| The chemical reactivity of ammonia-borane, {dollar}rm Hsb3NBHsb3{dollar}, was studied. It was demonstrated that {dollar}rm Hsb3NBHsb3{dollar} contains both protonic and hydridic hydrogen atoms within its structure. Reaction of {dollar}rm Hsb3NBHsb3{dollar} with either MH, M, or RLi (M = Li Na, K; R = CH{dollar}rmsb3, Csb4Hsb9){dollar} produced alkali metal aminoborohydride salts, M({dollar}rm Hsb2NBHsb3rbrack{dollar}. The colorless solids were characterized by {dollar}rmsp{lcub}11{rcub}B, sp1H{dollar}, and {dollar}sp7{dollar}Li NMR spectroscopy, IR spectroscopy, and X-ray powder diffraction. ({dollar}rm Hsb2NBHsb3rbracksp-{dollar} was found to react as either a hydride donor or as a ligand. It reacted as a hydride donor in reactions with {dollar}rm BHsb3THF, Fe(CO)sb5, Cr(CO)sb6{dollar} and {dollar}rm Rusb3(CO)sb{lcub}12{rcub}{dollar} producing (BH{dollar}rmsb4rbracksp-, lbrack Fe(CO)sb4CHOrbracksp-, lbrack Cr(CO)sb5CHOrbracksp-{dollar} and (HRu{dollar}rmsb3(CO)sb{lcub}11{rcub}rbracksp-{dollar}, respectively.) {dollar}rm Hsb2NBHsb3rbracksp-{dollar} behaved as a ligand during reaction with MgI{dollar}sb2{dollar} and ({dollar}rm Csb5Hsb5)sb2ZrClsb2{dollar} producing Mg(H{dollar}rmsb2NBHsb3)sb2, (Csb5Hsb5)sb2ZrCl(Hsb2NBHsb3){dollar} and (C{dollar}rmsb5Hsb5)sb2Zr(Hsb2NBHsb3)sb2{dollar}. With ZnCl{dollar}rmsb2, lbrack Hsb2NBHsb3rbracksp-{dollar} behaved as a ligand at low temperatures producing Zn({dollar}rm Hsb2NBHsb3)sb2{dollar}. Above 0{dollar}spcirc{lcub}rm C{rcub}{dollar}, reduction to metallic Zn occurred.; {dollar}rm Hsb3NBHsb3{dollar} reacted with HX (X = Cl, Br) to form ammonia-monohaloborane, {dollar}rm Hsb3NBHsb2X.{dollar} With Cl, it also produced ammonia-dichloroborane, {dollar}rm Hsb3NBHClsb2.{dollar} {dollar}rm Hsb3NBHsb2Cl{dollar} was characterized by {dollar}sp{lcub}11{rcub}{dollar}B and {dollar}sp1{dollar}H NMR spectroscopy, IR spectroscopy and X-ray powder diffraction. It was also heated to 1100{dollar}spcirc{lcub}rm C{rcub}{dollar} to produce turbostratic boron nitride. The BN was analyzed by X-ray powder diffraction, diffuse reflectance IR spectroscopy, elemental analysis, solid state {dollar}sp{lcub}11{rcub}{dollar}B NMR spectroscopy, SEM, EELS, ESCA, and EDS.; The gadolinium borane compounds {dollar}rm Gd(Bsb3Hsb8)sb3cdot{dollar}nDMF and {dollar}rm Gd(Bsb9Hsb{lcub}14{rcub})sb3cdot{dollar}nDMF were synthesized from anhydrous GdCl{dollar}sb3{dollar} and {dollar}rm KBsb{lcub}x{rcub}Hsb{lcub}y{rcub}{dollar} in dimethylformamide or dimethylacetamide solution. They were characterized by {dollar}sp{lcub}11{rcub}{dollar}B NMR spectroscopy and IR spectroscopy. |
