Cyclometallation of N,N-dimethyl-2-bromothiobenzamide and some related thioamides with palladium(0) and palladium(II)

Matsuo Nonoyama, Kiyohiko Nakajima, Masakazu Kita

Research output: Contribution to journalArticle

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Abstract

N,N-Dimethyl-2-X-thiobenzamide [XCl (abbreviated as Hcbt) and Br (Hbbt)] and N,N-dimethyl-2-(2-bromophenyl) thioacetamide (Hbpt) were cyclopalladated at one of the N-methyl groups upon reaction with lithium tetrachloroparalladate(II), while oxidative addition took place at the aryl-halogen bond of Hbbt, Hbpt and N,N-dimethyl-2-iodothiobenzamide (Hibt) upon reaction with bis(dibenzylideneacetone)palladium(0). The reaction products, and their tri-n-butylphosphine (PBu3) and 4-tert-butylpyridine (tbp) derivatives, were characterized by IR and NMR spectroscopies. All the complexes were composed of a palladathiaheterocycle with sulphur coordination of a thioamide group. The structure of (N,N-dimethylthiobenzamido) (N,N-diethyldithiocarbamato)palladium(II) was determined by X-ray analysis. There is steric hindrance between one of the NCH3 groups and one benzene ring hydrogen atom. This should result in disfavoured benzene ringccyclopalladation of N,N-dimethylthiobenzamide (Hbt) with lithium tetrachloropalladate(II) and induce NCH3 cyclopalladation.

Original languageEnglish
Pages (from-to)1035-1043
Number of pages9
JournalPolyhedron
Volume14
Issue number8
DOIs
Publication statusPublished - 1995
Externally publishedYes

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Thioamides
Palladium
Benzene
Lithium
palladium
Thioacetamide
Halogens
X ray analysis
lithium
Reaction products
benzene
Sulfur
Nuclear magnetic resonance spectroscopy
Hydrogen
Infrared spectroscopy
Derivatives
reaction products
Atoms
halogens
hydrogen atoms

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Cyclometallation of N,N-dimethyl-2-bromothiobenzamide and some related thioamides with palladium(0) and palladium(II). / Nonoyama, Matsuo; Nakajima, Kiyohiko; Kita, Masakazu.

In: Polyhedron, Vol. 14, No. 8, 1995, p. 1035-1043.

Research output: Contribution to journalArticle

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abstract = "N,N-Dimethyl-2-X-thiobenzamide [XCl (abbreviated as Hcbt) and Br (Hbbt)] and N,N-dimethyl-2-(2-bromophenyl) thioacetamide (Hbpt) were cyclopalladated at one of the N-methyl groups upon reaction with lithium tetrachloroparalladate(II), while oxidative addition took place at the aryl-halogen bond of Hbbt, Hbpt and N,N-dimethyl-2-iodothiobenzamide (Hibt) upon reaction with bis(dibenzylideneacetone)palladium(0). The reaction products, and their tri-n-butylphosphine (PBu3) and 4-tert-butylpyridine (tbp) derivatives, were characterized by IR and NMR spectroscopies. All the complexes were composed of a palladathiaheterocycle with sulphur coordination of a thioamide group. The structure of (N,N-dimethylthiobenzamido) (N,N-diethyldithiocarbamato)palladium(II) was determined by X-ray analysis. There is steric hindrance between one of the NCH3 groups and one benzene ring hydrogen atom. This should result in disfavoured benzene ringccyclopalladation of N,N-dimethylthiobenzamide (Hbt) with lithium tetrachloropalladate(II) and induce NCH3 cyclopalladation.",
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