| This thesis describes the synthesis, characterization, and reactivities of transition metal complexes containing five-membered nitrogen heterocycles. The first project focuses on Ru(arene) complexes with {dollar}pi{dollar}-bound indole and indoline ligands. Reactions of ((p-cymene)Ru(OTf){dollar}rmsb2rbracksb{lcub}x{rcub}{dollar} with indoles afforded ((cymene)Ru({dollar}etasp6{dollar}-indole)) (OTf) {dollar}sb2{dollar} complexes (3), which underwent deprotonation on neutral alumina to give ((cymene)Ru({dollar}etasp6{dollar}-indolyl)) (OTf) species (4). {dollar}etasp6{dollar}-Coordination of the indolyl ligand in the 2,3-dimethylindolyl complex, 4c (BPh{dollar}sb4{dollar}) was confirmed by an X-ray diffraction study. Reactions of 4c with Cl{dollar}sb2{dollar}Pd(PPh{dollar}sb3{dollar})(NCCH{dollar}sb3{dollar}) and (CuOTf) {dollar}sb2{dollar}(bz) gave the heteronuclear complexes ((cymene)Ru(2,3-Me{dollar}sb2{dollar}indolyl)) Pd(PPh{dollar}rmsb3)Clsb2{dollar} (OTf) (5) and {dollar}{lcub}{dollar} ((cymene)Ru(2,3-Me{dollar}sb2{dollar}indole)) {dollar}sb2{dollar}Cu(OTf){dollar}{rcub}{dollar} (OTf) {dollar}sb2{dollar} (6), respectively. The reaction of 6 with LiAl(OtBu){dollar}sb3{dollar}H at {dollar}-{dollar}78{dollar}spcirc{dollar}C, followed by a 0{dollar}spcirc{dollar}C workup resulted in hydride addition to C4 of each indolyl ligand, forming ((cymene)Ru(2,3-Me{dollar}sb2{dollar}-indolyl{dollar}cdot{dollar}H)) {dollar} sb2{dollar}Cu(OTf) (7a). Hydrogenation of 3a and 3b in the presence of Rh/C gave ((cymene)Ru({dollar}etasp6{dollar}-1-R-indoline)) (OTf) {dollar}sb2{dollar} (8a, R = H; 8c, R = Me). Complex 8a and its benzene analogue (8b) were also prepared by reacting 1-methylindoline with (Ru(arene)(OTf){dollar}rmsb2rbracksb{lcub}x{rcub}{dollar} complexes. Reactions of 8a and 8b with nucleophiles and electrophiles were investigated.; The second project involves studies on Cp{dollar}sp*{dollar}Ir(III) complexes with {dollar}pi{dollar}-bound heterocyles. The complexes (Cp{dollar}sp*{dollar}Ir({dollar}etasp6{dollar}-1-R-indole)) (OTf) {dollar}sb2{dollar} (10a, R = Me; 10b, R = H) were prepared by reacting (Cp{dollar}sp*{dollar}IrCl{dollar}sb2rbracksb2{dollar} with AgOTf, followed by the appropriate indole. Chromatography of 10b on neutral Al{dollar}rmsb2Osb3{dollar} generated (Cp{dollar}sp*{dollar}Ir({dollar}etasp6{dollar}-indolyl)) (OTf), 11. Reactions of 10a, 10b, and 11 with nucleophiles (LiAl(OtBu){dollar}sb3{dollar}H, LiCH(CO{dollar}sb2{dollar}Et){dollar}sb2{dollar}) resulted in nucleophilic addition to the indole six-membered ring. (Cp{dollar}sp*{dollar}Ir({dollar}etasp6{dollar}-1-Me-indoline)) (OTf) {dollar}sb2{dollar} (12) and (Cp{dollar}sp*{dollar}Ir({dollar}etasp5{dollar}-HNC{dollar}sb4{dollar}Me{dollar}sb4{dollar}Me{dollar}sb4){dollar}) (OTf) {dollar}sb2{dollar} (16) were also prepared, and their reactions with nucleophiles and other reagents will be discussed.; The final project focuses on square planar complexes containing {dollar}etasp1{dollar},N-bound indolyl and indoline ligands. Reactions of trans-IrCl(PPh{dollar}sb3)sb2{dollar}(CO) with indolyl lithium salts formed IrCl(PPh{dollar}sb3)sb2{dollar}(2,3-R{dollar}sb2{dollar}-indolyl) (18a, R = H; 18b, R = CH{dollar}sb3{dollar}). An X-ray diffraction study of 18b showed that iridium was {dollar}sigma{dollar}-bound to the indolyl nitrogen. Reaction of 18b with HOTf resulted in protonation at C3 to form (Ir(CO)(PPh{dollar}sb3)sb2{dollar}(2,3-Me{dollar}sb2{dollar}indolenine)) (OTf), 19. Reactions of the indolyl complexes with hydrogen, base, and hydrides were also investigated. Cl{dollar}sb2{dollar}Pd(PPh{dollar}sb3{dollar})({dollar}etasp1{dollar}-indoline) (22) was prepared by the reaction of Cl{dollar}sb2{dollar}Pd(PPh{dollar}sb3{dollar})(NCCH{dollar}sb3{dollar}) with indoline. An X-ray structure of 22 showed a pseudotetrahedral arrangement of ligands about the indoline nitrogen at... |
