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Technologie syntezy fluorofunkcyjnych związków krzemu

Maciejewski H., Karasiewicz J.

Chemik

2012

Vol. 66, nr 7

735-741

W artykule przedstawiono uniwersalną metodę syntezy dla różnorodnych fluorofunkcyjnych pochodnych krzemoorganicznych (silanów, polisiloksanów i silseskwioksanów) w oparciu o procesy hydrosililowania eterów allilowo-fluoroalkilowych, katalizowane siloksylowym kompleksem rodu [{Rh(?-OSiMe3)(cod)}2], im mobilizowanym w cieczy jonowej. Dla powyższego procesu przeprowadzono badania optymalizacyjne i określono podstawowe założenia technologiczne.

A versatile method was presented for synthesis of different fluorofunctional organosilicon derivatives (silanes, polysiloxanes and silsesquioxanes) based on hydrosilylation of allyl-fluoroalkyl ethers. The process of hydrosilylation was catalysed by rhodium siloxide complex [{Rh-OSiMe3)(cod)}2] immobilised in ionic liquid. Studies on optimisation of the above process were performed and a brief foredesign was worked out.

Rhodium complexes with HP(O)R2 (R=Ph, OPh) LIgands-Structure and Catalytic Reactions with Phenylacetylene

Trzeciak A., Ziółkowski J.

Polish Journal of Chemistry

2003

Vol. 77 / nr 5

749-756

In the reaction of Rh(acac)(CO)2 with HP(O)(OPh)2 the hydride rhodium(III) complex, HRh{[P(OPh)2O]2H}2 (1), was obtained. Complex (1) at room temperature catalyzes dimerization of phenylacetylene to trans-diphenylbutenyne (PhCH=CHC_CPh). The reaction of [RhCl(cod)]2 with HP(O)Ph2 and PPh3 led to the following new rhodium complexes: trans-RhCl[P(OH)Ph2]2(PPh3) (2), trans-RhCl[P(OH)Ph2](PPh3)2 (3), HRh[P(OH)Ph2]3 (4) and RhCl2{[PPh2O]2H}2[P(OH)Ph2]2 (5), characterized by 1H and 31P NMR spectra. The hydride complex (4) catalyzes a coupling of HP(O)Ph2 with PhC_CH (phosphorylation reaction) to 1-(diphenylphosphinyl)-2-phenylethene (PhCH=CHP(O)Ph2). In the first step of this reaction (4) reacts with PhC_CH forming alkene complex Rh(CH=CHPh)[P(OH)Ph2]3 (6).

Superoxo rhodium(III) complexes with higher carboxylic and amino-carboxylic acids as ligands

Moszner M., Ziółkowski J. J.

Polish Journal of Chemistry

1998

Vol. 72, nr 11

2357-2365

Replacement of H2O and/or OH(-) ligands in the [Rh2(O2(-))(OH)2(H2O)n](3+)cation by carboxylate ions: RCO2(-) (R=C2H5, C3H7, C4H9, (CH3)3), glycine, L-aspartic acid and L-proline have been studied by electronic and ESR spectra. Two new superoxo rhodium(III) carboxylates formulated as [Rh2(O2(-))(OH)(RCO2)4]n, (R=C2H5 (1), C3H7 (2)), have been synthesized in the reaction between the rhodium (III) superoxo hydroxide, assumed to be [Rh2(O2(-))(OH)2+m(H2O)n-m] with RCO2H. Reaction products were characterized by elemental analysis, UV-VIS, IR, ESR spetroscopies and magnetic susceptibility measurements. The results indicated the formation both the superoxo rhodium(III) carboxylates and amino-carboxylates, containing the [Rh2(O2(-))]5+ core of higher stability in the compounds with the amino-carboxylic acid anions.