Gallazanes and related compounds

• Main Author: Penland, Allen David
• Language: English
• Published: University of British Columbia 2011
• Subjects: Gallium
• Online Access: http://hdl.handle.net/2429/33243

This work involved preparation of cyclical dimeric or trimeric gallazanes of general formula: (RNHGaH₂)[subscript n omitted] where n= 2 or 3 and R = Et, Pr[superscript n omitted], Pr[superscript i omitted], Bu[superscript n omitted], Bu[superscript i omitted], Bu[superscript s omitted], or Bu[superscript t omitted]. The effect of larger R group on ring size ( n value ) was determined. Some deuterated analogues of these compounds were also prepared. These were (EtNHGaD₂)₃, (Bu[superscript t omitted]NHGaD₂)₂, and (Pr[superscript i omitted]NHGaD₂)₂. Attempted preparation of ØNHGaH₂ resulted in isolation of ØNH.GaH₂.NMe₃. Reactions were undertaken with ØNH.GaH₂.NMe₃ and it partially deuterated analogue ØNHGaD₂.NMe₃, and shown to involve proton transfer through a 4-centre transition state. Additional work on the effects of R group on the nitrogen within the gallazanes involved preparation of dimeric gallazanes of general formula ((CH₂)[subscript x omitted].N.GaH₂)₂ where x = 2,3,4 or 5. Additional work on double ring systems involved preparation of analogous alazanes of general formula ((CH₂)[subscript x omitted]N.AlH₂)[subscript n omitted] where x = 2,3,4,5 and n = 2 or 3. Similar borazanes were likewise prepared and were of general formula: ((CH₂)[subscript x omitted].N.BH₂)[subscript n omitted] where x = 2,3,4, 5 and n = 2 or 3. Adducts of general formula: (CH₂)₂NH.EMe₃ where E = B, Al, Ga, In, were also prepared. Upon pyrolysis these adducts yield methane plus materials of the general formula: ((CH₂)₂N.EMe₂)₃ where E = Al,Ga, In. Characterization of these materials as well as gaseous reaction products was accomplished by infrared spectroscopy. Additional data was obtained by 60MHz and 100MHz 'H nmr as well as mass spectrometry. Molecular weights were determined cryoscopically in benzene and analyses for galluim, aluminum or hydrolysable hydrogen carried out by standard means. === Science, Faculty of === Chemistry, Department of === Graduate