Nuclear magnetic resonance and electrochemical studies of boron hydride derivatives

Rights statement
Awarding institution
  • University of Strathclyde
Date of award
  • 1984
Thesis identifier
  • T4860
Qualification Level
Qualification Name
Department, School or Faculty
  • The new monosubstituted octahydrotriborate anions [B₃H₇(NCO)]⁻, [{B₃H₇(NC)}₂Ag]⁻, [B₃H₇(NCBH₂Cl)]⁻ and disubstituted octahydrotriborate anions [B₃H₆(Cl)₂]⁻, [B₃H₆(Cl)(NCS)]⁻, [B₃H₆(Cl)(NCBH₃)]⁻, [B₃H₆(Cl)(NCBH₂CI)]⁻, [{B₃H₆(Cl)(NC)}₂Ag]⁻ were prepared and their ¹¹B and ¹H n. m. r. spectra were studied. Cyclic and a. c. voltammetry and controlled potential electrolyses of [B₃H₇(NCS)]⁻, [B₃H₇(NCO)]⁻, [B₃H₆(Cl)₂]⁻ and [B₃H₆(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 [B₁₀H₁₃(PPh₃)]⁻ and [B₁₀H₁₃(SMe₂)]⁻ were investigated. The ¹¹B and ¹H n. m. r. evidence confirmed that [B₁₀H₁₃(PPh₃)]⁻ is isostructural to [B₁₀H₁₄]²⁻ whereas that of [B₁₀H₁₃(SMe₂)]⁻ suggested that it is similar to [B₁₀H₁₃]⁻ anion. Cyclic and a. c. voltammetry of these anions were studied in acetonitrile, 1,3-dioxalane, dichloromethane and tetramethylurea. Exhaustive electrolysis of [B₁₀H₁₃(PPh₃)]⁻ at Pt in acetonitrile led to [B₁₀H₁₂(PPh₃)(CH₃CN)] whereas that of [B₁₀H₁₃(SMe₂)]⁻ gave rise to B₁₀H₁₄ and B₉H₁₃[CH₃CN]. Anodic dissolution of Cu in acetonitrile solution of [B₁₀H₁₃(PPh₃)]⁻ yielded a product which showed a weak interaction between Cu(I) and the BH₂ group at the B(9) position of the starting anion. Similar dissoIution of Cu in a solution of [B₁₀H₁₃(SMe₂)]⁻ led to [B₁₀H₁₃]⁻ and possibly [B₁₀H₁₅]⁻. Anodic dissolution of Ni or Zn in acetonitrile solution of [B₁₀H₁₂(PPh₃)]⁻ led to [B₁₀H₁₂(PPh₃)(CH₃CN)]. Chemical reaction of [B₁₀H₁₃(PPh₃)]⁻ with Hg₂Cl₂ or HCI in acetonitrile also yielded [B₁₀H₁₂(PPh₃)(CH₃CN)] whereas in dichloromethane, B₉H₁₃[PPh₃] was obtained.
Resource Type
Date Created
  • 1984
Former identifier
  • 12416