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

8 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)70-81
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 - Synthesis, structural, DFT and biological studies

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

VL - 820

SP - 70

EP - 81

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

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