Copper(II), cobalt(II), cobalt(III), and tin(IV) 5,10,15,20-tetraphenyl tetrabenzoporphyrinates: Synthesis and properties
摘要:
The complexation reactions of 5,10,15,20-tetraphenyl tetrabenzoporphyrin and the metal exchange reactions of its cadmium(II) complex with copper(II), cobalt(II), and tin(II) acetates and chlorides in a chloroform-methanol mixture and dimethylformamide were studied spectrophotometrically. Corresponding copper(II), cobalt(II), cobalt(II), and tin(IV) porphyrinates were synthesized and identified.
Spectroscopic and Oxidation Studies of <i>meso</i>-Tetraphenyltetrabenzoporphyrin Carbonyl Complexes of Ruthenium(II): CO as the Probe to Elucidate the Bonding Characteristics of Porphyrins
作者:Ru-Jen Cheng、Shang-Ho Lin、Hsiao-Mei Mo
DOI:10.1021/om960653h
日期:1997.5.1
normal porphyrin systems (P). Oxidation studies of Ru(TPTBP)(CO), Ru(TPTBP)(CO)(py), and Ru(TPTBP)(py)2 have been carried out both electrochemically and chemically. 1H NMR, ESR, and electronic spectroscopic studies suggest that there are two different types of oxidation products. The sites of oxidation should both be on the porphyrin ring to give two different types of ruthenium(II) porphyrin π-cation
合成并通过FABMS,UV / vis,1 H NMR和IR光谱对(内-四苯基四苯并卟啉酮)钌(II)的羰基配合物Ru(TPTBP)(CO)进行了表征。研究了具有不同π键结合能力的配体(L = NEt 3,pip,1-MeIm,py,PBu 3)与CO配位的六配位络合物Ru(TPTBP)(CO)(L)。在ν的移位CO为这一系列配合物是其中M→COπ回接的存在相一致。与此相反,以什么将被氮碱度可以预期,ν CO为钌(TPTBP)(CO),钌(TPP)(CO),和Ru(OEP)(CO)的值是1959,1930,和1917厘米-1, 分别。这一结果表明,TPPTP应该比普通的卟啉系统(P)既是更好的σ供体,又是更好的π受体。Ru(TPTBP)(CO),Ru(TPTBP)(CO)(py)和Ru(TPTBP)(py)2的氧化研究已经在电化学和化学上进行。1 H NMR,ESR和电子光谱研究表明,存在
Complexation of Tetraphenyltetrabenzoporphine with Cu(II), Cd(II), Zn(II), and Co(II) Salts in Organic Solvents
作者:D. B. Berezin、O. V. Toldina
DOI:10.1023/b:ruco.0000037437.92306.c1
日期:2004.8
The rate and activation parameters of tetraphenyltetrabenzoporphine (H2TPTBP) complexation with 3d-metal acetates and acetylacetonates are shown to be determined by the solvent nature. With an increase in the electron-donor properties of a solvent, the reaction rate increases due to protonation of N-H bonds and decreases as MA(m)(Solv)(n-m) salt solvates become more stable. As the result, the rate of a reaction with ZnAc2 increases in the series: DMF < DMSO < Py < PrOH-1 < CH3CN < C6H6. In inert and weakly coordinating solvents, the transition state of a reaction is supposed to be formed according to the mechanism of contraction of the salt coordination sphere. The rate of H2TPTBP reaction with metal acetates in pyridine changes in the series: Cu(II) > Cd(II) > Zn(II) > Co(II), while the stability of the obtained complexes decreases in the series Cu(II) > Co(II) > Zn(II) > Cd(II). It is shown that the spectral criterion of the complex stability can be used in the series of metal complexes with one ligand, but it is violated if the ligand structure is changed.
Ligand trans-effect in octahedral complexes of 3d metals and its manifestation in the synthesis of metalloporphyrins in solution
作者:O. V. Toldina、D. B. Berezin、B. D. Berezin
DOI:10.1134/s003602360907016x
日期:2009.7
We study features of the indicator kinetic reaction of meso(tetraphenyl)tetrabenzoporhine with cobalt(II), nickel(II), and manganese(II) acetates in electron-donating organic solvents (N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and pyridine (Py)) and in their binary mixtures at temperatures in the range 348-368 K. Specific features of the trans-effect of solvent molecules on the rate and activation parameters of formation of manganese(II), cobalt(II), nickel(II), and copper(II) complexes with porphyrin are noted.
Berezin; Toldina, Russian Journal of Inorganic Chemistry, 2002, vol. 47, # 12, p. 1910 - 1916
作者:Berezin、Toldina
DOI:——
日期:——
Trans-Effect in Kinetics of Reactions of Mixed Solvates of Cu(II) Acetate with Tetraphenyltetrabenzoporphine in Organic Solvents
作者:D. B. Berezin、O. V. Toldina
DOI:10.1023/b:ruco.0000037438.29051.21
日期:2004.8
The kinetics of complex formation of tetraphenyltetrabenzoporphine with Cu(II) and Zn(II) acetates is studied in individual and mixed coordinating solvents on the basis of DMSO, DMF, and Py. The substantial increase in CuAc2 reactivity in mixed solvents is explained by the trans-effect of ligands in composition of the metal solvate sphere.