The protonation of chlorins (dihydroporphyrins)

Octaethylchlorin forms a violet mono-cation and a deep blue di-cation in two discrete stages on spectrophotometric titration with trifluoroacetic acid in chloroform solution, and similar results are obtained with chlorophyll derivatives although the colour changes are much less pronounced.     

Synthesis of non-aggregating chlorins and isobacteriochlorins from meso-tetrakis(pentafluorophenyl)porphyrin: a study using 1,3-dipolar cycloadditions under mild conditions

The 1,3-dipolar cycloaddition of meso-tetrakis(pentafluorophenyl)porphyrin and its nickel complex, with the bulky azomethine ylide dipole was studied under mild conditions, and yielded chlorin and isobacteriochlorin derivatives self-prevented from aggregation. The reactions were performed at room temperature or 0 °C, and we were able to establish a set of reaction conditions to obtain only the chlorin or the isobacteriochlorin. These compounds were evaluated in solution, and no aggregation was observed at less than 25 mM (∼30 mg mL⁻¹) using ¹H NMR experiments.     

The crystal and molecular structures of bis (pentafluorophenyl)disulphide and bis(pentafluorophenyl)diselenide

The structures of (C₆F₅)₂S₂ and (C₆F₅)₂Se₂ have been determined by single crystal, X-ray diffraction techniques. The compounds are isostructural although the molecules are packed differently in the crystal in comparison with their phenyl analogues. Important bond lengths and angles are: SS, 2.059(4)Å; SeSe, 2.319(4)Å; SC, 1.770Å; SeC, 1.910(15)Å; SSC, 101.3(3)°; SeSeC, 98.8(1)°.     

Neutral bis(pentafluorophenyl)triphenylarsinegold(III) complexes

The complexes XAu(C₆F₅)₂AsPh₃ have been prepared by substitution of chloro- or perchlorato-bis(pentafluorophenyl)triphenylarsinegold(III) with alkali or with silver salts MX (X = NO₃, CH₃COO, NO₂, CF₃COO, CN, SCN, N₃ and C₆H₅COO). Decomposition of the nitrato or acetato complex leads to C₆F₅AuAsPh₃.     

Cationic pentafluorophenyl complexes of platinum(II)

The complex [O₃ClOPt(C₆F₅)(PEt₃)₂] which we have prepared for the first time, is used as a precursor of a series of cationic complexes [LPt(C₆F₅)(PEt₃)₂]ClO₄ (L = PEt₃, AsPh₃, H₂O, CO, OPPh₃, SPPh₃, HNPr₂, py), which are easily obtained by adding L to the perchlorato complex.     

Dichloro-bis(pentafluorophenyl)(chelate) complexes of palladium(IV)

Four organometallic palladium(IV) complexes: Cl₂(C₆F₅)₂Pd(LL) (LL being a bidentate nitrogen-donor ligand) have been prepared by the oxidative addition of chlorine to the corresponding bis(pentafluorophenyl)palladium(II) complexes, (C₆F₅)₂Pd(LL). Some of their properties are described.     

Synthesis of blue imino(pentafluorophenyl)phosphane

The reaction of AgC(6)F(5) with monomeric iminophosphanes of Mes*-N═P-X (X = Cl, I) in CH(2)Cl(2) at ambient temperature gives imino(pentafluorophenyl)phosphane, Mes*N═P(C(6)F(5)) (1), in almost quantitative yield (96%), which could be isolated as a highly viscous blue oil. The same reaction with LiC(6)F(5) results in the formation of imino(amino)phosphane (C(6)F(5))(2)P-N(Mes*)-P═NMes* (2) (yield 93%). In the second series of experiments the analogous reaction of MC(6)F(5) (M = Ag, Li) with dimeric [Cl-P(μ-N-Dipp)](2) was studied, leading to the formation of [R-P(μ-N-Dipp)](2) (R = C(6)F(5)) (3) for M = Ag, while only decomposition products such as P(C(6)F(5))(3) were observed in the reaction with the Li salt. Highly labile Mes*-N═P-C(6)F(5) (1) decomposes at ambient temperatures, forming among other products the diphosphane (C(6)F(5))(2)P-P(C(6)F(5))(2) (4). Reaction of 1 with Fe(2)(CO)(9) yields the iron carbonyl complexes Mes*-N═P(C(6)F(5))·Fe(CO)(4) (5) and [Mes*-N═P(C(6)F(5))](2)·Fe(CO)(3) (6). The structure, bonding, and potential energy surface are discussed on the basis of B3LYP/6-31G(d,p) computations. According to time-dependent B3LYP calculations, the blue color of 1 arises from an n → π* electronic transition.     

Synthesis and structures of tris(pentafluorophenyl)silylamines

Tris(pentafluorophenyl)silylamines were synthesized by silylation of amines and imines with (C₆F₅)₃SiCl or (C₆F₅)₃SiOTf in the presence of triethylamine. The crystal structures of the (C₆F₅)₃SiN(H)CH₂Ph and (C₆F₅)₃SiN(CH=CMe₂)CH₂Ph compounds were studied by X-ray diffraction. The crystal packings were analyzed by quantum chemical calculations in terms of the density functional theory (PBE exchange-correlation functional). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1345–1352, July, 2007.     

Synthesis of tris(cyclopentadienyl)zirconium tetrakis(pentafluorophenyl)borate

Russian Chemical Bulletin - An efficient procedure for the synthesis of tris(cyclopentadienyl)zirconium tetrakis-(pentafluorophenyl)borate [Cp3Zr][B(C6F5)4] was suggested based on the reaction of...     

meso-四(烷氧基苯基)卟啉及其金属络合物的波谱研究

采用^1H NMR、MS、IR、UV、元素分析等分析测试表征手段确证了所合成的10个系列卟啉及其金属络合物的结构,研究了不同位置、不同链长烷氧基四苯基卟啉和不同金属离子卟啉络合物的结构与^1HNMR、IR和UV等波谱之间的关系,总结了卟啉配体及其金属络合物的^1H NMR、IR和UV判据,报道和解释了meso-四(烷氧基苯基)卟啉铜、锰络合物和meso-四(邻烷氧基苯基)卟啉钴络合物的^1H NMR研究结果,通过MS、^1H NMR、IR、UV、元素分析确证了我们所合成的铁卟啉为μ-氧桥联夹心二聚体结构,且存在两种典型构象,导致同系列络合物有四种类型^1H NMR谱图。