70423-99-3Relevant academic research and scientific papers
Multiple isomerism (cis/trans; syn/anti) in [(dmso) 2Pt(aryl)2] complexes: A combined structural, spectroscopic, and theoretical investigation
Klein, Axel,Schurr, Thilo,Knoedler, Axel,Gudat, Dietrich,Klinkhammer, Karl-Wilhelm,Jain, Vimal K.,Zalis, Stanislav,Kaim, Wolfgang
, p. 4125 - 4131 (2008/10/09)
The occurrence of cis or trans configurations in square planar diarylbis(dimethyl sulfoxide)-platinum(II) complexes with S-bonded dmso ligands and aryl = 2,3,4,5,6-pentamethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2-, 3-, and 4-methylphenyl, and phenyl has been investigated by multinuclear (1H, 13C, and 195Pt) NMR spectroscopy and crystal structure analysis. Both methods confirm the cis configuration for complexes with the smaller phenyl and methylphenyl (tolyl) ligands and the trans configuration for the compounds with the bulkier ligands, starting from 2,6-dimethylphenyl. Spectroscopic criteria could thus be established to identify configurational isomers. For the 2-tolyl complex an additional kind of isomerism arises from the relative orientation of the two methyl substituents on the same side (syn) or on different sides of the coordination plane (anti). 2D-NMR spectroscopy allowed us to identify the conformers and to study isomerization mechanisms. DFT calculation results agree well with the experimental structures and with the spectroscopic data.
Dissociative substitution in four-coordinate planar platinum (II) complexes. Kinetics of sulfoxide exchange and displacement by bidentate ligands in the reactions of cis-diarylbis(dimethyl sulfoxide)platinum(II) in chloroform and benzene
Lanza, Santo,Minniti, Domenico,Moore, Peter,Sachinidis, John,Romeo, Raffaello,Tobe, Martin L.
, p. 4428 - 4433 (2008/10/08)
The kinetics of the exchange of dimethyl sulfoxide with cis-[Pt(C6H5)2(Me2SO)2] in CDCl3 have been followed by stopped-flow 1H NMR, and the rate law, rate = (k1 + k2[Me2SO]) [complex], has been established. At 300 K, k1 = 7.9 × 10-2 s-1 and k2 = 1.0 × 10-1 M-1 s-1, the latter pathway making only a minor contribution that may be due to changes in the bulk solvent. The reaction cis-[Pt(Ph)2(Me2SO)2] + bpy = [Pt(Ph)2(bpy)] + 2Me2SO takes place in a single observable step whose rate is determined by the displacement of the first sulfoxide, and the kinetic form is consistent with competition between Me2SO and the chelate for a reactive intermediate. The reactions of the bis(sulfoxide) complex with 2,2′-bipyridyl, 1,10-phenanthroline, and 1,2-bis(diphenylphosphino)ethane have been studied spectrophotometrically in benzene. The sulfoxides are displaced, and the rate law -d[complex]/dt = {k1k3[L-L]/(k-1[Me2SO] + k3[L-L]) + k2[L-L]}[complex] is established. Only in the case where L-L = (diphenylphosphino)ethane does the k2 pathway make any significant contribution. k1 is independent of the nature of L-L, 1.8 × 10-2 s-1 at 303.2 K, ΔH1≠ = 15.3 ± 0.4 kcal mol-1, and ΔS1≠ = -16 ± 2 cal K-1 mol-1, while k3/k-1 = 0.049 ± 0.007, 0.26 ± 0.01, and 5.6 ± 0.8 for bpy, phen, and dppe, respectively, at 303.2 K. For dppe, k2 = 10 ± 0.7 M-1 s-1 at 303.2 K. The reactions of cis-[Pt(4-MeC6H4)2(Me2SO) 2] are similar. A dissociative mechanism with [Pt(R)2(Me2SO)] as reactive intermediate has been demonstrated in both solvents.
Synthesis of Platinum(II) Alkyl and Aryl Complexes from K2 and Tetraorganotin Compounds in Dimethyl Sulphoxide
Eaborn, Colin,Kundu, Kalipada,Pidcock, Alan
, p. 933 - 938 (2007/10/02)
Complexes cis- and cis-(dmso=dimethyl sulphoxide) are readily obtained from K2 and SnMe3R (R=aryl or Me) in dmso at 70-90 deg C.Hydrogen-1 n.m.r. spectra show that the dmso ligands are bound through sulphur in solution an
