Thesis

Nuclear magnetic resonance and electrochemical studies of boron hydride derivatives

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Awarding institution
  • University of Strathclyde
Date of award
  • 1984
Thesis identifier
  • T4860
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Department, School or Faculty
Abstract
  • The new monosubstituted octahydrotriborate anions [B?H?(NCO)]?, [{B?H?(NC)}?Ag]?, [B?H?(NCBH?Cl)]? and disubstituted octahydrotriborate anions [B?H?(Cl)?]?, [B?H?(Cl)(NCS)]?, [B?H?(Cl)(NCBH?)]?, [B?H?(Cl)(NCBH?CI)]?, [{B?H?(Cl)(NC)}?Ag]? were prepared and their ¹¹B and ¹H n. m. r. spectra were studied. Cyclic and a. c. voltammetry and controlled potential electrolyses of [B?H?(NCS)]?, [B?H?(NCO)]?, [B?H?(Cl)?]? and [B?H?(Cl)(NCS)]? in various solvents such as acetonitrile, 1,3-dioxalane, dichloromethane and benzonitrile were carried out and attempts to prepare metallaboranes at Cu or Ni anodes were described. The ¹¹B and ¹H n. m. r. and electrochemistry of [B??H??(PPh?)]? and [B??H??(SMe?)]? were investigated. The ¹¹B and ¹H n. m. r. evidence confirmed that [B??H??(PPh?)]? is isostructural to [B??H??]²? whereas that of [B??H??(SMe?)]? suggested that it is similar to [B??H??]? anion. Cyclic and a. c. voltammetry of these anions were studied in acetonitrile, 1,3-dioxalane, dichloromethane and tetramethylurea. Exhaustive electrolysis of [B??H??(PPh?)]? at Pt in acetonitrile led to [B??H??(PPh?)(CH?CN)] whereas that of [B??H??(SMe?)]? gave rise to B??H?? and B?H??[CH?CN]. Anodic dissolution of Cu in acetonitrile solution of [B??H??(PPh?)]? yielded a product which showed a weak interaction between Cu(I) and the BH? group at the B(9) position of the starting anion. Similar dissoIution of Cu in a solution of [B??H??(SMe?)]? led to [B??H??]? and possibly [B??H??]?. Anodic dissolution of Ni or Zn in acetonitrile solution of [B??H??(PPh?)]? led to [B??H??(PPh?)(CH?CN)]. Chemical reaction of [B??H??(PPh?)]? with Hg?Cl? or HCI in acetonitrile also yielded [B??H??(PPh?)(CH?CN)] whereas in dichloromethane, B?H??[PPh?] was obtained.
Resource Type
DOI
EThOS ID
  • uk.bl.ethos.371093
Date Created
  • 1984
Former identifier
  • 12416

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