Novel hemi-labile pyridyl-imine palladium complexes: Synthesis, molecular structures and reactions with ethylene

William M. Motswainyana; Stephen O. Ojwach; Martin O. Onani; Emmanuel I. Iwuoha; James Darkwa

doi:10.1016/j.poly.2011.07.004

Novel hemi-labile pyridyl-imine palladium complexes: Synthesis, molecular structures and reactions with ethylene

William M. Motswainyana, Stephen O. Ojwach, Martin O. Onani, Emmanuel I. Iwuoha, James Darkwa

Chemical Sciences

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

29 Citations (Scopus)

Abstract

Ligands (2-pyridyl-2-furylmethyl)imine, (L1), (2-pyridyl-2-thiophenemethyl) imine (L2), and (2-pyridyl-2-thiopheneethyl)imine (L3) were synthesized by condensation reactions and obtained in good yields. Reactions of L1-L3 with either [PdClMe(cod)] or [PdCl₂(cod)] gave the corresponding monometallic palladium(II) complexes 1-5 in very good yields. Molecular structures of complexes 1, 4 and 5 indicated that the ligands are bidentate and coordinate to the palladium metal through the imine and pyridine nitrogen atoms. When complexes 3-5 were treated with NaBAr₄, cationic species, 3a, 4a, and 5a were produced which catalyzed polymerization of ethylene though with very low activities. ¹H NMR spectroscopy studies showed that these cationic species were very stable in solution. DFT calculations showed high ethylene coordination barriers to the cationic species 3a, 4a and 5a.

Original language	English
Pages (from-to)	2574-2580
Number of pages	7
Journal	Polyhedron
Volume	30
Issue number	15
DOIs	https://doi.org/10.1016/j.poly.2011.07.004
Publication status	Published - 21 Sept 2011

Keywords

DFT calculations
Ethylene
Hemi-lability
Molecular structures
Palladium complexes
Pyridyl-imine

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.poly.2011.07.004

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title = "Novel hemi-labile pyridyl-imine palladium complexes: Synthesis, molecular structures and reactions with ethylene",

abstract = "Ligands (2-pyridyl-2-furylmethyl)imine, (L1), (2-pyridyl-2-thiophenemethyl) imine (L2), and (2-pyridyl-2-thiopheneethyl)imine (L3) were synthesized by condensation reactions and obtained in good yields. Reactions of L1-L3 with either [PdClMe(cod)] or [PdCl2(cod)] gave the corresponding monometallic palladium(II) complexes 1-5 in very good yields. Molecular structures of complexes 1, 4 and 5 indicated that the ligands are bidentate and coordinate to the palladium metal through the imine and pyridine nitrogen atoms. When complexes 3-5 were treated with NaBAr4, cationic species, 3a, 4a, and 5a were produced which catalyzed polymerization of ethylene though with very low activities. 1H NMR spectroscopy studies showed that these cationic species were very stable in solution. DFT calculations showed high ethylene coordination barriers to the cationic species 3a, 4a and 5a.",

keywords = "DFT calculations, Ethylene, Hemi-lability, Molecular structures, Palladium complexes, Pyridyl-imine",

author = "Motswainyana, {William M.} and Ojwach, {Stephen O.} and Onani, {Martin O.} and Iwuoha, {Emmanuel I.} and James Darkwa",

year = "2011",

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doi = "10.1016/j.poly.2011.07.004",

language = "English",

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T1 - Novel hemi-labile pyridyl-imine palladium complexes

T2 - Synthesis, molecular structures and reactions with ethylene

AU - Motswainyana, William M.

AU - Ojwach, Stephen O.

AU - Onani, Martin O.

AU - Iwuoha, Emmanuel I.

AU - Darkwa, James

PY - 2011/9/21

Y1 - 2011/9/21

N2 - Ligands (2-pyridyl-2-furylmethyl)imine, (L1), (2-pyridyl-2-thiophenemethyl) imine (L2), and (2-pyridyl-2-thiopheneethyl)imine (L3) were synthesized by condensation reactions and obtained in good yields. Reactions of L1-L3 with either [PdClMe(cod)] or [PdCl2(cod)] gave the corresponding monometallic palladium(II) complexes 1-5 in very good yields. Molecular structures of complexes 1, 4 and 5 indicated that the ligands are bidentate and coordinate to the palladium metal through the imine and pyridine nitrogen atoms. When complexes 3-5 were treated with NaBAr4, cationic species, 3a, 4a, and 5a were produced which catalyzed polymerization of ethylene though with very low activities. 1H NMR spectroscopy studies showed that these cationic species were very stable in solution. DFT calculations showed high ethylene coordination barriers to the cationic species 3a, 4a and 5a.

AB - Ligands (2-pyridyl-2-furylmethyl)imine, (L1), (2-pyridyl-2-thiophenemethyl) imine (L2), and (2-pyridyl-2-thiopheneethyl)imine (L3) were synthesized by condensation reactions and obtained in good yields. Reactions of L1-L3 with either [PdClMe(cod)] or [PdCl2(cod)] gave the corresponding monometallic palladium(II) complexes 1-5 in very good yields. Molecular structures of complexes 1, 4 and 5 indicated that the ligands are bidentate and coordinate to the palladium metal through the imine and pyridine nitrogen atoms. When complexes 3-5 were treated with NaBAr4, cationic species, 3a, 4a, and 5a were produced which catalyzed polymerization of ethylene though with very low activities. 1H NMR spectroscopy studies showed that these cationic species were very stable in solution. DFT calculations showed high ethylene coordination barriers to the cationic species 3a, 4a and 5a.

KW - DFT calculations

KW - Ethylene

KW - Hemi-lability

KW - Molecular structures

KW - Palladium complexes

KW - Pyridyl-imine

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DO - 10.1016/j.poly.2011.07.004

M3 - Article

AN - SCOPUS:80052261015

SN - 0277-5387

VL - 30

SP - 2574

EP - 2580

JO - Polyhedron

JF - Polyhedron

IS - 15

ER -

Novel hemi-labile pyridyl-imine palladium complexes: Synthesis, molecular structures and reactions with ethylene

Abstract

Keywords

ASJC Scopus subject areas

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