Reactivity of rhenium(V) oxo Schiff base complexes with phosphine ligands: rearrangement and reduction reactions

The symmetric rhenium(V) oxo Schiff base complexes trans-[ReO(OH2)(acac2en)]Cl and trans-[ReOCl(acac2pn)], where acac2en and acac2pn are the tetradentate Schiff base ligands N,N'-ethylenebis(acetylacetone) diimine and N,N'-propylenebis(acetylacetone) diimine, respectively, were reacted with monodentate phosphine ligands to yield one of two unique cationic phosphine complexes depending on the ligand backbone length (en vs pn) and the identity of the phosphine ligand. Reduction of the Re(V) oxo core to Re(III) resulted on reaction of trans-[ReO(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[Re(III)(PR3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[Re(V)O(PEt3)(acac2en)]+ complex. Reactions of trans-[Re(V)O(acac2pn)Cl] with the same phosphine ligands yielded only the rearranged asymmetric cis-[Re(V)O(PR3)(acac2pn)]+ complexes in quantitative yield. The compounds were characterized using standard spectroscopic methods, elemental analyses, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic data for the structures reported are as follows: trans-[Re(III)(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re.PF6), 1, triclinic (P), a = 18.8261(12) A, b = 16.2517(10) A, c = 15.4556(10) A, alpha = 95.522(1) degrees , beta = 97.130(1) degrees , gamma = 91.350(1) degrees , V = 4667.4(5) A(3), Z = 4; trans-[Re(III)(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re.PF6), 2, orthorhombic (Pccn), a = 10.4753(6) A, b =18.4315(10) A, c = 18.9245(11) A, V = 3653.9(4) A3, Z = 4; cis-[Re(V)O(PEt3)(acac2en)]PF6 (H33C18N2O3PRe.1.25PF6, 3, monoclinic (C2/c), a = 39.8194(15) A, b = 13.6187(5) A, c = 20.1777(8) A, beta = 107.7730(10) degrees , V = 10419.9(7) A3, Z = 16; cis-[Re(V)O(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe.PF6), 4, triclinic (P), a = 10.3094(10) A, b =12.1196(12) A, c = 14.8146(15) A, alpha = 105.939(2) degrees , beta = 105.383(2) degrees , gamma = 93.525(2) degrees , V = 1698.0(3) A3, Z = 2; cis-[Re(V)O(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe.PF6), 5, monoclinic (P2(1)/n), a = 18.1183(18) A, b = 11.580(1) A, c = 28.519(3) A, beta = 101.861(2) degrees , V = 5855.9(10) A(3), Z = 4.     

Four-wave-mixing suppression in Er-fiber amplifiers by backward pumping

Amplification of chirped fs-pulses in an Erbium doped fiber amplifier upto 0.8 μJ resulted in an additional peak in the spectrum at 1584 nm. This peak, attributable to four-wave-mixing between the signal centered at 1559 nm and amplified spontaneous emission at 1534 nm, hinders the temporal recompression of the amplified chirped pulse. Compared to the forward pumping configuration, this four-wave-mixing in the amplifier was largely reduced in a backward pumping configuration. Based on simulations, explanations for the observed influence of the pump direction on the four-wave-mixing efficiency are presented. The results pointed out that the gain spectrum distribution along the fiber strongly influences four-wave-mixing effects in fiber amplifiers even for constant overall gain spectrum.     

Ultrafast thulium-doped fiber-oscillator with pulse energy of 4.3 nJ

A femtosecond fiber laser based on thulium-doped double-clad silica fiber with an internal dispersion compensation is presented that generates pulses at a center wavelength of 1976 nm with an energy of 4.3 nJ and a duration of 1.2 ps. The dechirped pulse duration is 294 fs. The pulse energy is more than 2 orders of magnitude above the pulse energy demonstrated previously. Mode locking is achieved using additive pulse mode locking, and dispersion compensation is facilitated by a grating stretcher arrangement.     

Ein Beitrag zur Chemie des Sauerstoff-difluorids

Zusammenfassung Die Gasphasenreaktionen von Sauerstoff-difluorid mit Schwefeldioxid, Thionylfluorid und Schwefeltetrafluorid wurden untersucht, und die hauptsächlich gaschromatographisch bestimmten Reaktionsprodukte werden mitgeteilt. Die für diese Umsetzungen notwendigen relativ hohen Reaktionstemperaturen verhindern die Bildung von Substanzen mit einer Sauerstoff-Fluor-Bindung, so daß nur stabile und bereits bekannte Verbindungen gefunden wurden.     

Über die Darstellung von S2O5F2 aus Fluorsulfonsäure

Zusammenfassung Während die Umsetzung von HSO₃F mit P₂O₅ zu POF₃ führt, kann die Reaktion mit As₂O₅ AsF₅ oder ein flüchtiges Arsenfluoridfluosulfonat ergeben, welches sich zu Pyrosulfuryl-fluorid zersetzen läßt. S₂O₅F₂ ist thermisch in Glas bis über 300° stabil.Herrn Prof. Dr.A. Klemenc zum 70. Geburtstag gewidmet.