Oxidative Addition of RX to Soluble and Polymer‐Bound Molybdenum Carbonyl Complexes

Abstract

Oxidative addition of PhSnCl 3 or allyl halides to molybdenum tetracarbonyl complexes proceeds both in solution and on polymer matrices. The structures of the soluble Mo II complexes have been determined by single-crystal X-ray diffraction in the solid state and by NMR and IR spectroscopy in solution. The identity and stability of the polymer-bound

Solid‐ and Solution‐Phase Synthesis of a Library of Mixed‐Metal Complexes

“…The diffuse-reflectance spectra of the polymer-bound dinuclear complexes 8bϪ16b show broad absorptions in the visible spectral region which can be assigned to the MLCT transitions of the two {(diimine)M(CO) n } chromophores (n ϭ 3 at lower energy; n ϭ 4 at higher energy; Table 4). [4,6] These absorption bands are considerably shifted to lower energy relative to the MLCT bands of the soluble complexes as previously observed for similar immobilised complexes [4Ϫ6] ( Tables 1 and 4). As the energy of the MLCT absorptions is dominated by the solvent polarity (see above and ref.…”

Polymer‐Supported Dioxido‐MoVI Complexes as Truly Functional Molybdenum Oxotransferase Model Systems

“…The immobilised bis(chelate) complex 1b is prepared analogously to 1a employing polymer-supported chelate ligands (Scheme 1 and Scheme 3; ligand loading 0.6-0.8 mmol g -1 polymer; polymer = polystyrene/2 % divinylbenzene). [27][28][29][30][31][32] The amount of molybdenum incorporated by 1b is compatible with the required 2:1 ligand/metal stoichiometry as shown by molybdenum uptake measurements. [23] Thus the molybdenum complexes are anchored to the polymeric backbone by two attachment points which should guarantee the desired site isolation effect (at least for some sites within the polymer).…”

“…Cleaving the Si-O bonds of 1b with fluoride ions releases the hydroxy analogue of 1a into solution confirming the correct formation of 1b. [27][28][29][30][31][32] PMe 3 is oxidised by 1b to OPMe 3 as shown by 31 The anchored Mo VI and Mo IV complexes 1b and 3b were subjected to one-electron reduction and oxidation, respectively (CEPT chemistry). Reaction of 1b with cobaltocene Co(C 5 H 5 ) 2 [33] gave polymer 4b which is EPR-active.…”

Heteroleptic Cu(II) Dipyrromethene Complexes Linked via Hydrogen Bonds, Coordinative Bonds, and Covalent Bonds: Probing the Coordination Environment by Electron Paramagnetic Resonance Spectroscopy

“…There is currently an intense research effort to develop coordination polymers based on molecular precursors held together by forces of varying strength such as hydrogen bonds, coordinative bonds, and covalent bonds for magnetic and electronic materials as well as new classes of adsorbents, sensors, and storage materials. , The covalent immobilization of complexes on polymers has been used in heterogeneous catalysis, , chromatography, and sensing applications , as well as in metal-complex-assisted solid-phase organic synthesis 8-14 and solid-phase synthesis of metal complexes. − …”