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Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

Publisher Summary This chapter discusses advances in the theoretical and physical aspects of spin–spin coupling constants. From both theoretical and experimental points of view, the analysis of high-resolution NMR parameters is an important problem, and its significance for the understanding of molecular electronic structure can hardly be stressed enough. When both approaches are taken together, an excellent example of the Born–Opperheimer approximation is obtained because experimentalists measure transitions among nuclear states that are modified by the interactions among magnetic nuclei, external magnetic field, and electrons, while theoreticians study the way the electronic wave function is modified owing to those interactions. The empirical Hamiltonian describes the way nuclear spin energy levels are modified both by the static magnetic field provided by a spectrometer and by the interactions between magnetic nuclei and electrons belonging to a given molecule.

Advances in theoretical and physical aspects of spin-spin coupling constants

4,4’-Bipyridine (1) and its N-alkylated congeners are classic organic building blocks that have been utilized in a variety of fields, such as photochemistry, electrochemistry, solarenergy conversion, and as bridging ligands in metallosupramolecular assemblies, or molecular wires. Methylviologen MV, or paraquat, easily accessible from 4,4’-bipyridine by methylation (Scheme 1), is frequently used as a photo-

3,7‐Diazadibenzophosphole Oxide: A Phosphorus‐Bridged Viologen Analogue with Significantly Lowered Reduction Threshold

A series of dithieno[3,2-b:2′,3′-d]phosphole-based transition metal complexes, including Au, Fe, Pt, Rh and W as central metals have been synthesised and characterised. Structural investigations by X-ray single crystal crystallography supported the high degree of π-conjugation in the dithienophosphole ligands. This essential requirement for potential applications in molecular electronics and optoelectronics provides small band gaps for the materials. Investigations toward the optoelectronic properties of the respective complexes by fluorescence spectroscopy indicated that systematic alterations of the electronic structure are connected to different variables such as transition metal employed, functionalisation of the dithienophosphole ligands as well as complex geometries. The investigated Pt-based complexes exhibit only poor photoluminescence whereas Rh-, W- and Fe-based species with silyl functionalised dithienophosphole ligands show appreciable photophysical properties. The Au complexes investigated exhibit strong photoluminescence properties with very intriguing features in terms of excitation and emission wavelengths, intensity as well as selectivity.

Synthesis and optoelectronic properties of transition metal complexes incorporating dithieno[3,2-b:2′,3′-d]phosphole ligands

Eine einfache synthese von tripod-liganden H3CC(CH2PAr2)3: Anwendungsbreite und komplexchemie

Chromium, molybdenum, and tungsten carbonyl complexes of phenyldibenzophosphole

Synthesis of unsymmetrical bidentate and tridentate phosphines by [4+2] Diels-Alder cycloadditions and michael additions of (phosphole)- and (vinylphosphine)molybdenum carbonyl complexes

Proton and 13C NMR parameters have been determined for phenyldibenzophosphole and its oxide, sulfide, selenide and W(CO)5 complex from high-resolution one- and two-dimensional (COSY, HETCOR and 2DJ) experiments at 4.7, 7.1 and 9.4 tesla. Assignments of chemical shifts and coupling constants have been made and verified by computer simulation of the proton spectra. The data are discussed in relation to the geometry and electron density at phosphorus and the diamagnetic anisotropy of the W(CO)5 group.

1H and 13C nuclear magnetic resonance of phenyldibenzophosphole and derivatives: Complete assignment using two-dimensional J-resolved and shift correlation methods

Electrochemistry of 1-phenyldibenzophosphole complexes of group 6 metal carbonyls

Synthesis of Unsymmetrical Bidentate and Tridentate Phosphines by (4 + 2) Diels-Alder Cycloadditions and Michael Additions of (Phosphole)- and (Vinylphosphine)molybdenum Carbonyl Complexes.

Salina. Affandi

Papers

Chromium, molybdenum, and tungsten carbonyl complexes of phenyldibenzophosphole

Synthesis of unsymmetrical bidentate and tridentate phosphines by [4+2] Diels-Alder cycloadditions and michael additions of (phosphole)- and (vinylphosphine)molybdenum carbonyl complexes

1H and 13C nuclear magnetic resonance of phenyldibenzophosphole and derivatives: Complete assignment using two-dimensional J-resolved and shift correlation methods

Electrochemistry of 1-phenyldibenzophosphole complexes of group 6 metal carbonyls

Synthesis of Unsymmetrical Bidentate and Tridentate Phosphines by (4 + 2) Diels-Alder Cycloadditions and Michael Additions of (Phosphole)- and (Vinylphosphine)molybdenum Carbonyl Complexes.