TY - JOUR
T1 - Linkage isomerism of (diamine)platinum(II) complexes of sulfur-containing ylidenemalonate ligands
AU - Kim, Kwan Mook
AU - Jun, Moo Jin
AU - Sohn, Youn Soo
PY - 1997
Y1 - 1997
N2 - A 1H NMR study has been carried out on (diamine)platinum(II) complexes of 1,3-dithian-2-ylidenemalonate (DTAYM) and 1,3-dithiepane-2-ylidenemalonate (DTEYM) ligands as anionic leaving group in aqueous solution. Only the O,S-chelated isomer was observed in solution for all the DTAYM complexes regardless of the kind of carrier ligand amine as was in the solid state. However, both O,S- and S,S′-chelated isomers were observed in solution for DTEYM complexes, which show linkage isomerism from the O,S-chelate to the thermodynamically more stable S,S′-chelate. The rate of linkage isomerism of the DTEYM complexes was found to be dependent on their amine co-ligands. Molecular dynamics of the DTAYM complexes was also discussed based on their temperature-dependent NMR spectra. The crystal structure of the S,S′-isomer of (NH3)2Pt(DTEYM) · H2O was determined whereas that of the O,S-isomer could not be obtained due to its poor crystallinity.
AB - A 1H NMR study has been carried out on (diamine)platinum(II) complexes of 1,3-dithian-2-ylidenemalonate (DTAYM) and 1,3-dithiepane-2-ylidenemalonate (DTEYM) ligands as anionic leaving group in aqueous solution. Only the O,S-chelated isomer was observed in solution for all the DTAYM complexes regardless of the kind of carrier ligand amine as was in the solid state. However, both O,S- and S,S′-chelated isomers were observed in solution for DTEYM complexes, which show linkage isomerism from the O,S-chelate to the thermodynamically more stable S,S′-chelate. The rate of linkage isomerism of the DTEYM complexes was found to be dependent on their amine co-ligands. Molecular dynamics of the DTAYM complexes was also discussed based on their temperature-dependent NMR spectra. The crystal structure of the S,S′-isomer of (NH3)2Pt(DTEYM) · H2O was determined whereas that of the O,S-isomer could not be obtained due to its poor crystallinity.
KW - (diamine)platinum(II)
KW - 1,3-dithian-2-ylidenemalonate
KW - 1,3-dithiepane-2-ylidenemalonate
KW - Linkage isomerism
KW - O,S-chelate
KW - S,S′-chelate
UR - http://www.scopus.com/inward/record.url?scp=0037807782&partnerID=8YFLogxK
U2 - 10.1016/s0277-5387(97)00163-0
DO - 10.1016/s0277-5387(97)00163-0
M3 - Article
AN - SCOPUS:0037807782
SN - 0277-5387
VL - 16
SP - 3705
EP - 3711
JO - Polyhedron
JF - Polyhedron
IS - 21
ER -