The complex cis,trans,cis-[PtCl(2)(OAc)(2)NH(3)(c-C(6)H(11)NH(2))] (JM-216) is currently undergoing clinical evaluation as an antitumor agent. In support of characterization and analysis of this complex a study of its isomers and other complexes [PtCl(m)()(OAc)((4)(-)(m)()())NH(3)(c-C(6)H(11)NH(2))] (m = 0-4) has been undertaken. The complexes have been obtained by a variety of synthetic routes which now extend the scope for the preparation of platinum(IV) antitumor complexes. As platinum(IV) complexes are very stable to substitution in the absence of catalysis, use has been made of both light and base catalysis to promote substitution. Oxidative addition to platinum(II) using hypervalent iodine reagents has also been used. The stereochemistry of the complexes has been confirmed by spectroscopic studies, primarily NMR including natural abundance (15)N NMR spectroscopy.
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http://dx.doi.org/10.1021/ic951548n | DOI Listing |
Inorg Chem
January 2025
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Science, 630090 Novosibirsk, Russia.
The photoinduced reaction of [Pt(NO)] with pyridine or its derivatives (L) was found to result in the formation of [PtL](NO) salts in high yield. This transformation was successfully probed for methyl- and carboxyethyl-substituted pyridines, and the corresponding [PtL](NO) salts were isolated and fully characterized using single-crystal X-ray diffraction (SCXRD). Anation of the [Pt(py)] cationic complex with N was studied by H NMR spectroscopy in aqueous and water/dimethyl sulfoxide solutions of [Pt(py)](NO).
View Article and Find Full Text PDFDalton Trans
January 2025
Institute of Inorganic Chemistry, Georg-August-Universität Göttingen, Göttingen Tammannstrasse 4, D-37077, Germany.
The reactions of LAlH (L = HC(CMeNAr), Ar = 2,6-PrCH) (1) with diphenylphosphane oxide [PhP(O)H], diphenylphosphinamide [PhP(O)NH], and diaryl/alkyl phosphane [(RO)P(O)H (R = Ph, or Pr)] afford their corresponding compounds with compositions LAl(H)OP(Ph) (2), LAl[OP(Ph)] (3), LAl{[N(H)P(O)(Ph)][OP(Ph)]} (4), LAl(OPr) (5), and LAl(OPh) (6), respectively. These reactions probably undergo a process of dehydrogenation coupling, deaminating dehydrogenation coupling, or chain-breaking coupling. It is noteworthy to mention that the reaction of compound 1 with 2 equiv.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemical and Biomolecular Engineering, University of Houston, Houston, Texas 77204, United States.
Here we demonstrate how a biologically relevant molecule, riboflavin (vitamin B2), operates by a dual mode of action to effectively control crystallization of ammonium urate (NHHU), which is associated with cetacean kidney stones. In situ microfluidics and atomic force microscopy experiments confirm a strong interaction between riboflavin and NHHU crystal surfaces that substantially inhibits layer nucleation and spreading by kinetic mechanisms of step pinning and kink blocking. Riboflavin does not alter the distribution of tautomeric urate isomers, but its adsorption on NHHU crystal surfaces does interfere with the effects of minor urate tautomer by limiting its ability to induce NHHU crystal defects while also suppressing NHHU nucleation and inhibiting crystal growth by 80% at an uncharacteristically low modifier concentration.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
The photochemistry of nitrous acid (HONO) plays a crucial role in atmospheric chemistry as it serves as a key source of hydroxyl radicals (OH) in the atmosphere; however, our comprehension of the underlying mechanism for the photochemistry of HONO especially in the presence of water is far from being complete as the transient intermediates in the photoreactions have not been observed. Herein, we report the photochemistry of microsolvated HONO by water in a cryogenic N matrix. Specifically, the 1:1 hydrogen-bonded water complex of HONO was facially prepared in the matrix through stepwise photolytic O oxidation of the water complex of imidogen (NH-HO) via the intermediacy of the elusive water complex of peroxyl isomer HNOO.
View Article and Find Full Text PDFInorg Chem
January 2025
Institute of Resource Ecology, Helmholtz-Zentrum Dresden-Rossendorf, Dresden 01328, Germany.
Heteroleptic An (An = U, Np) chlorido-ketoenaminate complexes of the type [AnCl(TFB-BuA)(THF)] ( type: , ; TFB-BuA = 4-(-butylamino)-1,1,1-trifluorobut-3-en-2-one) and the homoleptic Np heteroarylalkenolate complexes [Np(PyTFP)] (, PyTFP = 1-(pyridin-2-yl)-3,3,3-trifluoroprop-1-en-2-ol) and [Np(DMOTFP)] (, DMOTFP = 1-(4,5-dimethyloxazol-2-yl)-3,3,3-trifluoroprop-1-en-2-ol) were synthesized and characterized (SC-XRD, NMR, Vis-NIR, MS). While their solid-state structures compare well to those of their uranium analogues, the behavior in solution showed significant differences. The binding motif of the DMOTFP ligand in complex can change to form two different complex isomers, as seen by paramagnetic chemical shifts in NMR experiments.
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