Synthesis, structural characterization, computational study, and catalytic activity of metal complexes based on tetradentate pyridine/N-heterocyclic carbene ligand

Pei Ling Chiu, Chun Liang Lai, Chiung Fang Chang, Ching Han Hu, Hon Man Lee

Research output: Contribution to journalArticle

127 Citations (Scopus)

Abstract

The ligand precursor [LH2]2+·2Br- (1) for the bis(NHC) ligand with N-picolyl moieties is synthesized in 83% yield. Complexation of 1 with palladium and nickel acetates produced [PdL] 2+·2Br- (2) and [NiL]2+·2Br - (3), respectively, in quantitative yields. Metathesis reactions of 2 and 3 with AgPF6 give the corresponding bromide-free complexes [PdL]2+·2PF6 - (4) and [NiL] 2+·2PF6 - (5). Complexes 2-4 were characterized by X-ray structural determinations, which reveal a highly twisted helical coordination of L around the metal ions. In solution, however, the tetradentate chelate ring undergoes a rapid fluxional process of ring twisting. A theoretical study confirms that the tetradentate coordination of L in 2 and 3 is energetically more favorable than the bidentate chelation mode with dangling picolyl groups. A preliminary application of [NiL]2+·2Br - in Suzuki coupling of aryl halides with phenylboronic acid shows effective activity.

Original languageEnglish (US)
Pages (from-to)6169-6178
Number of pages10
JournalOrganometallics
Volume24
Issue number25
DOIs
StatePublished - Dec 5 2005
Externally publishedYes

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Coordination Complexes
carbenes
catalytic activity
Catalyst activity
pyridines
Ligands
ligands
chelation
metathesis
rings
Palladium
twisting
synthesis
Chelation
Complexation
Bromides
chelates
metals
halides
Metal ions

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Synthesis, structural characterization, computational study, and catalytic activity of metal complexes based on tetradentate pyridine/N-heterocyclic carbene ligand. / Chiu, Pei Ling; Lai, Chun Liang; Chang, Chiung Fang; Hu, Ching Han; Lee, Hon Man.

In: Organometallics, Vol. 24, No. 25, 05.12.2005, p. 6169-6178.

Research output: Contribution to journalArticle

Chiu, Pei Ling ; Lai, Chun Liang ; Chang, Chiung Fang ; Hu, Ching Han ; Lee, Hon Man. / Synthesis, structural characterization, computational study, and catalytic activity of metal complexes based on tetradentate pyridine/N-heterocyclic carbene ligand. In: Organometallics. 2005 ; Vol. 24, No. 25. pp. 6169-6178.
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AU - Hu, Ching Han

AU - Lee, Hon Man

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N2 - The ligand precursor [LH2]2+·2Br- (1) for the bis(NHC) ligand with N-picolyl moieties is synthesized in 83% yield. Complexation of 1 with palladium and nickel acetates produced [PdL] 2+·2Br- (2) and [NiL]2+·2Br - (3), respectively, in quantitative yields. Metathesis reactions of 2 and 3 with AgPF6 give the corresponding bromide-free complexes [PdL]2+·2PF6 - (4) and [NiL] 2+·2PF6 - (5). Complexes 2-4 were characterized by X-ray structural determinations, which reveal a highly twisted helical coordination of L around the metal ions. In solution, however, the tetradentate chelate ring undergoes a rapid fluxional process of ring twisting. A theoretical study confirms that the tetradentate coordination of L in 2 and 3 is energetically more favorable than the bidentate chelation mode with dangling picolyl groups. A preliminary application of [NiL]2+·2Br - in Suzuki coupling of aryl halides with phenylboronic acid shows effective activity.

AB - The ligand precursor [LH2]2+·2Br- (1) for the bis(NHC) ligand with N-picolyl moieties is synthesized in 83% yield. Complexation of 1 with palladium and nickel acetates produced [PdL] 2+·2Br- (2) and [NiL]2+·2Br - (3), respectively, in quantitative yields. Metathesis reactions of 2 and 3 with AgPF6 give the corresponding bromide-free complexes [PdL]2+·2PF6 - (4) and [NiL] 2+·2PF6 - (5). Complexes 2-4 were characterized by X-ray structural determinations, which reveal a highly twisted helical coordination of L around the metal ions. In solution, however, the tetradentate chelate ring undergoes a rapid fluxional process of ring twisting. A theoretical study confirms that the tetradentate coordination of L in 2 and 3 is energetically more favorable than the bidentate chelation mode with dangling picolyl groups. A preliminary application of [NiL]2+·2Br - in Suzuki coupling of aryl halides with phenylboronic acid shows effective activity.

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