75231-76-4Relevant academic research and scientific papers
Dibenzo[b,f]phosphepines: Novel phosphane-olefin ligands for transition metals
Lyaskovskyy, Volodymyr,Van Dijk-Moes, Relinde J. A.,Burck, Sebastian,Dzik, Wojciech I.,Lutz, Martin,Ehlers, Andreas W.,Slootweg, J. Chris,De Bruin, Bas,Lammertsma, Koop
, p. 363 - 373 (2013/03/14)
New, stable heterobidentate phosphane-olefin ligands based on the dibenzo[b,f]phosphepine backbone are reported together with their redox properties and coordination chemistry to rhodium(I). The X-ray crystal structures and DFT calculations show different conformations for the P-phenyl (6a) and P-mesityl (6b) derivatives. Cyclic voltammetry (vs Fc/Fc+) of 6a supported by UV-vis spectroelectrochemistry showed two cathodic waves, a reversible one at E1/2 = -2.62 V (If/Ib = 1.0) and a quasi-reversible (If/Ib ≈ 1.2) one at E 1/2 = -3.03 V. Reduction with sodium afforded a mixture of the radical anion [6a?]-, characterized by EPR spectroscopy, and dianion [6a]2-, for which an X-ray crystal structure was obtained. Both 6a and 6b bind to RhI centers, giving rise to 3:1 (8a) and 2:1 (8b) ligand:Rh complexes, respectively. Two dibenzo[b,f]phosphepines in 8a and 8b act as heterobidentate ligands in which both the phosphorus atom and the olefinic double bond coordinate to rhodium, but the third ligand in 8a binds as a monodentate P-donor. The cyclic voltammogram of 8b showed two close-lying waves, a one-electron reversible wave at -1.45 V and a two-electron quasi-reversible wave at -1.80 V (If/Ib ≈ 1.3). 8a showed a reversible wave at -1.71 V and irreversible waves at lower potentials.
Synthesis of the Group 15 1-Benzoheteroepines, Dibenzoheteroepines and Dibenzoheteroepines involving the First Isolated Examples of Arsepines and Bismepines
Yasuike, Shuji,Ohta, Hideo,Shiratori, Shinichi,Kurita, Jyoji,Tsuchiya, Takashi
, p. 1817 - 1819 (2007/10/02)
The C-unsubstituted fully unsaturated Group 15 (P, As, Sb and Bi) 1-benzoheteroepines 6, dibenzoheteroepines 8 and dibenzoheteroepines 10 have been prepared from the dibromo compounds 3,7 and 9 having a 1,6-dibromohexatriene system, and their thermal stabilities have been examined.
SYNTHESIS, REACTIVITY AND CONFORMATION OF 10,11-DIHYDRODIBENZO-PHOSPHEPIN AND DIBENZOPHOSPHEPIN DERIVATIVES. PHOSPHORUS ANALOGUES OF IMINOBIBENZYL ANTIDEPRESSANTS
Segall, Yoffi,Shirin, Ezra,Granoth, Itshak
, p. 243 - 254 (2007/10/02)
Derivatives of the novel dibenzophosphepin system are prepared from 10,11-dihydro-5-phenyl-5H-bibenzophosphepin 5-oxide (2).New members in the 10,11-dihydro-5H-dibenzophophepin series, including phosphorus analogues (7, 10) of the antidepressant drug imipramine (30), are also reported.Products of the nucleophilic substitution at tetrahedral phosphorus in 2 appear to be determined by the relative apicophilicity of the nucleophile.Conformational analysis based on 1H NMR data suggests folded ("butterfly") conformation for the tricyclic compounds.The twisted boat conformation of the central ring in the 10,11-dihydro compounds bears a pseudo-equatorial P=O oxygen or a P=S sulfur, in solution.Symmetric AA'BB' spin systems are found in 4, 5 and 7, and their solution conformations appear to be similar to those of analogous 10,11-dihydrodibenzoazepine derivatives.The interaction of some compounds with NMR shift reagents and their mass spectral fragmentations are discussed.
