Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/4943
Título: Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes
Autor: Arroyo, Marta
Gomez-Iglesias, Patricia
Anton, Noelia
Garcia-Rodriguez, Raul
Alegria, Elisabete C. B. A.
Pombeiro, Armando J. L.
Miguel, Daniel
Villafane, Fernando
Palavras-chave: Tricarbonylrhenium(I) bromide complexes
Coordination compounds
Crystal structure
Molecular structure
Electrochemical parametrization
Spectroscopic properties
Asymmetric catalysis
Pyrazole complexes
Ru(II) complexes
Data: 2014
Editora: Royal Society of Chemistry
Citação: ARROYO, Marta; [et al] – Homo-And Heteropolymetallic 3-(2-Pyridyl)Pyrazolate Manganese and Rhenium complexes. Dalton Transactions. ISSN: 1477-9226. Vol. 43, nr. 10 (2104), pp. 4009-4020
Resumo: fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.
Peer review: yes
URI: http://hdl.handle.net/10400.21/4943
DOI: 10.1039/c3dt53439a
ISSN: 1477-9226
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