1162-70-5Relevant academic research and scientific papers
Synthetic access and luminescence tuning in a series of β-H and β-silyl substituted phospholes
Klintuch, Dieter,Kirchmeier, Andreas,Bruhn, Clemens,Pietschnig, Rudolf
, (2020/04/27)
Starting from substituted 1,3-diynes a straightforward strategy to prepare phospholes has been explored for a series of substituents with electron poor and electron rich character (C6H5, C6H4CF3, C6F4OCH3, C5H4N, C4H3S, C4H3O, C6H4OCH3). The reaction involves formal addition of PhPTMSLi to the diyne resulting in the respective β-silyl phosphole bearing the substituents of the diyne in the α-positions. Subsequent desilylation afforded the corresponding β-H substituted phospholes which otherwise are difficult to obtain or inaccessible. The β-H phospholes showed attractive luminescence features including high quantum yields. Their β-silyl analogs revealed hypsochromic shifts in their absorption bands as a consequence of reduced coplanarity of the adjacent rings in vicinity of the silyl unit owing to steric repulsion. The structure property relationship was established on structural data from the solid state, quantum chemical DFT calculations and experimental UV vis and luminescence spectra. The identity of all new compounds was established using multinuclear NMR, mass spectrometry, elemental analysis and XRD where available.
Practical Synthesis and Properties of 2,5-Diarylarsoles
Ishidoshiro, Makoto,Matsumura, Yoshimasa,Imoto, Hiroaki,Irie, Yasuyuki,Kato, Takuji,Watase, Seiji,Matsukawa, Kimihiro,Inagi, Shinsuke,Tomita, Ikuyoshi,Naka, Kensuke
, p. 4854 - 4857 (2015/10/12)
2,5-Diarylarsoles were easily synthesized from nonvolatile arsenic precursors. Diiodoarsine was generated in situ and reacted with titanacyclopentadienes to give 2,5-diarylarsoles. The structures and optical properties were studied in comparison with those of 2,5-diarylphosphole. It was found that the arsoles were much more stable in the air than the phosphole. Single crystal X-ray diffraction revealed the arsenic atoms adopted a trigonal pyramidal structure, reflecting on the s-character of the lone pair. The obtained 2,5-diarylarsoles and 2,5-diarylphosphole showed intense emission in solutions and solid state. In addition, the optical properties were controlled by transition-metal coordination.
New pinene-derived pyridines as bidentate chiral ligands
Malkov, Andrei V.,Stewart-Liddon, Angus J.P.,Teply, Filip,Kobr, Luká?,Muir, Kenneth W.,Haigh, David,Ko?ovsky, Pavel
, p. 4011 - 4025 (2008/09/20)
A synthesis of new bidentate pyridines 8a-d, 9, and 10 has been developed, starting from triflate 14, readily available from β-pinene 11. A copper complex of the pyridine-oxazoline ligands 8a has been found to catalyze asymmetric allylic oxidation of cyclic olefins 36a-c with good conversion rates and acceptable enantioselectivity (≤67% ee). The imidazolium salt 10 has been identified as a precursor of the corresponding N,N′-unsymmetrical N-heterocyclic carbene ligand, whose complex with palladium catalyzed the intramolecular amide enolate α-arylation leading to oxindole 45 in excellent yield but with low enantioselectivity.
Structure and stereochemistry of a 7-phosphabicyclohept-2-ene-7-oxide from X-ray, multinuclear NNR, and 2D-J resolved NMR studies
Hocking, Martin B.,Bushnell, Gordon W.
, p. 1020 - 1028 (2007/10/02)
Preparations of a 7-phosphanorbornene, from the reaction of 1,2,5-triphenylphosphole-1-oxide with inhibited acrylonitrile in benzene, were repeated under various conditions to determine if one, or more than one, stereoisomer was formed.Adduct formation fa
MOESSBAUER STUDIES ON FERROCENE COMPLEXES. IX. PHOSPHAFERROCENES AND THEIR PROTONATED DERIVATIVES
Lukas, B.,Roberts, R. M. G.,Silver, J.,Wells, A. S.
, p. 103 - 110 (2007/10/02)
A number of mono- and di-phosphaferrocenes have been synthesised and their NMR (1H, 31P) and Moessbauer spectra measured.The presence of a phosphorus atom in the cyclopentadienyl (Cp) moiety causes a reduction of about 0.3 mm s-1 in the quadrupole splitting (QS) compared with that of ferrocene.The effect appears to be additive, as does the effect of Cp ring substituents.Thus 2,5-diphenylphosphaferrocene (I), 3,3',4,4'-tetramethyldiphosphaferrocene (II) and 2,2',5,5'-tetraphenyldiphosphaferrocene (III) have QS values of 2.03, 1.82 and 1.52 mm s-1, respectively.III dissolves readily and reversibly in triflic acid (CF3SO3H) to give a phenyl ring protonated species.The Moessbauer spectrum of the frozen solution shows a significant increase in QS to 1.77 mm s-1 which is interpreted in terms of iron participation in the stabilisation of the ? complex.H/D exchange reactions and oxidation of phosphaferrocenes are briefly reported together with an improved synthesis of the important precursor, 1,2,5-triphenylphosphole.
SYNTHESIS AND PHOTOCHEMICAL REACTION OF DIELS-ALDER ADDUCT OF PHOSPHOLE OXIDE AND CYCLOPENTADIENE
Tomioka, Hideo,Miura, Shinichi,Izawa, Yasuji
, p. 3353 - 3356 (2007/10/02)
Irradiation of 1-phenylphosphole oxide-cyclopentadiene adduct gave a caged product, whereas similar irradiation of 1,2,5-triphenylphosphole oxide-cyclopentadiene adduct afforded a cleavaged product.
