Copper(II) complexes bearing cyclobutanecarboxylate and pyridine ligands: a new series of dinuclear paddle-wheel complexes

Monatshefte für Chemie - Chemical Monthly - Four members of a new series of paddle-wheel copper(II) complexes bearing cyclobutanecarboxylate as bridging ligand with pyridine derived ligands in...     

Syntheses, crystal structures, reactivity, and photochemistry of gold(III) bromides bearing N-heterocyclic carbenes

Gold(I) complexes bearing N-heterocyclic carbenes (NHC) of the type (NHC)AuBr (3a/3b) [NHC = 1-methyl-3-benzylimidazol-2-ylidene (= MeBnIm), and 1,3-dibenzylimidazol-2-ylidene (= Bn(2)Im)] are prepared by transmetallation reactions of (tht)AuBr (tht = tetrahydrothiophene) and (NHC)AgBr (2a/2b). The homoleptic, ionic complexes [(NHC)(2)Au]Br (6a/6b) are synthesized by the reaction with free carbene. Successive oxidation of 3a/3b and 6a/6b with bromine gave the respective (NHC)AuBr(3) (4a/4b) and [(NHC)(2)AuBr(2)]Br (7a/7b) in good overall yields as yellow powders. All complexes were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Reactions of the Au(III) complexes towards anionic ligands like carboxylates, phenolates and thiophenolates were investigated and result in a complete or partial reduction to a Au(I) complex. Irradiation of the Au(III) complexes with UV light yield the Au(I) congeners in a clean photo-reaction.     

Synthesis and characterization of a stable bismuth(III) A3-corrole

An efficient metalation procedure for bismuth complexes with meso-substituted corrole ligands is presented. Reaction of 5,10,15-tris-pentafluorophenylcorrole H(3)(TpFPC) with Bi{N(SiMe(3))(3)} converts the free ligand H(3)(TpFPC) to a neutral low-valent species Bi(TpFPC), which has been characterized by different spectroscopic techniques. (Spectro)electrochemical studies were performed in order to describe the redox potentials of the Bi(TpFPC) complex and to ascribe the sites of electron transfer. The first crystal structure of a bismuth corrole is presented and compared to the geometry-optimized molecular structure obtained with density functional theory (DFT) calculations. We show an example of a 4-coordinate metallocorrole with a very large out-of-plane displacement and significant doming. The electronic structure of the novel bismuth corrole system is discussed in detail. Time-dependent DFT results support the proposed assignment of electronic transitions observed for the Bi(TpFPC) derivative. To account for the reactivity we investigated the photocatalytic properties of the Bi(TpFPC) complex.     

5-Organyl-5-phosphaspiro[4.4]nonanes: a contribution to the structural chemistry of spirocyclic tetraalkylphosphonium salts and pentaalkylphosphoranes

Spirocyclic phosphonium salts of the type [(CH(2))(4)P(CH(2))(4)](+) X(-) with X = I(3) (1a), I (1b), picrate (1c), benzoate (1d), and Cl (1e) were prepared from 1,4-diiodobutane and elemental phosphorus followed by metathesis reactions. The crystal structures of 1b and 1c and of 1d(H(2)O) have been determined by X-ray diffraction methods. In the cations of these salts the phosphorus atoms are shared by two five-membered rings in envelop conformations. In the picrate 1c the cations show an unsymmetrical ring folding pattern (point group C(1)), while the geometry of the cations of the iodide 1b and the benzoate hydrate [1d(H(2)O)] approaches the symmetry of point group C(2). These structures can be taken as models for the as yet unknown molecular geometries of the corresponding hydrocarbon (CH(2))(4)C(CH(2))(4) and silane (CH(2))(4)Si(CH(2))(4). Treatment of 1e with organolithium reagents RLi affords spirocyclic pentaorganophosphoranes RP[(CH(2))(4)](2) with R = Me, Et, n-Bu, Vi, and Ph (2a-e) in good (R = Me, Et, n-Bu) to low yields (R = Vi, Ph). The products are isolated as colorless liquids, of which only 2a, 2b, and 2d can be distilled without decomposition. Single crystals of 2a were obtained by low-temperature in situ crystal growth. The molecule has a trigonal bipyramidal configuration with the methyl group in an equatorial position and the two five-membered rings spanning axial/equatorial positions of the polyhedron. Deviations from the standard trigonal bipyramidal geometry are small. The compounds 2a-e are fluctional in solution as demonstrated by NMR spectroscopy.     

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

The heteroaromatic polynitrile compound tetracyanopyridine (TCNPy) is introduced as a new electron acceptor for the formation of deeply colored charge‐transfer complexes. In MeCN, TCNPy is characterized by a quasireversible one‐electron‐reduction process at ?0.51 V (versus SCE). The tetracyanopyridine radical anion undergoes a secondary chemical reaction, which is assigned to a protonation step. TCNPy has been demonstrated to generate 1:1 complexes with various electron donors, including tetrathiafulvalene (TTF) and dihydroxybenzene derivatives, such as p‐hydroquinone and catechol. Visible‐ or NIR‐light‐induced excitation of the intense charge‐transfer bands of these compounds leads to a direct optical electron‐transfer process for the formation of the corresponding radical‐ion pairs. The presence of available electron donors that contain protic groups in close proximity to the TCNPy acceptor site opens up a new strategy for the photocontrolled generation of pyridinium radicals in a stepwise proton‐coupled electron‐transfer (PCET) sequence.     

Silver and gold complexes with a new 1,10-phenanthroline analogue N-heterocyclic carbene: a combined structural, theoretical, and photophysical study

Unusual coordination for gold: an imidazolium salt was synthesized and used as a precursor for an N-heterocyclic carbene, which can be considered as the carbene analogue of 1,10-phenanthroline. Like the diimine congener, this ligand gives luminescent metal complexes. Remarkably, the Au(III) complex features a gold atom in an unusual environment: it is surrounded by six donor atoms, two of which interact electrostatically with the Au atom.     

Unsuccessful/successful attempts to produce penta(heteroaryl)-phosphoranes/-arsoranes R5E (E = P, As; R = 2-furyl, 2-thienyl)

Tri(2-thienyl)phosphine (1) has been transformed into chlorotri(2-thienyl)phosphonium chloride (3) in the reaction with hexachloroethane, into tetra(2-thienyl)phosphonium bromide (4) in a NiBr2-catalyzed quaternization with 2-bromothiophene, and into the p-tolylsulfonyliminotri(2-thienyl)phosphorane (6) using "chloramine T". Attempts to generate the homoleptic penta(2-thienyl)phosphorane (2-C4H3S)5P (5) by treating 3, 4, 6 or the known (PhO)3P=NSO2C6H4-2-Me (9) with 2-thienyllithium were unsuccessful. Tri(2-furyl)phosphine (2) was converted into the related imine 7, but the reaction of 7 or of 9 with 2-furyllithium failed to give (2-C4H3O)5P (8). It was only with the strained phosphorane Ph(C12H8)P=NSO2C6H4-4-Me (C12H8= 2,2'-biphenylylene) (10) that with 2-C4H3OLi the corresponding phosphorane Ph(C12H8)P(C4H3O-2)2 (11) could be obtained (31P NMR: delta-106.7 ppm). In the arsenic series, tri(2-thienyl)- and tri(2-furyl)arsine (12, 13) were converted into the tosylimino compounds (14, 15) and successfully transformed into the homoleptic arsoranes with 2-C4H3E-Li: penta(2-thienyl)- (16) and penta(2-furyl)-arsorane (17) are stable colourless crystalline solids, the NMR spectra of which indicate rapid pseudo-rotation in solution. The single crystal structure analysis of 17 shows an only slightly distorted trigonal-bipyramidal configuration. In crystals of the phosphine 2 and the arsine 13 the molecules have a propeller configuration with approximate C3v symmetry for the former, but Cs symmetry for the latter. The crystal structures of the precursors or intermediates 3, 4, 6, 9, and 10 have also been determined.