TY - JOUR
T1 - Cyclometallation of N,N-dimethyl-2-bromothiobenzamide and some related thioamides with palladium(0) and palladium(II)
AU - Nonoyama, Matsuo
AU - Nakajima, Kiyohiko
AU - Kita, Masakazu
N1 - Funding Information:
tute for Molecular Science, Okazaki, for allowing the use of facilities for X-ray diffraction measurement and computation. Thanks are also due to Miss S. Nomura of the Chemical Materials Centre, Institute for Molecular Science, for elemental analyses. The present study was partly supported by a Grant-in-Aid for Scientific Research No. 06640720 from the Ministry of Education, Science and Culture.
PY - 1995/4
Y1 - 1995/4
N2 - 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.
AB - 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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U2 - 10.1016/0277-5387(94)00346-G
DO - 10.1016/0277-5387(94)00346-G
M3 - Article
AN - SCOPUS:0040899353
SN - 0277-5387
VL - 14
SP - 1035
EP - 1043
JO - Polyhedron
JF - Polyhedron
IS - 8
ER -