TY - JOUR
T1 - Synthesis and structural characterization of cobalt(III) complexes of hybrid donor-type didentate or tetradentate ligands bearing dimethylphosphino and thioether groups
AU - Kashiwabara, Kazuo
AU - Taguchi, Norihiko
AU - Takagi, Hideo D.
AU - Nakajima, Kiyohiko
AU - Suzuki, Takayoshi
N1 - Funding Information:
by a Grant-in-Aid for Scientific Research No. 08640709 from Ministry of Education, Science and Culture, Japan.
PY - 1998
Y1 - 1998
N2 - The preparation and characterization of new hybrid donor-type phosphine-thioether ligands, a linear tetradentate Me2P(CH2)2S(CH2) 3S(CH2)2PMe2 (dmdtn) and a didentate Me2P(CH2)2SR [R = Me (mtdmp) or Et (etdmp)], and their cobalt(III) complexes are described. The reaction of trans-[CoCl2(py)4]Cl (py = pyridine) with dmdtn, followed by anion metathesis with NaPF6, afforded green crystals of trans(Cl,Cl)-[CoCl2{weio(S)-dmdtn}]PF6 (1), whose geometrical structure and configuration around S atoms were determined by X-ray analysis. Further reaction of 1 with Li(acac) (acac = pentane-2,4-dionate) and crystallization with LiBF4 gave red crystals of the acac complex 2. The X-ray analysis of 2 confirmed the structure and configuration of cisβ-[Co(acac) {racemic(S)-dmdtn}](BF4)2, indicating the configurational inversion at one sulfur during the derivation of complex 2. An analogous N.N-dimethyldithiocarbamate (dtc) complex 3 was also prepared, and the electrochemical properties of complexes 1-3 were discussed. For analogous mtdmp and etdmp (P-S) complexes, (rans(Cl,Cl)cis(P,P)-[CoCl2(P-S)2]PF6 reacted with Li(acac) to give not only trans(P,S)-[Co(acac)(P-S)2](PF6)2 but also [Co(acac)2(P-S)]PF6. Similar reactions with Na(dtc) yielded cis-[Co(dtc)2(P-S-κP)2] (14 for P-S = mtdmp), together with trans(P,S)-[Co(dtc)(P-S)2](PF6)2 and [Co(dtc)2(P-S)]PF6. The structures of these complexes were characterized by NMR and UV-visible spectroscopy and X-ray analysis of 14. These results suggested that the didentate ligands were hemilabile as similar to previously described SPPS-type tetradentate ligands, but the tetradentate dmdtn ligand was not.
AB - The preparation and characterization of new hybrid donor-type phosphine-thioether ligands, a linear tetradentate Me2P(CH2)2S(CH2) 3S(CH2)2PMe2 (dmdtn) and a didentate Me2P(CH2)2SR [R = Me (mtdmp) or Et (etdmp)], and their cobalt(III) complexes are described. The reaction of trans-[CoCl2(py)4]Cl (py = pyridine) with dmdtn, followed by anion metathesis with NaPF6, afforded green crystals of trans(Cl,Cl)-[CoCl2{weio(S)-dmdtn}]PF6 (1), whose geometrical structure and configuration around S atoms were determined by X-ray analysis. Further reaction of 1 with Li(acac) (acac = pentane-2,4-dionate) and crystallization with LiBF4 gave red crystals of the acac complex 2. The X-ray analysis of 2 confirmed the structure and configuration of cisβ-[Co(acac) {racemic(S)-dmdtn}](BF4)2, indicating the configurational inversion at one sulfur during the derivation of complex 2. An analogous N.N-dimethyldithiocarbamate (dtc) complex 3 was also prepared, and the electrochemical properties of complexes 1-3 were discussed. For analogous mtdmp and etdmp (P-S) complexes, (rans(Cl,Cl)cis(P,P)-[CoCl2(P-S)2]PF6 reacted with Li(acac) to give not only trans(P,S)-[Co(acac)(P-S)2](PF6)2 but also [Co(acac)2(P-S)]PF6. Similar reactions with Na(dtc) yielded cis-[Co(dtc)2(P-S-κP)2] (14 for P-S = mtdmp), together with trans(P,S)-[Co(dtc)(P-S)2](PF6)2 and [Co(dtc)2(P-S)]PF6. The structures of these complexes were characterized by NMR and UV-visible spectroscopy and X-ray analysis of 14. These results suggested that the didentate ligands were hemilabile as similar to previously described SPPS-type tetradentate ligands, but the tetradentate dmdtn ligand was not.
KW - Cobalt(III)
KW - Dimethylphosphino group
KW - Hemilabile
KW - Hybrid donor-type ligand
KW - Tetradentate ligand
KW - Thioether
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U2 - 10.1016/S0277-5387(97)00526-3
DO - 10.1016/S0277-5387(97)00526-3
M3 - Article
AN - SCOPUS:0000887422
SN - 0277-5387
VL - 17
SP - 1817
EP - 1829
JO - Polyhedron
JF - Polyhedron
IS - 11-12
ER -