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Some reactions of metal chlorides with phosphines and alkyl halides.

Taylor, Nicholas Justin. (1971) Some reactions of metal chlorides with phosphines and alkyl halides. Doctoral thesis, University of Surrey (United Kingdom)..

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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.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors :
Taylor, Nicholas Justin.
Date : 1971
Contributors :
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1971.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 14:26
Last Modified : 06 Nov 2018 16:53

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