178381-38-9Relevant academic research and scientific papers
Cyclic aromatic analogues of the hendrickson reagent; NMR studies and electrophilic properties
Moussa, Ziad
, p. 460 - 468 (2012)
Two novel cyclic aromatic analogues of the Hendrickson POP reagent, 1,1,3,3-tetraphenyl-1,3-dihydro-2,1,3-benzoxadiphosphole-1,3-diium bis(trifluoromethanesulfinate) and bis(trifluoromethanesulfonate), have been readily prepared by the treatment of 1,2-bis(diphenylphosphino)benzene or 1,2-bis(diphenylphosphoryl)benzene, respectively, with trifluoromethanesulfonic anhydride in dichloromethane. 31P and 19F NMR studies indicated that while the latter complex is formed as the sole product, the former species was shown to be the predominant component in equilibrium with 1-(diphenylphosphino)-2-[diphenyl(trifluoromethylsulfonyloxy)phosphonio]benzene trifluoromethanesulfinate and 1,2-bis[diphenyl(trifluoromethylsulfonyloxy) phosphonio]benzene bis(trifluoromethanesulfinate). The dehydrating POP systems were exploited in the conversion of aldoximes into nitriles. The dehydration occurred rapidly at room temperature and produced high yields with a variety of alkyl- and arylaldoximes, tolerating a wide range of substrates and functional groups. Georg Thieme Verlag Stuttgart New York.
Bisphosphine monoxides with o-phenylene backbones in Pt, Pd and Fe complexes
Farrer, Nicola J.,McDonald, Robert,Piga, Toria,McIndoe, J. Scott
experimental part, p. 254 - 261 (2010/04/04)
A new route to aromatic bisphosphine monoxides has been explored through ortholithiation of triphenylphosphine oxide and subsequent reaction of the lithiated intermediate with a range of alkyl and aryl phosphine chlorides. Routes to the known bisphosphine monoxide (BMPO) (o-C6H4){P(O)Ph2}PPh2 (2aO) and a range of new BPMOs of the type Ph2P(O)(o-C6H4)PR2 where R2 = iPr2, Cy2, Et2 are described. Reaction of 2aO with MCl2(cod) (M = Pd, Pt; cod = cyclooctadiene) gives products of the form [MCl(κ1-P-2aO)(κ2-P,O-2aO)]+ Cl- and MCl2(κ2-P,O-2aO); the former exhibits fluxional behaviour which has been analysed by 195Pt NMR and 31P variable-temperature NMR spectroscopy. The bidentate complex is not fluxional for either the Pd or the Pt example; the Pt complex PtCl2(κ2-P,O-2aO) has been characterised by X-ray crystallography. By comparison of the product distribution seen by 31P NMR spectroscopy and ESI-MS it was established that the different coordination modes of 2aO result in quite different behaviour of the complexes when studied by ESI-MS; when the O is formally coordinated to the metal its ionisation efficiency is very low. Synthesis of Fe(CO)4(2aO) confirmed the ability of the 2aO ligand to render a neutral complex with no alternative pathways for ionisation to be readily detected by ESI-MS.
