Cyclometalated platinum(II) complexes of 2,2'-bipyridine N-oxide containing 1,1'-bis(diphenylphosphino)ferrocene ligand: Structural, computational and electrochemical studies

Hamid R. Shahsavari, Masood Fereidoonnezhad, Maryam Niazi, S. Talaat Mosavi, Sayed Habib Kazemi, Reza Kia, Shima Shirkhan, Siamak Abdollahi Aghdam, Paul R. Raithby

Research output: Contribution to journalArticle

5 Citations (Scopus)
113 Downloads (Pure)

Abstract

The preparation and characterization of new heteronuclear-platinum(II) complexes containing 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ2N,C-bipyO-H)(SMe2)], A, in which bipyO-H is a cyclometalated “rollover” 2,2'-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of corresponding binuclear complex [Pt2Me22N,C-bipyO-H)2(µ-dppf)], 1, or mononuclear complex [PtMe(κ1C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelateing ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by single-crystal X-ray diffraction method and it was shown that the chelateing dppf ligand in this complex was arranged “synclinal-staggered” conformation. Also, the occurrence of intermolecular C–HCp…ObipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.
Original languageEnglish
Pages (from-to)2013-2022
Number of pages10
JournalDalton Transactions
Volume46
Issue number6
Early online date13 Jan 2017
DOIs
Publication statusPublished - 14 Feb 2017

Fingerprint

2,2'-Dipyridyl
Platinum
Oxides
Ligands
Molecular orbitals
Nuclear magnetic resonance spectroscopy
Electronic structure
Density functional theory
Conformations
Absorption spectra
ferrocene
1,1'-bis(diphenylphosphino)ferrocene
Single crystals
X ray diffraction
Geometry
Chemical analysis

Cite this

Cyclometalated platinum(II) complexes of 2,2'-bipyridine N-oxide containing 1,1'-bis(diphenylphosphino)ferrocene ligand: Structural, computational and electrochemical studies. / Shahsavari, Hamid R.; Fereidoonnezhad, Masood; Niazi, Maryam; Mosavi, S. Talaat; Kazemi, Sayed Habib ; Kia, Reza; Shirkhan, Shima; Aghdam, Siamak Abdollahi; Raithby, Paul R.

In: Dalton Transactions , Vol. 46, No. 6, 14.02.2017, p. 2013-2022.

Research output: Contribution to journalArticle

Shahsavari, Hamid R. ; Fereidoonnezhad, Masood ; Niazi, Maryam ; Mosavi, S. Talaat ; Kazemi, Sayed Habib ; Kia, Reza ; Shirkhan, Shima ; Aghdam, Siamak Abdollahi ; Raithby, Paul R. / Cyclometalated platinum(II) complexes of 2,2'-bipyridine N-oxide containing 1,1'-bis(diphenylphosphino)ferrocene ligand: Structural, computational and electrochemical studies. In: Dalton Transactions . 2017 ; Vol. 46, No. 6. pp. 2013-2022.
@article{4e54c5bfacce478494abe3b62650d3b3,
title = "Cyclometalated platinum(II) complexes of 2,2'-bipyridine N-oxide containing 1,1'-bis(diphenylphosphino)ferrocene ligand: Structural, computational and electrochemical studies",
abstract = "The preparation and characterization of new heteronuclear-platinum(II) complexes containing 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ2N,C-bipyO-H)(SMe2)], A, in which bipyO-H is a cyclometalated “rollover” 2,2'-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of corresponding binuclear complex [Pt2Me2(κ2N,C-bipyO-H)2(µ-dppf)], 1, or mononuclear complex [PtMe(κ1C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelateing ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by single-crystal X-ray diffraction method and it was shown that the chelateing dppf ligand in this complex was arranged “synclinal-staggered” conformation. Also, the occurrence of intermolecular C–HCp…ObipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.",
author = "Shahsavari, {Hamid R.} and Masood Fereidoonnezhad and Maryam Niazi and Mosavi, {S. Talaat} and Kazemi, {Sayed Habib} and Reza Kia and Shima Shirkhan and Aghdam, {Siamak Abdollahi} and Raithby, {Paul R.}",
year = "2017",
month = "2",
day = "14",
doi = "10.1039/C6DT04085C",
language = "English",
volume = "46",
pages = "2013--2022",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "6",

}

TY - JOUR

T1 - Cyclometalated platinum(II) complexes of 2,2'-bipyridine N-oxide containing 1,1'-bis(diphenylphosphino)ferrocene ligand: Structural, computational and electrochemical studies

AU - Shahsavari, Hamid R.

AU - Fereidoonnezhad, Masood

AU - Niazi, Maryam

AU - Mosavi, S. Talaat

AU - Kazemi, Sayed Habib

AU - Kia, Reza

AU - Shirkhan, Shima

AU - Aghdam, Siamak Abdollahi

AU - Raithby, Paul R.

PY - 2017/2/14

Y1 - 2017/2/14

N2 - The preparation and characterization of new heteronuclear-platinum(II) complexes containing 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ2N,C-bipyO-H)(SMe2)], A, in which bipyO-H is a cyclometalated “rollover” 2,2'-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of corresponding binuclear complex [Pt2Me2(κ2N,C-bipyO-H)2(µ-dppf)], 1, or mononuclear complex [PtMe(κ1C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelateing ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by single-crystal X-ray diffraction method and it was shown that the chelateing dppf ligand in this complex was arranged “synclinal-staggered” conformation. Also, the occurrence of intermolecular C–HCp…ObipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.

AB - The preparation and characterization of new heteronuclear-platinum(II) complexes containing 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand are described. The reaction of the known starting complex [PtMe(κ2N,C-bipyO-H)(SMe2)], A, in which bipyO-H is a cyclometalated “rollover” 2,2'-bipyridine N-oxide, with the dppf ligand in a 2 : 1 ratio or an equimolar ratio led to the formation of corresponding binuclear complex [Pt2Me2(κ2N,C-bipyO-H)2(µ-dppf)], 1, or mononuclear complex [PtMe(κ1C-bipyO-H)(dppf)], 2, respectively. According to the reaction conditions, the dppf ligand in 1 and 2 behaves as either a bridging or chelateing ligand. All complexes were characterized by NMR spectroscopy. The solid-state structure of 2 was determined by single-crystal X-ray diffraction method and it was shown that the chelateing dppf ligand in this complex was arranged “synclinal-staggered” conformation. Also, the occurrence of intermolecular C–HCp…ObipyO-H interactions in the solid-state gave rise to an extended 1-D network. The electronic absorption spectra and the electrochemical behavior of these complexes are discussed. Density functional theory (DFT) was used for geometry optimization of the singlet states in solution and for electronic structure calculations. The analysis of the molecular orbital (MO) compositions in terms of occupied and unoccupied fragment orbitals in 2 was performed.

UR - http://dx.doi.org/10.1039/C6DT04085C

U2 - 10.1039/C6DT04085C

DO - 10.1039/C6DT04085C

M3 - Article

VL - 46

SP - 2013

EP - 2022

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 6

ER -