J. Appl. Cryst.の発刊に際して

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

N-Heterocyclic Carbenes in Late Transition Metal Catalysis

The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of β-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Keywords: Time-Resolved Fluorescence ; Resonance Energy-Transfer ; Near-Infrared Luminescence ; Double-Stranded Dna ; Prostate-Specific Antigen ; Photoinduced Electron-Transfer ; Europium-Tetracycline Complex ; Sybr-Green-I ; Terbium Complexes ; Optical Probes Reference EPFL-ARTICLE-149396doi:10.1021/cr900362eView record in Web of Science Record created on 2010-06-17, modified on 2017-05-12

Lanthanide Luminescence for Biomedical Analyses and Imaging

Isolation of C–H⋯C(π) complexes from the reaction of stable carbenes with hydrocarbons

Reaction of (tris(trimethylsilyl)silyl)lithium with halophosphines. A novel silicon-halogen exchange reaction

The Reaction of (CF3P)4 with Some Compounds with Nonmetal–Nonmetal Bonds

The first tandem autotransformations of heteroaromatic carbenes have been found. These reactions involve cleavage of the 1-tert-butyl-3,4-diaryl-1,2,4-triazol-5-ylidenes 1a-d to form benzonitriles and the respective carbodiimides, followed by further reactions of the latter with carbenes 1a-d to afford the 3,4-diaryl-5-(1-tert-butyl-3-arylamidin-2-yl)-1,2,4-triazoles 5a-d. The X-ray structures of the carbene 1-tert-butyl-3-phenyl-4-n-bromophenyl-1,2,4-triazol-5- ylidene (1a) and the amidinotriazole 3-phenyl-4-p-bromophenyl-5-(1-tert-butyl-3-p- bromophenylamidin-2-yl)-1,2,4-triazole (5a) were determined. The reactions of 1a with the electrophiles diphenylcarbodiimide, acetonitrile, and diphenyldiazomethane are also described.

Tandem transformations of 1,2,4-triazol-5-ylidenes into 5-amidino-1,2,4-triazoles

Treatment of Na[Co2(CO)2(η-C5H5)2] with R1PCl2(R1= 2,4,6-But3C6H2) results in a dicobalt phosphinidene complex, [Co2(CO)2(η-C5H5)2(µ-PR1)], of the ‘open’ type containing a trigonal-planar phosphorus, no metal–metal bond, and some degree of Co–P multiple bonding as established by an X-ray diffraction study. The attempted synthesis of di-iron phosphinidene complexes via the reaction of [NEt4]2[Fe2(CO)8] with dichlorophosphines RPCl2 failed to produce an isolable species containing the desired phosphinidene fragment. For R =(Me3Si)2CH a large number of products were formed, two of which were isolated and identified within the same crystal structure by X-ray crystallography. Both complexes were found to contain a di-iron centre bridged by a phosphido ligand: [Fe2(CO)6(µ-OH){µ-PH[CH(SiMe3)2]}] and [Fe2(CO)7(µ-H){µ-P(OH)[CH(SiMe3)2]}]. In contrast, for R = R1, a mixture of mono- and di-nuclear iron species were observed by 31P n.m.r. spectroscopy, these being [Fe2(CO)6(µ-PHR1)2], [Fe(CO)4{PH[CH2C(Me)2C6H2But2]}], [Fe(CO)4(PH2R1)], and also the diphosphine R1PHPHR1. In addition to the synthetic and structural studies, extended Huckel molecular orbital calculations have been carried out on model phosphinidene complexes in an attempt to understand their electronic and structural features.

Alan H. Cowley

Papers

Isolation of C–H⋯C(π) complexes from the reaction of stable carbenes with hydrocarbons

Reaction of (tris(trimethylsilyl)silyl)lithium with halophosphines. A novel silicon-halogen exchange reaction

The Reaction of (CF3P)4 with Some Compounds with Nonmetal–Nonmetal Bonds

Tandem transformations of 1,2,4-triazol-5-ylidenes into 5-amidino-1,2,4-triazoles

Synthesis and structures of phosphinidene and phosphido complexes of iron and cobalt