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Ligating properties of thionitrosoamines: IV. Cationic complexes of rhodium(I), rhodium(III), and ruthenium(II) containing N-thionitrosodimethylamine
Institution:1. Grupo de Pesquisa em Síntese e Caracterização Molecular de Mato Grosso do Sul, Instituto de Química, Universidade Federal de Mato Grosso do Sul (Laboratório 2), Av. Senador Filinto Muller 1555, Campo Grande, MS 79074-460, Brazil;2. Laboratório de Síntese Inorgânica e Cristalografia, Instituto de Química, Universidade de Brasília, Caixa postal 4478, Brasília, DF 70904-970, Brazil;3. Departamento de Química, Universidade Federal de Santa Maria, Santa Maria, RS 97105-900, Brazil;4. Centro de Desenvolvimento de Tecnologias Químicas, Universidade Estadual de Mato Grosso do Sul, Rua Emilio Mascoli, 275, Naviraí, MS 79950-000, Brazil;1. Department of Chemistry, Pondicherry University, Pondicherry, 605 014, India;2. Department of Chemistry and Biochemistry, School of Basic Science and Research, Sharda University, Greater Noida, 201306, India;1. Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK;2. CatSci Ltd., CBTC2, Capital Business Park, Wentloog, Cardiff CF3 2PX, UK;1. State Environmental Protection Key Lab of Environmental Risk Assessment and Control on Chemical Processes, School of Resources & Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China;2. Université Clermont Auvergne, CNRS, Sigma-Clermont, Institut de Chimie de Clermont-Ferrand, F-63178 Aubière, France;3. Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, PR China;4. Département de Chimie, Université de Skikda, 21000, Algeria;5. Univ Lyon, Université Claude Bernard Lyon 1, CNRS-UMR 5256, IRCELYON, F-69626, 2 Avenue Albert Einstein, Villeurbanne, France
Abstract:The solvento species obtained by treatment of the complexes Rh(1,5-cyclooctadiene)Cl]2, Rh(norbornadiene)Cl]2, Rh(CO)2Cl]2, C5H5Rh(CO)I2, C5Me5RhCl2]2, and Ru(C6H6)Cl2]2 with AgPF6 in acetone or acetonitrile react with a large excess of Me2NNS to give the compounds Rh(1,5-C8H12)-(SNNMe2)2]PF6 (1a), Rh(C7H8)(SNNMe2)2]PF6 (1b), Rh(CO)2(SNNMe2)2]PF6 (2), C5H5Rh(SNNMe2)3](PF6)2 (3), C5Me5Rh(SNNMe2)3](PF6)2 (4), and Ru(C6H6(SNNMe2)3](PF6) (5). If the thionitroso ligand is not preent in large excess decomposition often occurs. The use of AgClO4 allows isolation of the perchlorate salts of 1a, 1b, 2, 4, and 5, and the complexes C5H5Rh-(SNNMe2)2(ClO4)ClO4 (6) and Rh(1,5-C8H12)(SNNMe2)(ClO4) (7). In the H1 NMR spectra the methyl protons of Me2NNS are observed as two quadruplets, in the range δ 3.75–4.25 (4J(HH) ca. 0.7 Hz) because of restricted rotation around the NN bond. The rhodium(I) complexes (1a, 1b, and 2) reacts with PPh3 or p-tolylPPh2 to give labile products, and only Rh(1,5-C8H12)(SNNMe2)(PPh3)]ClO4 (8) and Rh(1,5-C8H12)(SNNMe2)(p-tolylPPh2)]ClO4 (9) were isolated and characterized.
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