Neutral and cationic half-sandwich arene ruthenium, Cp*Rh and Cp*Ir oximato and oxime complexes: Synthesis, structural, DFT and biological studies

Sanjay Adhikari, Narasinga Rao Palepu, Dipankar Sutradhar, Samantha L. Shepherd, Roger M. Phillips, Werner Kaminsky, Asit K. Chandra, Mohan Rao Kollipara

Research output: Contribution to journalArticle

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Abstract

The reaction of [(p-cymene)RuCl2]2 and [Cp*MCl2]2 (M = Rh/Ir) with chelating ligand 2-pyridyl cyanoxime {pyC(CN)NOH} leads to the formation of neutral oximato complexes having the general formula [(arene)M{pyC(CN)NO}Cl] {arene = p-cymene, M = Ru, (1); Cp*, M = Rh (2); Cp*, M = Ir (3)}. Whereas the reaction of 2-pyridyl phenyloxime {pyC(Ph)NOH} and 2-thiazolyl methyloxime {tzC(Me)NOH} with precursor compounds afforded the cationic oxime complexes bearing formula [(arene)M{pyC(ph)NOH}Cl]+ and [(arene)M{tzC(Me)NOH}Cl]+ {arene = p-cymene M = Ru, (4), (7); Cp*, M = Rh (5), (8); Cp*, M = Ir (6), (9)}. The cationic complexes were isolated as their hexafluorophosphate salts. All these complexes were fully characterized by analytical, spectroscopic and X-ray diffraction studies. The molecular structures of the complexes revealed typical piano stool geometry around the metal center within which the ligand acts as a NN′ donor chelating ligand. The Chemo-sensitivity activities of the complexes evaluated against HT-29 (human colorectal cancer), and MIAPaCa-2 (human pancreatic cancer) cell line showed that the iridium-based complexes are much more potent than the ruthenium and rhodium analogues. Theoretical studies were carried out to have a deeper understanding about the charge distribution pattern and the various electronic transitions occurring in the complexes.

LanguageEnglish
Pages70-81
Number of pages12
JournalJournal of Organometallic Chemistry
Volume820
Early online date4 Aug 2016
DOIs
Publication statusPublished - 1 Oct 2016

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Oximes
Ruthenium
Discrete Fourier transforms
ruthenium
Ligands
Chelation
ligands
Bearings (structural)
synthesis
cancer
Iridium
Rhodium
Charge distribution
iridium
Molecular Structure
rhodium
Pancreatic Neoplasms
cultured cells
X-Ray Diffraction
charge distribution

Cite this

Adhikari, Sanjay ; Palepu, Narasinga Rao ; Sutradhar, Dipankar ; Shepherd, Samantha L. ; Phillips, Roger M. ; Kaminsky, Werner ; Chandra, Asit K. ; Kollipara, Mohan Rao. / Neutral and cationic half-sandwich arene ruthenium, Cp*Rh and Cp*Ir oximato and oxime complexes : Synthesis, structural, DFT and biological studies. In: Journal of Organometallic Chemistry. 2016 ; Vol. 820. pp. 70-81.
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abstract = "The reaction of [(p-cymene)RuCl2]2 and [Cp*MCl2]2 (M = Rh/Ir) with chelating ligand 2-pyridyl cyanoxime {pyC(CN)NOH} leads to the formation of neutral oximato complexes having the general formula [(arene)M{pyC(CN)NO}Cl] {arene = p-cymene, M = Ru, (1); Cp*, M = Rh (2); Cp*, M = Ir (3)}. Whereas the reaction of 2-pyridyl phenyloxime {pyC(Ph)NOH} and 2-thiazolyl methyloxime {tzC(Me)NOH} with precursor compounds afforded the cationic oxime complexes bearing formula [(arene)M{pyC(ph)NOH}Cl]+ and [(arene)M{tzC(Me)NOH}Cl]+ {arene = p-cymene M = Ru, (4), (7); Cp*, M = Rh (5), (8); Cp*, M = Ir (6), (9)}. The cationic complexes were isolated as their hexafluorophosphate salts. All these complexes were fully characterized by analytical, spectroscopic and X-ray diffraction studies. The molecular structures of the complexes revealed typical piano stool geometry around the metal center within which the ligand acts as a NN′ donor chelating ligand. The Chemo-sensitivity activities of the complexes evaluated against HT-29 (human colorectal cancer), and MIAPaCa-2 (human pancreatic cancer) cell line showed that the iridium-based complexes are much more potent than the ruthenium and rhodium analogues. Theoretical studies were carried out to have a deeper understanding about the charge distribution pattern and the various electronic transitions occurring in the complexes.",
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Neutral and cationic half-sandwich arene ruthenium, Cp*Rh and Cp*Ir oximato and oxime complexes : Synthesis, structural, DFT and biological studies. / Adhikari, Sanjay; Palepu, Narasinga Rao; Sutradhar, Dipankar; Shepherd, Samantha L.; Phillips, Roger M.; Kaminsky, Werner; Chandra, Asit K.; Kollipara, Mohan Rao.

In: Journal of Organometallic Chemistry, Vol. 820, 01.10.2016, p. 70-81.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Neutral and cationic half-sandwich arene ruthenium, Cp*Rh and Cp*Ir oximato and oxime complexes

T2 - Journal of Organometallic Chemistry

AU - Adhikari, Sanjay

AU - Palepu, Narasinga Rao

AU - Sutradhar, Dipankar

AU - Shepherd, Samantha L.

AU - Phillips, Roger M.

AU - Kaminsky, Werner

AU - Chandra, Asit K.

AU - Kollipara, Mohan Rao

PY - 2016/10/1

Y1 - 2016/10/1

N2 - The reaction of [(p-cymene)RuCl2]2 and [Cp*MCl2]2 (M = Rh/Ir) with chelating ligand 2-pyridyl cyanoxime {pyC(CN)NOH} leads to the formation of neutral oximato complexes having the general formula [(arene)M{pyC(CN)NO}Cl] {arene = p-cymene, M = Ru, (1); Cp*, M = Rh (2); Cp*, M = Ir (3)}. Whereas the reaction of 2-pyridyl phenyloxime {pyC(Ph)NOH} and 2-thiazolyl methyloxime {tzC(Me)NOH} with precursor compounds afforded the cationic oxime complexes bearing formula [(arene)M{pyC(ph)NOH}Cl]+ and [(arene)M{tzC(Me)NOH}Cl]+ {arene = p-cymene M = Ru, (4), (7); Cp*, M = Rh (5), (8); Cp*, M = Ir (6), (9)}. The cationic complexes were isolated as their hexafluorophosphate salts. All these complexes were fully characterized by analytical, spectroscopic and X-ray diffraction studies. The molecular structures of the complexes revealed typical piano stool geometry around the metal center within which the ligand acts as a NN′ donor chelating ligand. The Chemo-sensitivity activities of the complexes evaluated against HT-29 (human colorectal cancer), and MIAPaCa-2 (human pancreatic cancer) cell line showed that the iridium-based complexes are much more potent than the ruthenium and rhodium analogues. Theoretical studies were carried out to have a deeper understanding about the charge distribution pattern and the various electronic transitions occurring in the complexes.

AB - The reaction of [(p-cymene)RuCl2]2 and [Cp*MCl2]2 (M = Rh/Ir) with chelating ligand 2-pyridyl cyanoxime {pyC(CN)NOH} leads to the formation of neutral oximato complexes having the general formula [(arene)M{pyC(CN)NO}Cl] {arene = p-cymene, M = Ru, (1); Cp*, M = Rh (2); Cp*, M = Ir (3)}. Whereas the reaction of 2-pyridyl phenyloxime {pyC(Ph)NOH} and 2-thiazolyl methyloxime {tzC(Me)NOH} with precursor compounds afforded the cationic oxime complexes bearing formula [(arene)M{pyC(ph)NOH}Cl]+ and [(arene)M{tzC(Me)NOH}Cl]+ {arene = p-cymene M = Ru, (4), (7); Cp*, M = Rh (5), (8); Cp*, M = Ir (6), (9)}. The cationic complexes were isolated as their hexafluorophosphate salts. All these complexes were fully characterized by analytical, spectroscopic and X-ray diffraction studies. The molecular structures of the complexes revealed typical piano stool geometry around the metal center within which the ligand acts as a NN′ donor chelating ligand. The Chemo-sensitivity activities of the complexes evaluated against HT-29 (human colorectal cancer), and MIAPaCa-2 (human pancreatic cancer) cell line showed that the iridium-based complexes are much more potent than the ruthenium and rhodium analogues. Theoretical studies were carried out to have a deeper understanding about the charge distribution pattern and the various electronic transitions occurring in the complexes.

KW - Cytotoxicity

KW - Iridium

KW - Oximes

KW - Rhodium

KW - Ruthenium

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U2 - 10.1016/j.jorganchem.2016.08.004

DO - 10.1016/j.jorganchem.2016.08.004

M3 - Article

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JO - Journal of Organometallic Chemistry

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