversion centres combined with the screw-axis/glide plane are the dominating packing operators (56%) followed by the inversion centre (21%). The cis and trans influence in cis/trans-PtCl(2)L(2) compounds has been investigated using data from the CSD. The cis influence is small for donor atoms in groups 15 and 16. The trans influence is small for group 16 donor atoms and for nitrogen, but for phosphorus it is significantly greater than the other donor atoms studied.
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http://dx.doi.org/10.1107/S0108768108005211 | DOI Listing |
Chem Sci
January 2025
Chemistry and Physics of Materials Unit, School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur Bangalore 560064 India https://www.jncasr.ac.in/faculty/tmaji.
Coordination-driven metallo-supramolecular polymers hold significant potential as highly efficient catalysts for photocatalytic CO reduction, owing to the covalent integration of the light harvesting unit, catalytic center and intrinsic hierarchical nanostructures. In this study, we present the synthesis, characterization, and gelation behaviour of a novel low molecular weight gelator (LMWG) integrating a benzo[1,2-:4,5-']dithiophene core with terpyridine (TPY) units alkyl amide chains (TPY-BDT). The two TPY ends of the TPY-BDT unit efficiently chelate with metal ions, enabling the formation of a metallo-supramolecular polymer that brings together the catalytic center and a photosensitizer in close proximity, maximizing catalytic efficiency for CO reduction.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
The lanthanide contraction is a widely known phenomenon in which the ionic radii of the Ln ions decrease across the series from La to Lu. As a result, the distance (Ln-Y), where Y is a ligand donor atom, decreases across the series. As shown previously, the decrease normally has a linear dependence on the number of 4f Ln electrons, , and the net change, Δ', is between 0.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland.
Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable "switchable" reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity.
View Article and Find Full Text PDFIUCrJ
March 2025
Department of Chemistry, Università degli Studi di Milano, via Golgi 19, 20133 Milano, Italy.
A detailed study of the X...
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Chemistry Division, Bhabha Atomic Research Centre, Mumbai, 400085, India.
The present study focuses on designing mutant peptides derived from the lanthanide binding tag (LBT) to enhance selectivity for trivalent actinide (An) ions over lanthanide (Ln) metal ions (M). The LBT is a short peptide consisting of only 17 amino acids, and is known for its high affinity towards Ln. LBT was modified by substituting hard-donor ligands like asparagine (ASN or N) and aspartic acid (ASP or D) with softer ligand cysteine (CYS or C) to create four mutant peptides: M-LBT (wild-type), M-N103C, M-D105C, and M-N103C-D105C.
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