Ruthenium and palladium complexes incorporating amino-azo-phenol ligands: Synthesis, characterization, structure and reactivity

Poulami Pattanayak; Sankar Prasad Parua; Debprasad Patra; C. K. Lai; Paula Brandão; Vitor Felix; Surajit Chattopadhyay

doi:10.1016/j.ica.2015.02.002

Ruthenium and palladium complexes incorporating amino-azo-phenol ligands: Synthesis, characterization, structure and reactivity

Poulami Pattanayak, Sankar Prasad Parua, Debprasad Patra, C. K. Lai, Paula Brandão, Vitor Felix, Surajit Chattopadhyay

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

The ligands 2-((2-aminophenyl)diazenyl)phenol, HOL¹-NH₂, 1a; 2-((2-aminophenyl)diazenyl)-5-methylphenol, HOL²-NH₂, 1b; and 2-((2-aminophenyl) diazenyl)-5-chlorophenol, HOL³-NH₂, 1c, which are abbreviated as HOL-NH₂, 1, afforded the complexes of compositions [(OL-NH)Pd(PPh₃)], 2, and [(OL-NH)Ru(CO)(PPh₃)₂], 3, upon reaction with Na₂PdCl₄ and Ru(CO)₃(PPh₃)₃ respectively. In all the complexes the metals ions, Pd(II) or Ru(II), are coordinated by deprotonated ligand (OL-NH)^2- in tridentate (N, N, O) fashion. X-ray structures of [(OL²-NH)Pd(PPh₃)], 2b, and [(OL¹-NH)Ru(CO)(PPh₃)₂], 3a, were determined to confirm the molecular structures. The cyclic voltammograms of [(OL-NH)Ru(CO)(PPh₃)₂] exhibited two quasi reversible oxidative response near 0.25 and 1.12 V vs. SCE. The nature of HOMO as obtained by DFT calculations has been inspected to have an insight into the redox orbitals. The newly synthesized [(OL-NH)Pd(PPh₃)], 2a, complexes exhibited catalytic activity toward the Suzuki, Heck, Cyanation and amination reactions. Catalytic activity of complex [(OL¹-NH)Ru(CO)(PPh₃)₂], 3a, was examined for the conversion of ketones to corresponding alcohols by transfer hydrogen reactions.

Original language	English
Pages (from-to)	122-131
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	429
DOIs	https://doi.org/10.1016/j.ica.2015.02.002
State	Published - 1 Apr 2015

Keywords

2-((2-Aminophenyl)azo)phenol
C-C coupling reaction
C-N coupling reactions
Crystal structure
Hydrogen transfer reaction
Pd(II) Ru(II)

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10.1016/j.ica.2015.02.002

CCDC 1010802: Experimental Crystal Structure Determination
Pattanayak, P. (Creator), Parua, S. P. (Creator), Patra, D. (Creator), Lai, C. (Creator), Brandão, P. (Creator), Felix, V. (Creator) & Chattopadhyay, S. (Creator), The Cambridge Structural Database, 2015
DOI: 10.5517/cc12xtjb, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12xtjb&sid=DataCite
Dataset
CCDC 1010803: Experimental Crystal Structure Determination
Pattanayak, P. (Creator), Parua, S. P. (Creator), Patra, D. (Creator), Lai, C. (Creator), Brandão, P. (Creator), Felix, V. (Creator) & Chattopadhyay, S. (Creator), The Cambridge Structural Database, 2015
DOI: 10.5517/cc12xtkc, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12xtkc&sid=DataCite
Dataset

Cite this

@article{729f75408df34245a6069c74fb666e32,

title = "Ruthenium and palladium complexes incorporating amino-azo-phenol ligands: Synthesis, characterization, structure and reactivity",

abstract = "The ligands 2-((2-aminophenyl)diazenyl)phenol, HOL1-NH2, 1a; 2-((2-aminophenyl)diazenyl)-5-methylphenol, HOL2-NH2, 1b; and 2-((2-aminophenyl) diazenyl)-5-chlorophenol, HOL3-NH2, 1c, which are abbreviated as HOL-NH2, 1, afforded the complexes of compositions [(OL-NH)Pd(PPh3)], 2, and [(OL-NH)Ru(CO)(PPh3)2], 3, upon reaction with Na2PdCl4 and Ru(CO)3(PPh3)3 respectively. In all the complexes the metals ions, Pd(II) or Ru(II), are coordinated by deprotonated ligand (OL-NH)2- in tridentate (N, N, O) fashion. X-ray structures of [(OL2-NH)Pd(PPh3)], 2b, and [(OL1-NH)Ru(CO)(PPh3)2], 3a, were determined to confirm the molecular structures. The cyclic voltammograms of [(OL-NH)Ru(CO)(PPh3)2] exhibited two quasi reversible oxidative response near 0.25 and 1.12 V vs. SCE. The nature of HOMO as obtained by DFT calculations has been inspected to have an insight into the redox orbitals. The newly synthesized [(OL-NH)Pd(PPh3)], 2a, complexes exhibited catalytic activity toward the Suzuki, Heck, Cyanation and amination reactions. Catalytic activity of complex [(OL1-NH)Ru(CO)(PPh3)2], 3a, was examined for the conversion of ketones to corresponding alcohols by transfer hydrogen reactions.",

keywords = "2-((2-Aminophenyl)azo)phenol, C-C coupling reaction, C-N coupling reactions, Crystal structure, Hydrogen transfer reaction, Pd(II) Ru(II)",

author = "Poulami Pattanayak and Parua, {Sankar Prasad} and Debprasad Patra and Lai, {C. K.} and Paula Brand{\~a}o and Vitor Felix and Surajit Chattopadhyay",

year = "2015",

month = apr,

day = "1",

doi = "10.1016/j.ica.2015.02.002",

language = "???core.languages.en_GB???",

volume = "429",

pages = "122--131",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

}

TY - JOUR

T1 - Ruthenium and palladium complexes incorporating amino-azo-phenol ligands

T2 - Synthesis, characterization, structure and reactivity

AU - Pattanayak, Poulami

AU - Parua, Sankar Prasad

AU - Patra, Debprasad

AU - Lai, C. K.

AU - Brandão, Paula

AU - Felix, Vitor

AU - Chattopadhyay, Surajit

PY - 2015/4/1

Y1 - 2015/4/1

N2 - The ligands 2-((2-aminophenyl)diazenyl)phenol, HOL1-NH2, 1a; 2-((2-aminophenyl)diazenyl)-5-methylphenol, HOL2-NH2, 1b; and 2-((2-aminophenyl) diazenyl)-5-chlorophenol, HOL3-NH2, 1c, which are abbreviated as HOL-NH2, 1, afforded the complexes of compositions [(OL-NH)Pd(PPh3)], 2, and [(OL-NH)Ru(CO)(PPh3)2], 3, upon reaction with Na2PdCl4 and Ru(CO)3(PPh3)3 respectively. In all the complexes the metals ions, Pd(II) or Ru(II), are coordinated by deprotonated ligand (OL-NH)2- in tridentate (N, N, O) fashion. X-ray structures of [(OL2-NH)Pd(PPh3)], 2b, and [(OL1-NH)Ru(CO)(PPh3)2], 3a, were determined to confirm the molecular structures. The cyclic voltammograms of [(OL-NH)Ru(CO)(PPh3)2] exhibited two quasi reversible oxidative response near 0.25 and 1.12 V vs. SCE. The nature of HOMO as obtained by DFT calculations has been inspected to have an insight into the redox orbitals. The newly synthesized [(OL-NH)Pd(PPh3)], 2a, complexes exhibited catalytic activity toward the Suzuki, Heck, Cyanation and amination reactions. Catalytic activity of complex [(OL1-NH)Ru(CO)(PPh3)2], 3a, was examined for the conversion of ketones to corresponding alcohols by transfer hydrogen reactions.

AB - The ligands 2-((2-aminophenyl)diazenyl)phenol, HOL1-NH2, 1a; 2-((2-aminophenyl)diazenyl)-5-methylphenol, HOL2-NH2, 1b; and 2-((2-aminophenyl) diazenyl)-5-chlorophenol, HOL3-NH2, 1c, which are abbreviated as HOL-NH2, 1, afforded the complexes of compositions [(OL-NH)Pd(PPh3)], 2, and [(OL-NH)Ru(CO)(PPh3)2], 3, upon reaction with Na2PdCl4 and Ru(CO)3(PPh3)3 respectively. In all the complexes the metals ions, Pd(II) or Ru(II), are coordinated by deprotonated ligand (OL-NH)2- in tridentate (N, N, O) fashion. X-ray structures of [(OL2-NH)Pd(PPh3)], 2b, and [(OL1-NH)Ru(CO)(PPh3)2], 3a, were determined to confirm the molecular structures. The cyclic voltammograms of [(OL-NH)Ru(CO)(PPh3)2] exhibited two quasi reversible oxidative response near 0.25 and 1.12 V vs. SCE. The nature of HOMO as obtained by DFT calculations has been inspected to have an insight into the redox orbitals. The newly synthesized [(OL-NH)Pd(PPh3)], 2a, complexes exhibited catalytic activity toward the Suzuki, Heck, Cyanation and amination reactions. Catalytic activity of complex [(OL1-NH)Ru(CO)(PPh3)2], 3a, was examined for the conversion of ketones to corresponding alcohols by transfer hydrogen reactions.

KW - 2-((2-Aminophenyl)azo)phenol

KW - C-C coupling reaction

KW - C-N coupling reactions

KW - Crystal structure

KW - Hydrogen transfer reaction

KW - Pd(II) Ru(II)

UR - http://www.scopus.com/inward/record.url?scp=84923592282&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2015.02.002

DO - 10.1016/j.ica.2015.02.002

M3 - 期刊論文

AN - SCOPUS:84923592282

SN - 0020-1693

VL - 429

SP - 122

EP - 131

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Ruthenium and palladium complexes incorporating amino-azo-phenol ligands: Synthesis, characterization, structure and reactivity

Abstract

Keywords

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Datasets

CCDC 1010802: Experimental Crystal Structure Determination

CCDC 1010803: Experimental Crystal Structure Determination

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