fac-/mer-[RuCl(3)(NO)(P-N)] (P-N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine): Synthesis, characterization and DFT calculations


Autoria(s): SILVA, Juliana P. da; CAETANO, Fabio R.; CAVARZAN, Deividi A.; FAGUNDES, Francisco D.; ROMUALDO, Lincoln L.; ELLENA, Javier; JAWORSKA, Maria; LODOWSKI, Piotr; BARISON, Andersson; ARAUJO, Marcio P. de
Contribuinte(s)

UNIVERSIDADE DE SÃO PAULO

Data(s)

20/10/2012

20/10/2012

2011

Resumo

Complex fac-[RuCl(3)(NO)(P-N)] (1) was synthesized from the reaction of [RuCl(3)(H(2)O)(2)(NO)] and the P-N ligand, o-[(N,N-dimethylamino)phenyl]diphenylphosphine) in refluxing methanol solution, while complex mer,trans-[RuCl(3)(NO)(P-N)] (2) was obtained by photochemical isomerization of (1) in dichloromethane solution. The third possible isomer mer, cis-[RuCl(3)(NO)(P-N)] (3) was never observed in direct synthesis as well as in photo-or thermal-isomerization reactions. When refluxing a methanol solution of complex (2) a thermally induced isomerization occurs and complex (1) is regenerated. The complexes were characterized by NMR ((31)P{(1)H}, (15)N{1H} and 1H), cyclic voltammetry, FTIR, UV-Vis, elemental analysis and X-ray diffraction structure determination. The (31)P{(1)H} NMR revealed the presence of singlet at 35.6 for (1) and 28.3 ppm for (2). The (1)H NMR spectrum for (1) presented two singlets for the methyl hydrogens at 3.81 and 3.13 ppm, while for (2) was observed only one singlet at 3.29 ppm. FTIR Ru-NO stretching in KBr pellets or CH(2)Cl(2) solution presented 1866 and 1872 cm(-1) for (1) and 1841 and 1860 cm(-1) for (2). Electrochemical analysis revealed a irreversible reduction attributed to Ru(II)-NO(+) -> Ru(II)-NO(0) at -0.81 V and -0.62 V, for (1) and (2), respectively; the process Ru(II) -> Ru(III), as expected, is only observed around 2.0 V, for both complexes. Studies were conducted using (15)NO and both complexes were isolated with (15)N-enriched NO. Upon irradiation, the complex fac-[RuCl(3)(NO)(P-N)] (1) does not exchange (14)NO by (15)NO, while complex mer, trans-[RuCl(3)(NO)(P-N)] (2) does. Complex mer, trans-[RuCl(3)((15)NO)(P-N)] (2`) was obtained by direct reaction of mer, trans-[RuCl(3)(NO)(P-N)] (2) with (15)NO and the complex fac-[RuCl(3)((15)NO)(P-N)] (1`) was obtained by thermal-isomerization of mer, trans-[RuCl(3)((15)NO)(P-N)] (2`). DFT calculation on isomer energies, electronic spectra and electronic configuration were done. For complex (1) the HOMO orbital is essentially Ru (46.6%) and Cl (42.5%), for (2) Ru (57.4%) and Cl (39.0%) while LUMO orbital for (1) is based on NO (52.9%) and is less extent on Ru (38.4%), for (2) NO (58.2%) and Ru (31.5%). (C) 2011 Elsevier B. V. All rights reserved.

CNPq

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

CAPES

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

FINEP

Financiadora de Estudos e Projetos (FINEP)

Johnson Matthey plc

Johnson Matthey plc

Identificador

INORGANICA CHIMICA ACTA, v.373, n.1, p.8-18, 2011

0020-1693

http://producao.usp.br/handle/BDPI/29893

10.1016/j.ica.2011.03.042

http://dx.doi.org/10.1016/j.ica.2011.03.042

Idioma(s)

eng

Publicador

ELSEVIER SCIENCE SA

Relação

Inorganica Chimica Acta

Direitos

restrictedAccess

Copyright ELSEVIER SCIENCE SA

Palavras-Chave #Nitrosyl #Ruthenium #(15)N-enriched NO #Isomerization #P-N ligand #DFT #X-RAY-STRUCTURE #NITROSYL-RUTHENIUM COMPLEXES #ELECTRONIC-STRUCTURE #NITRIC-OXIDE #PHOSPHINE/DIIMINE COMPLEXES #CATALYTIC-PROPERTIES #EXCITED-STATE #LIGANDS #BOND #DENSITY #Chemistry, Inorganic & Nuclear
Tipo

article

original article

publishedVersion