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Durham e-Theses
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Spectroscopic and structural studies of some new organophosphorus compounds

Deng, R.M.K. (1981) Spectroscopic and structural studies of some new organophosphorus compounds. Doctoral thesis, Durham University.



The acceptor properties of the alkyl-substituted phosphoranes MePC1(_4) and EtPC1(_4) towards chloride and pyridine ligands have been studied by (^31)P n.m.r. spectroscopy. In PhN0(_2) they react with R(_4) 'NC1 to produce six-coordinate anions, which equilibrate with the parent compound. RPC1(_4) + C1(^-) RPC1(_5)(^-1) (R = Me or Et) With pyridine, MePC1(_4) forms a five-coordinate cation (MePC1(_3)py(^+)Cl(^-)) in solution, whereas EtPC1(_4) gives a white precipitate which analysed as a 1:1 adduct. Cationic species RPC1(_3)L'(^+)C1(^-) are formed with bidentate ligands L' (L' = bipy or phen). RPC1(_3)(^+)SbC1(_6) salts also react with the bidentate pyridines to form six-coordinate complexes, which exist in two isomeric forms. Introduction of more than one alkyl group into the compound R(_n)PC1(_4-n)(^+)Cl(^-) reduces the acceptor properties, however, and no adduct formation has been detected. - CatPBr(_3) decomposes on addition of bromide ion to give catPBr and Br(_3)(^-), while cat(_2)PBr is inert to this ion. cat(_2)PBr and a cationic species with six-coordinate cationic derivatives Pyridine gives a 1:1 molecular adduct with catPBr(_3), whereas bidentate pyridines form cat(_2)PL'(^+) and catPBr(_2)L'(^+) respectively. PhPBr(_4) like catPBr(_3), decomposes in the presence of a bromide ion to give PhPBr(_2) and Br(_3)(^-) , and shows no acceptor properties towards mono- or bidentate pyridines, but the adduct PhPBr(_3)(^+)BBr(_4)(^-) forms six-coordinate complexes with bipy or phen. 31 Several new compounds have been isolated and further characterised by (^31)P.n.m.r. vibrational spectroscopy and elemental analysis. The organophosphorus dicyanides RP (CN)(_2) (R = Me, Et, Ph) add on halide (Cl(^-), Br(^-), I(^-)) or thiocyanate ions to form four coordinate anionic derivatives. The addition of CN(^-) to these cyanides, however, yields organocyanophosphide (I) ions, and cyanogen. Unlike. the cyanides the organophosphorus halides RPC1(_2) (R = Me, t-Bu, Ph) show no tendency to coordinate, although they react with

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1981
Copyright:Copyright of this thesis is held by the author
Deposited On:15 Jul 2013 14:42

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