15531-40-5Relevant academic research and scientific papers
Selective borane reduction of phosphinoferrocene carbaldehydes to phosphinoalcohol-borane adducts. the coordination behaviour of 1-(diphenylphosphino)- 1′-(methoxymethyl)ferrocene, a new ferrocene O,P-hybrid donor prepared from such an adduct
Stepnicka, Petr,Cisarova, Ivana
, p. 3373 - 3389 (2013/04/10)
The reduction of ferrocene phosphino-aldehydes, R2PfcCHO (R = Ph, 2; Cy, 3; fc = ferrocene-1,1′-diyl, Cy = cyclohexyl) and (S p)-[Fe(η5-C5H3-1-CHO-2-PPh 2)(η5-C5H5)] ((S p)-4), with BH3·THF or BH3· SMe2 in THF at 0 °C selectively afforded the corresponding phosphinoalcohol-borane adducts, R2PfcCH2OH·BH 3 (R = Ph, 5; Cy, 6) and (Sp)-[Fe(η5-C 5H3-1-CH2OH-2-PPh2) (η5-C5H5)]·BH3 ((S p)-7), in quantitative yields. In contrast, the reactions performed at elevated temperatures favoured the formation of methyl derivatives (e.g., Ph2PfcCH3·BH3 (8)) resulting from overreduction (deoxygenation). The crystal structures of 3, 5, (S p)-7, 8 and Cy2PfcBr (9) have been determined by single-crystal X-ray diffraction analysis. The crystal assemblies of adducts 5 and (Sp)-7 are built up by means of C-H...O contacts, O-H...HB dihydrogen bonds and other soft interactions but, surprisingly, not via the conventional O-H...O hydrogen bonds. Adduct 5 was smoothly deprotected to give the corresponding free phosphine, Ph2PfcCH 2OH (1), and was further used for the preparation of a hybrid phosphinoether ligand, Ph2PfcCH2OMe (11). The latter compound was studied as a donor for Group 8-10 metal ions and for Cu(i), whereupon the following complexes were isolated and structurally characterised: [(η6-p-cymene)RuCl2(11-κP)] (12*), [(η6-p-cymene)RuCl(11-κP)(MeCN)][SbF6] (13*), [RhCl(cod)(11-κP)] (cod = η2: η2-cycloocta-1,5-diene; 14), trans-[PdCl2(11-κP) 2] (trans-15*), [PdCl(μ-Cl)(11-κP)]2 (16*), cis- and trans-[PtCl2(11-κP)2] (cis-17 and trans-17*), and [Cu(CF3SO3-κO)(11- κP)(H2O)] (18) (the asterisk indicates that the crystal structure was determined). In all these compounds, ligand 11 behaves as a P-monodentate donor while its ether group remains uncoordinated. This probably reflects structural flexibility of 11 resulting from the presence of the methylene linker and also distinguishes 11 from its known, non-spaced analogue Ph2PfcOMe.
Synthesis of palladium(II) and platinum(II) complexes with crown ether phosphane ligands: Stille coupling of aryl iodides in water
Fresneda, Jorge,De Jesus, Ernesto,Gomez-Sal, Pilar,Mardomingo, Carmen Lopez
, p. 1468 - 1476 (2007/10/03)
The crown ether phosphanes PAr*Ph2 (1) and PAr*2R [Ar* = 3,4-(18-crown-6)-phenyl; R = Me (2); R = Ph (3)], prepared from PCl2R and Ar*Li, have been studied. The syntheses and characterization of their oxides (4-6), and their BH3 (7-9), PdCl2 (10-12), and PtCl2 (13-15) complexes are reported. The molecular structure of the borane complex PAr* 2Ph·BH3 (9) has been determined by X-ray structural analysis. Spectroscopic data suggest that phosphanes 1-3 have similar electronic properties and steric requirements to the corresponding phenylphosphane ligands PPh2Me and PPh3. Crown ether methylphosphane 2 and its complexes are remarkably water soluble, but 1 and 3 are only slightly soluble. Palladium(II) complexes 14 and 15 have been tested as catalysts in the Stille coupling of phenyltrichlorostannanes and aryl iodides in water.
Reactions of Sodium and Potassium Tetrahydroborates with Triethylenediamine in Diethyl Ether
Mal'tseva,Golovanova
, p. 1221 - 1224 (2008/10/08)
Reactions of sodium and potassium tetrahydroborates with triethylenediamine (TEDA) in diethyl ether is studied. Insoluble in diethyl ether, the tetrahydroborates pass into solution by forming an MBH4 · TEDA complex which, if heated, decomposes to aminoborane and a binary metal hydride. The compounds obtained were characterized by chemical analysis, X-ray diffraction, DTA, IR spectroscopy, and thin-layer chromatography.
