TY - JOUR
T1 - Kinetic studies on thiolato-ligand substitution reactions with halide ions of square-planar palladium(II) complex with bis(2-(diphenylphosphino)ethyl)phenylphosphine
AU - Aizawa, Sen ichi
AU - Sone, Yasushi
AU - Kawamoto, Tatsuya
AU - Yamada, Shinkichi
AU - Nakamura, Motoshi
N1 - Funding Information:
This research was supported by Grant-in-Aid for Scientific Research (No. 12640583) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
PY - 2002/10/14
Y1 - 2002/10/14
N2 - The square-planar thiolato palladium(II) complex with a terdentate phosphine bound ligand, [Pd(pt)(p3)](BF4) (p3=bis(2-(diphenylphosphino)ethyl)phenylphosphine, pt=1-propanethiolate) has been synthesized and characterized by 31P NMR spectroscopy. The solid state structure of [PdI(p3)]I was determined by an X-ray crystal structure analysis. The kinetic parameters for the thiolato-ligand substitution reactions with halide ions, [Pd(pt)(p3)]++X-→[PdX(p3)] ++pt- (X-=Cl-, Br-, I-), in chloroform were obtained as follows: k298=7.22, 1.68 and 10.1×10-4 s-1, ΔH‡=67±2, 56±2 and 63±3 kJ mol-1 and ΔS‡=-80±7, -128±6 and -92±11 J mol-1 K-1, respectively. These kinetic results are compared with those for the corresponding reactions of the trigonal-bipyramidal complex with an analogous phosphine bound ligand, [Pd(pt)(pp3)](BF4) (pp3=tris(2-(diphenylphosphino)ethyl)phosphine).
AB - The square-planar thiolato palladium(II) complex with a terdentate phosphine bound ligand, [Pd(pt)(p3)](BF4) (p3=bis(2-(diphenylphosphino)ethyl)phenylphosphine, pt=1-propanethiolate) has been synthesized and characterized by 31P NMR spectroscopy. The solid state structure of [PdI(p3)]I was determined by an X-ray crystal structure analysis. The kinetic parameters for the thiolato-ligand substitution reactions with halide ions, [Pd(pt)(p3)]++X-→[PdX(p3)] ++pt- (X-=Cl-, Br-, I-), in chloroform were obtained as follows: k298=7.22, 1.68 and 10.1×10-4 s-1, ΔH‡=67±2, 56±2 and 63±3 kJ mol-1 and ΔS‡=-80±7, -128±6 and -92±11 J mol-1 K-1, respectively. These kinetic results are compared with those for the corresponding reactions of the trigonal-bipyramidal complex with an analogous phosphine bound ligand, [Pd(pt)(pp3)](BF4) (pp3=tris(2-(diphenylphosphino)ethyl)phosphine).
KW - Reaction mechanism
KW - Square-planar palladium(II) complexes
KW - Substitution reaction
KW - Thiolato complexes
UR - http://www.scopus.com/inward/record.url?scp=0037078716&partnerID=8YFLogxK
U2 - 10.1016/S0020-1693(02)00981-7
DO - 10.1016/S0020-1693(02)00981-7
M3 - 学術論文
AN - SCOPUS:0037078716
SN - 0020-1693
VL - 338
SP - 235
EP - 239
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -