The Phosphinophosphinidene-phosphoranes tBu2P? P = P(R)tBu2 from Li(THF)2[η2-(tBu2P)2P] and Alkyl Halides We report the formation of tBu2P? P = P(R)tBu2 a and (tBu2)2PR b (with R = Me, Et, nPr, iPr, nBu, PhCH2, H2C = CH? CH2 and CF3) reactions of Li(THF)2[η2-(tBu2P)2P] 2 with MeCl, MeI, EtCl, EtBr, nPrCl, nPrBr, iPrCl, nBuBr, PhCH2Cl, H2C = CH? CH2Cl or CF3Br. In THF solutions the ylidic compounds a predominate, whereas in pentane the corresponding triphosphanes b are preferrably formed. With ClCH2? CH = CH2 only b is produced; CF3Br however yields both tBu2P? P = P(Br)tBu2 and tBu2P? P = P(CF3)tBu2, but no b . The ratio of a:b is influenced by the reaction temperature, too. The compounds tBu2P? P = P(Et)tBu2 4a and (tBu2P)2PEt 4 b , e. g., are produced in a ratio of 4:3 at ?70°C in THF, and 1:1 at 20°C; whereas 1:1 is obtained at ?70°C in pentane, and 1:2 at 20°C. Neither tBuCl nor H2C = CHCl react with 2 . The compounds a decompose thermally or under UV irradiation forming tBu2PR and the cyclophosphanes (tBu2P)nPn. 相似文献
Synthesis, Crystal Structure and Spectroscopic Characterization of [Au12(PPh)2(P2Ph2)2(dppm)4Cl2]Cl2 The reaction of [(AuCl)2dppm] (dppm = Ph2PCH2PPh2) with P(Ph)(SiMe3)2 in CHCl3 results in the formation of [Au12(PPh)2(P2Ph2)2(dppm)4Cl2]Cl2 ( 1 ), the crystal structure of which was determined by single crystal X‐ray analysis (space group P21/c, a = 1425.3(3) pm, b = 2803.7(6) pm, c = 2255.0(5) pm, β = 95.00(3)°, V = 8977(3)·106 pm3, Z = 2). The dication in 1 consists of two Au6P3 units built by highly distorted Au3P and Au2P2 heterotetrahedra, connected via four bidentate phosphine ligands. Additionally, the compound was characterized by IR‐, UV‐ and NMR spectroscopy. The 31P{1H} NMR spectrum is discussed in detail. 相似文献
Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu2P? P?P(Me)tBu21, tBu(Me3Si)P? P?P(Me)tBu22, and tBu2P? P?P(Br)tBu23 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me2SO4 or CH3Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P21/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R2P? P(?)? P(+)(X)R2. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R2P? P(X)? PR2. 相似文献
me3Si? CCl2?Sime2Cl (me ? CH3) läßt sich mit n-buLi (bu ? C4H9) bei–100°C (Lösungsmittel THF/Äther) in me3Si? CCl(Li)? Sime2Cl a überführen. das mit meJ me3Si? CClme? Sime2Cl bildet. Wird a in Abwesenheit eines Abfangreagenzes langsam erwärmt, so bildet sich unter Abspaltung von LiCl (Cl aus der SiCl-Gruppe) über eine reaktive Zwischenstufe des Bicyclobutans b . Die Struktur von b ist durch NMR-Untersuchung, Röntgenstrukturanalyse und Abbaureaktionen gesichert. Mit HBr bzw. CH3OH werden die Si? C-Bindungen der Dreiringe in b gespalten, so daß sich me3Si? CH2? C(Sime2X)2Sime3 (X ? Br, OCH3) bildet. Formation of Organosilicon Compounds. 85. Formation, Reactions, and Structure of 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl)-1,3-disilabicyclo[1, 1, 0]butane me3Si? CCl2? Sime2Cl (me ? CH3) with n-buLi (bu ? C4H9) at –100°C (solvent: THF/ether) yields me3Si? CCl(Li)? Sime2Cl a , which forms me3Si? CClme? Sime2Cl with meI. By warming a slowly in absence of any trapping reagent the bicyclobutane b is obtained via a reactive intermediate under elimination of LiCl (Cl from the SiCl group). The structure of b is established by nmr investigations, X-ray structure determination and chemical derivatisation. 相似文献
Infusions of medicinal plants are investigated by potentiometry using a system of K3[Fe(CN)6]/K4[Fe(CN)6]. Models of some flavonoids, phenol carbonic acids, ascorbic acid, and their mixtures are studied. The total polyphenol concentration in these samples is determined by the Folin–Ciocalteu method. Dependences of antioxidant activity on extraction time are obtained. 相似文献
Dinuclear complexes of CuII with 3-(3,5-dimethylpyrazol-1-yl)-6-(2-hydroxyethylami-no)-1,2,4,5-tetrazine (1) and CoII with 3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5- tetrazine (2) were synthesized and structurally characterized, and the magnetic (SQUID) and resonance (EPR) properties of van der Waals crystals based on these complexes were studied. Unusual behavior of the effective magnetic moment μeff(T) is observed at T < 60 K. A nonmonotonic increase in μeff(?) for 1 (s~6 %) and a 20% reduction of μeff(?) for 2 have a common origin and are due to the influence of spin-orbital coupling on the character of the splitting between the t2g and eg levels of the central ion. Distortions of the coordination site “switch on” a positive (1) or negative (2) contribution of the orbital magnetic moment near 6 K. Irreversible temperature behavior of μeff(T) in the heating and cooling regimes in the vicinity of 60 K suggests that the character of structural distortions and the magnetic properties are related to ligand geometry. This factor plays a significant role in crystal engineering of magnetoactive structures with polynitrogen ligands. 相似文献
We present the results of synthesis and study of the electrocatalytic activity of gold and silver nanoparticles of different composition (individual metals, core–shell particles, nanoalloys, and particles synthesized electrochemically), immobilized on the surface of a glassy carbon electrode, with respect to cholesterol. A surfactant (cetyltrimethylammonium bromide) is selected to create an aqueous–organic emulsion of cholesterol. It is demonstrated that nanoparticles with a gold core and a silver shell with the regression equation of I = 1.4 × 10–5cchol + 5.8 × 10–5 (R2 = 0.97) and silver nanoparticles synthesized electrochemically with the regression equation of I = 1.0 × 10–5cchol + 3.0 × 10–4 (R2 = 0.95) possess optimal electrocatalytic characteristics. 相似文献