A novel and simple route for bromide replacement in pyrazolyl-pyridazine ReI tricarbonyl complexes leads to a zwitterion stabilized by hydrogen bonding

Marianela Saldías, Pablo Mella, Nancy Pizarro, Andrés Vega

Resultado de la investigación: Article

Resumen

The reaction of 3-pyrazolyl-pyridazine-6-carboxylic (LCOOH) and 3-3,5-dimethylpyrazolyl-pyridazine-6-carboxylic (Me2LCOOH) acids with bromotricarbonyl-tetrahydrofuran-rhenium(I) dimer in DMF solution followed by water addition, leads simple and cleanly to the rhenium(I) de-halided fac-aquo-tricarbonyl-complexes [(LCOO)(H2O)Re(CO)3] and [(Me2LCOO)(H2O)Re(CO)3] respectively, without the requirement of using a silver salt. It was possible to isolate each compound with the pyrazolyl-pyridazine carboxylate ligand showing the chelating N,O-mode ([(N,O-LCOO)(H2O)Re(CO)3] and [(N,O-Me2LCOO)(H2O)Re(CO)3]). For the [(Me2LCOO)(H2O)Re(CO)3] compound, it was also possible to isolate the ligand as a chelating diimine ([(N,N-Me2LCOO)(H2O)Re(CO)3]). This last coordination mode leads to a zwitterionic but neutral molecule, with a naked carboxylate as negative extreme and the metal with positive charge in the other side. The negative formal charge in the carboxylate is stabilized within the crystal structure of [(N,N-Me2LCOO)(H2O)Re(CO)3] through hydrogen bonds to water molecules from neighboring molecules dimers, with donor acceptor distances (D···A) of 2.566(10)Å and 2.645(6)Å. DFT optimization of the zwitterion in the gas phase suggests that its geometry would twist to allow the formation of an intramolecular hydrogen bond between carboxylate and the coordinated water molecule. This shows the key stabilizing effect of the hydrogen bond for the negative charge of the carboxylate into the zwitterion crystal structure.

Idioma originalEnglish
Número de artículo107621
PublicaciónInorganic Chemistry Communications
Volumen111
DOI
EstadoPublished - ene 2020

Huella dactilar

zwitterions
Carbon Monoxide
Bromides
carboxylates
bromides
Hydrogen bonds
routes
Molecules
Rhenium
hydrogen
Chelation
Dimers
rhenium
hydrogen bonds
Crystal structure
Ligands
molecules
Water
dimers
water

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Citar esto

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title = "A novel and simple route for bromide replacement in pyrazolyl-pyridazine ReI tricarbonyl complexes leads to a zwitterion stabilized by hydrogen bonding",
abstract = "The reaction of 3-pyrazolyl-pyridazine-6-carboxylic (LCOOH) and 3-3,5-dimethylpyrazolyl-pyridazine-6-carboxylic (Me2LCOOH) acids with bromotricarbonyl-tetrahydrofuran-rhenium(I) dimer in DMF solution followed by water addition, leads simple and cleanly to the rhenium(I) de-halided fac-aquo-tricarbonyl-complexes [(LCOO)(H2O)Re(CO)3] and [(Me2LCOO)(H2O)Re(CO)3] respectively, without the requirement of using a silver salt. It was possible to isolate each compound with the pyrazolyl-pyridazine carboxylate ligand showing the chelating N,O-mode ([(N,O-LCOO)(H2O)Re(CO)3] and [(N,O-Me2LCOO)(H2O)Re(CO)3]). For the [(Me2LCOO)(H2O)Re(CO)3] compound, it was also possible to isolate the ligand as a chelating diimine ([(N,N-Me2LCOO)(H2O)Re(CO)3]). This last coordination mode leads to a zwitterionic but neutral molecule, with a naked carboxylate as negative extreme and the metal with positive charge in the other side. The negative formal charge in the carboxylate is stabilized within the crystal structure of [(N,N-Me2LCOO)(H2O)Re(CO)3] through hydrogen bonds to water molecules from neighboring molecules dimers, with donor acceptor distances (D···A) of 2.566(10){\AA} and 2.645(6){\AA}. DFT optimization of the zwitterion in the gas phase suggests that its geometry would twist to allow the formation of an intramolecular hydrogen bond between carboxylate and the coordinated water molecule. This shows the key stabilizing effect of the hydrogen bond for the negative charge of the carboxylate into the zwitterion crystal structure.",
author = "Marianela Sald{\'i}as and Pablo Mella and Nancy Pizarro and Andr{\'e}s Vega",
year = "2020",
month = "1",
doi = "10.1016/j.inoche.2019.107621",
language = "English",
volume = "111",
journal = "Inorganic Chemistry Communication",
issn = "1387-7003",
publisher = "Elsevier BV",

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T1 - A novel and simple route for bromide replacement in pyrazolyl-pyridazine ReI tricarbonyl complexes leads to a zwitterion stabilized by hydrogen bonding

AU - Saldías, Marianela

AU - Mella, Pablo

AU - Pizarro, Nancy

AU - Vega, Andrés

PY - 2020/1

Y1 - 2020/1

N2 - The reaction of 3-pyrazolyl-pyridazine-6-carboxylic (LCOOH) and 3-3,5-dimethylpyrazolyl-pyridazine-6-carboxylic (Me2LCOOH) acids with bromotricarbonyl-tetrahydrofuran-rhenium(I) dimer in DMF solution followed by water addition, leads simple and cleanly to the rhenium(I) de-halided fac-aquo-tricarbonyl-complexes [(LCOO)(H2O)Re(CO)3] and [(Me2LCOO)(H2O)Re(CO)3] respectively, without the requirement of using a silver salt. It was possible to isolate each compound with the pyrazolyl-pyridazine carboxylate ligand showing the chelating N,O-mode ([(N,O-LCOO)(H2O)Re(CO)3] and [(N,O-Me2LCOO)(H2O)Re(CO)3]). For the [(Me2LCOO)(H2O)Re(CO)3] compound, it was also possible to isolate the ligand as a chelating diimine ([(N,N-Me2LCOO)(H2O)Re(CO)3]). This last coordination mode leads to a zwitterionic but neutral molecule, with a naked carboxylate as negative extreme and the metal with positive charge in the other side. The negative formal charge in the carboxylate is stabilized within the crystal structure of [(N,N-Me2LCOO)(H2O)Re(CO)3] through hydrogen bonds to water molecules from neighboring molecules dimers, with donor acceptor distances (D···A) of 2.566(10)Å and 2.645(6)Å. DFT optimization of the zwitterion in the gas phase suggests that its geometry would twist to allow the formation of an intramolecular hydrogen bond between carboxylate and the coordinated water molecule. This shows the key stabilizing effect of the hydrogen bond for the negative charge of the carboxylate into the zwitterion crystal structure.

AB - The reaction of 3-pyrazolyl-pyridazine-6-carboxylic (LCOOH) and 3-3,5-dimethylpyrazolyl-pyridazine-6-carboxylic (Me2LCOOH) acids with bromotricarbonyl-tetrahydrofuran-rhenium(I) dimer in DMF solution followed by water addition, leads simple and cleanly to the rhenium(I) de-halided fac-aquo-tricarbonyl-complexes [(LCOO)(H2O)Re(CO)3] and [(Me2LCOO)(H2O)Re(CO)3] respectively, without the requirement of using a silver salt. It was possible to isolate each compound with the pyrazolyl-pyridazine carboxylate ligand showing the chelating N,O-mode ([(N,O-LCOO)(H2O)Re(CO)3] and [(N,O-Me2LCOO)(H2O)Re(CO)3]). For the [(Me2LCOO)(H2O)Re(CO)3] compound, it was also possible to isolate the ligand as a chelating diimine ([(N,N-Me2LCOO)(H2O)Re(CO)3]). This last coordination mode leads to a zwitterionic but neutral molecule, with a naked carboxylate as negative extreme and the metal with positive charge in the other side. The negative formal charge in the carboxylate is stabilized within the crystal structure of [(N,N-Me2LCOO)(H2O)Re(CO)3] through hydrogen bonds to water molecules from neighboring molecules dimers, with donor acceptor distances (D···A) of 2.566(10)Å and 2.645(6)Å. DFT optimization of the zwitterion in the gas phase suggests that its geometry would twist to allow the formation of an intramolecular hydrogen bond between carboxylate and the coordinated water molecule. This shows the key stabilizing effect of the hydrogen bond for the negative charge of the carboxylate into the zwitterion crystal structure.

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DO - 10.1016/j.inoche.2019.107621

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