1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

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Chemical Redox Agents for Organometallic Chemistry

Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications.

Propolis is a resinous substance collected by honeybees from various plant sources. The composition of propolis depends on time, vegetation, and the area of collection. This study examined the antioxidant activity of propolis from various areas of Korea:  Chilgok, Cheongju, Geochang, Muju, Pocheon, and Sangju. Ethanol extracts of propolis (EEP) were prepared and evaluated for their antioxidant activity by β-carotene bleaching, 1,1-diphenyl-2-picrylhydrazyl free radical scavenging, and 2,2‘-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation decolorization assays. Furthermore, the major constituents in EEP were identified by high-performance liquid chromatography analysis with a photodiode array and mass spectrometric detection, and each component was quantitatively analyzed. EEP from Cheongju and Muju had relatively strong antioxidant activity accompanied by high total polyphenol contents. Propolis from Cheongju contained large amounts of antioxidative compounds, such as caffeic acid, kaempfer...

Antioxidant Activity and Constituents of Propolis Collected in Various Areas of Korea

Phosphoraneiminato complexes of transition metals

Bis(diphenylphosphino)amine and related chemistry

Iodine oxidation of the isoelectronic anions [N(PPh2)2]– and [HC(PPh2)2]– affords the structurally characterized P–P coupling product Ph2P–NPPh2–PPh2N–PPh2 and the P–C coupling product (Ph2P)2CPPh2–CH2–PPh2, respectively; the P–P heterocoupling product Ph2P–NPPh2–PPh2CH–PPh2 is obtained in the cross-coupling experiment of Li[N(PPh2)2] and Li[HC(PPh2)2] with iodine at –40 °C.

Polyfunctional ligands: comparative oxidative coupling of [E(PPh2)2]–(E = CH, N) with iodine

Cyclophosphazene Metal Oxides, a New Class of Compounds, and Model Compounds for the Polymerization of Phosphazenes

Cyclophosphazenmetalloxide, eine neue Verbindungsklasse, und Modellverbindungen für Polymerisationen von Phosphazenen

The reaction of HN[P(NMe2)2NSiMe3]2 with NaH and KH in 1 : 1 molar ratio yielded a dimer {NaN[P(NMe2)2NSiMe3]2}21 and a polymer {KN[P(NMe2)2NSiMe3]22 with a zigzag chain structure, respectively. The reaction of Ca[N(SiMe3)2]2·2thf (thf = tetrahydrofuran) with the phosphazene in 1 : 2 molar ratio in hexane resulted in the formation of a monomeric spirocyclic phosphazene complex Ca{N[P(NMe2)2NSiMe3]2}23 where the mode of chelation is tridentate. The crystal structures of 1–3 have been determined.

Metallation of the acyclic phosphazene ligand HN[P(NMe2)2NSiMe3]2. Synthesis and crystal structure of {NaN[P(NMe2)2NSiMe3]2}2, {KN[P(NMe2)2NSiMe3]2}∞ and Ca{N[P(NMe2)2NSiMe3]2}2

TiCl4 bildet mit S(NSiMe3)2 und Me2S(NSiMe3)2 ein 1 : 1 Addukt (1, 2), wahrend Ph2S(NSiMe3)2 die disubstituierte Verbindung Ph2S(NTiCl3)2X4 THF 3 ergibt, die in der Raumgruppe P1 kristallisiert. Setzt man TiCl4 mit (Me3Si)2NPPh2NPPh2NSiMe3 um, so wird die imidische Silylgruppe gegen eine TiCl3-Einheit ausgetauscht. Das Molekul, in dem das Ti-Atom nur vierfach koordiniert ist, bildet in der Raumgruppe P21/c Einkristalle. In den Komplexen von CpTiCl3, Cp*TiCl3 und Cp*TiF3 mit Ph2P(NSiMe3)2H erfolgt ebenfalls keine Chelatisierung wie die Einkristall-Rontgenstrukturanalyse von Cp*TiCl2NPPh2NHSiMe36 belegt. Verbindung 6 kristallisiert in der Raumgruppe P1.



New Complexes of Titanium with Silylated Aminoiminophosphorane and Sulfodiimide Ligands



TiCl4 forms a 1 : 1 adduct with S(NSiMe3)2 to give compound 1 and with Me2S(NSiMe3)2 compound 2, respectively. The reaction of TiCl4 with Ph2S(NSiMe3)2 yields the disubstituted compound Ph2S(NTiCl3)2X4THF 3 which crystallizes in space group P1. Reaction of TiCl4 with (Me3Si)2NPPh2NPPh2NSiMe3 leads to an exchange of one silyl group with a TiCl3 moiety. In this molecule the Ti-atom is only four-coordinated. The compound crystallizes in the space group P21/c. No chelate complexes are formed by reactions of CpTiCl3, Cp*TiCl3 and Cp*TiF3 with Ph2P(NSiMe3)2H, this is shown by X-ray structural analysis of Cp*TiCl2NPPh2NHSiMe36. Crystals of 6 are obtained in space group P1.

Reinhard Hasselbring

Papers

Polyfunctional ligands: comparative oxidative coupling of [E(PPh2)2]–(E = CH, N) with iodine

Cyclophosphazene Metal Oxides, a New Class of Compounds, and Model Compounds for the Polymerization of Phosphazenes

Cyclophosphazenmetalloxide, eine neue Verbindungsklasse, und Modellverbindungen für Polymerisationen von Phosphazenen

Metallation of the acyclic phosphazene ligand HN[P(NMe2)2NSiMe3]2. Synthesis and crystal structure of {NaN[P(NMe2)2NSiMe3]2}2, {KN[P(NMe2)2NSiMe3]2}∞ and Ca{N[P(NMe2)2NSiMe3]2}2

Neue Komplexe des Titans mit silylierten Aminoiminophosphoran- und Sulfodiimidliganden