Thesis

Chemical and electrochemical studies of Borane Anions and Metallaboranes

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Awarding institution
  • University of Strathclyde
Date of award
  • 1985
Thesis identifier
  • T5150
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Department, School or Faculty
Abstract
  • Several new monosubstituted anionic derivatives of [B?H?]? of the type [B?H?(X)]?(X = NCSe, NCBPh?, NCBH?NCBH?, NCB?H?,NCBH?CN and NCBH?CNB?H?) have been prepared. The disubstituted anions [B?H?(Cl)(X)]?(X = NCBH?NCBH?, NCBH?CN and NCB?H?) and [B?H?(Br) NCB?H?(Br)]/? have also been prepared and studied by various spectroscopic techniques. Two-dimensional n. m. r. spectroscopy was shown to be useful in the qualitative determination of the bonding employed in these anions. The electrochemical properties of these anions have been investigated by various techniques. It was found that when the substituent was varied the oxidative stability of the anions varied. Metallaboranes of some of these anions have been prepared by anodic dissolution of a suitable metal in a solution of the anion. The structures and dynamics of substituted derivatives of the [B?H??]? ion have been studied. The anions [B?H??(X)?(X = CINCSe, NCBPh?, NCBH?NCBH?, NCBH?CN, NCBH?CNB?H??, CN, and NCAgCNB?H??) and [B?H??(CN?]? have been prepared. ¹¹B and ¹H n. m. r. spectroscopy indicated that when the substituent contained electron withdrawing groups (e. g. the hydrogen atoms on NCBH?NCBH?) the anion was static at room temperature on the n. m. r. time scale. If no electron withdrawing groups were present on the substituent then the molecule was fluxional at room temperature on the n. m. r. time scale. The electrochemistry of these anions was also studied and it was found that, in some cases, oxidation resulted in cage closure to give substituted nido-derivatives. Anodic dissolution of Cu or Ag in solutions of some of the anions produced metallaboranes. The chemistry and electrochemistry of [B?H??]? was also studied and the crystal structure of the (N(PPh?)?]? salt was obtained. Several new substituted metallaboranes have been prepared by reaction of the substituted octahydrotriborate (1-) or substituted tetradecahydrononaborate (1-) anions with Cu(PPh?)?(BH?). The reactions of Mn(CO)? Br with [B?H??(X)]?(X = NCSe, NCBH?NCBH? and NCBPh?) have also been investigated.
Resource Type
DOI
EThOS ID
  • uk.bl.ethos.371962
Date Created
  • 1985
Former identifier
  • 14508

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