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Title: Some reactions of metal chlorides with phosphines and alkyl halides
Author: Taylor, Nicholas Justin
ISNI:       0000 0001 3511 5770
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1971
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The well-known reaction of aluminium trichloride with phosphorus trichloride and an alkyl chloride to give a complex of the type (RPCl[3+])(AlCl[4-]) has been investigated with the chlorides AlCl[3], BCl[3], SiCl[4], GeCl[4], SnCl[4], TiCl[4], ZrCl[4], NbCl[5], TaCl[4], MoCl[5], WCl[6] and ReCl[5]. The alkylating agent used was t-butyl chloride. The chlorides BCl[3], GeCl[4], SnCl[4], TiCl[4], NbCl[5], TaCl[5] and WCl[6] have also been used with methyl-dichlorophosphine and t-butyl chloride. No reaction occurred with SiCl[4] and GeCl[4]. Vacuum line and glove box preparative techniques have been used. The compounds prepared are ionic complexes containing either the t-butyltrichlorophosphonium or t-butylmethyldichlorophosphonium cations. With the use of infrared and Raman spectroscopy, the anions BCl[4-], AlCl[4], SnCl[5-], Ti[2]Cl[9-], Zr[2]Cl[9-], NbCl[6-], TaCl[6-], Mo[2]Cl[9-], WCl[6-] and Re[4]Cl[15] have been identified. The latter species was found to be the mixed system, (ReCl[6][2-])(Re[3]Cl[9]). The results for molybdenum, tungsten and rhenium are supplemented with magnetic data and solid-state, ultraviolet and visible, diffuse reflectance spectra. The mass spectrum of the ReCl15 complex is reported. The general reaction schemes Bu[t]Cl + PCl[3] + nMClx ? (Bu[t]PCl[3+])(MnCl[2n+1]) and Bu[t]Cl + MePCl[2] + nMCl[x] ? (Bu[t]MePCl[2+]) (MnCl 2n+1) are proposed. With MoCl5, WCl6 and ReCl5, the reactions are accompanied by simultaneous reduction of the metal ion. The reaction BCl3 + NePCl2 + Bu t Cl did not give the expected complex (Bu[t]MePCl[2+])(BCl[4-]) but the adduct MePCl[2].BCl[3] was obtained which is in equilibrium with an ionic complex (MePCl[+]) (BCl[4-]). The same product was obtained in absence of t-butyl chloride. The reaction TiCl[4] + PBr[3] + Bu[t]Cl was found to give the complex (Bu[t]PBr[3+]) (Ti[2]Cl[9-]). A tentative reaction mechanism is suggested. The reaction TiCl[4] + PCl[3] + Bu[t]Cl in the presence of benzene has been found to give the complex (Bu[t]PCl[3+])(Ti[2]Cl[9-]) and a hydrocarbon of formula C[18]H[30]. Several possible structures are suggested on the basis of infrared and mass spectral data.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available