Chemical and photochemical behavior of ruthenium nitrosyl complexes with terpyridine ligands in aqueous media
Por:
Labra-Vazquez, Pablo, Boce, Mathilde, Tasse, Marine, Mallet-Ladeira, Sonia, Lacroix, Pascal G., Farfan, Norberto, Malfant, Isabelle
Publicada:
14 mar 2020
Categoría:
Inorganic chemistry
Resumen:
The synthesis and behavior in water of a set of various
cis(Cl,Cl)-[R-tpyRuCl(2)(NO)](PF6) and
trans(Cl,Cl)-[R-tpyRuCl(2)(NO)](PF6) (R = fluorenyl, phenyl,
thiophenyl; tpy = 2,2':6',2 `'-terpyridine) complexes are presented. In
any case, one chlorido ligand is substituted by a hydroxo ligand and the
final species arises as a single trans(NO,OH) isomer, whatever the
nature of the starting cis/trans(Cl,Cl) complexes. Six X-ray crystal
structures are presented for
cis(Cl,Cl)-[thiophenyl-tpyRuCl(2)(NO)](PF6) (cis-3a),
trans(Cl,Cl)-[thiophenyl-tpyRuCl(2)(NO)](PF6) (trans-3a),
trans(NO,OH)-[phenyl-tpyRu(Cl)(OH)(NO)](PF6) (4a),
trans(NO,OH)-[thiophenyl-tpyRu(Cl)(OH)(NO)](PF6) (4b),
trans(NO,OEt)-[phenyl-tpyRu(Cl)(OEt)(NO)](PF6) (5a), and
trans(NO,OH)-[phenyl-tpyRu(Cl)(OEt)(NO)](PF6) (5b) compounds. The
different cis/trans(Cl,Cl) complexes exhibit an intense low-lying
transition in the lambda = 330-390 nm range, which appears to be
slightly blue-shifted after Cl -> OH substitution. In water, both
cis/trans(Cl,Cl) isomers are converted to a single trans(NO,OH) isomer
in which one chlorido- is replaced by one hydroxo-ligand, which avoids
tedious separation workout. The water stable trans(NO,OH)-species all
release NO with quantum yields of 0.010 to 0.075 under irradiation at
365 nm. The properties are discussed with computational analysis
performed within the framework of Density Functional Theory.
Filiaciones:
Labra-Vazquez, Pablo:
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, Toulouse, F-31077, France
Facultad de Química, Departamento de Química Orgánica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Ciudad de México, 04510, Mexico
CNRS, Lab Chim Coordinat, 205 Route Narbonne, F-31077 Toulouse, France
Univ Nacl Autonoma Mexico, Fac Quim, Dept Quim Organ, Ciudad Univ, Ciudad De Mexico 04510, Mexico
Boce, Mathilde:
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, Toulouse, F-31077, France
CNRS, Lab Chim Coordinat, 205 Route Narbonne, F-31077 Toulouse, France
Tasse, Marine:
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, Toulouse, F-31077, France
CNRS, Lab Chim Coordinat, 205 Route Narbonne, F-31077 Toulouse, France
Mallet-Ladeira, Sonia:
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, Toulouse, F-31077, France
CNRS, Lab Chim Coordinat, 205 Route Narbonne, F-31077 Toulouse, France
Lacroix, Pascal G.:
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, Toulouse, F-31077, France
CNRS, Lab Chim Coordinat, 205 Route Narbonne, F-31077 Toulouse, France
Farfan, Norberto:
Facultad de Química, Departamento de Química Orgánica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Ciudad de México, 04510, Mexico
Univ Nacl Autonoma Mexico, Fac Quim, Dept Quim Organ, Ciudad Univ, Ciudad De Mexico 04510, Mexico
Malfant, Isabelle:
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, Toulouse, F-31077, France
CNRS, Lab Chim Coordinat, 205 Route Narbonne, F-31077 Toulouse, France
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