Brown, Loren2019-06-042019-06-042019-06-03vt_gsexam:21089http://hdl.handle.net/10919/89732Rh(III) and Ir(III) dimeric complexes with tunable cyclopentadienyl (Cp) rings have proven versatile for both catalysis and as synthetic precursors. An efficient microwave method to synthesize Rh(III) and Ir(III) dimeric complexes [(η5-ring)MCl]2(μ2-Cl)2, (where (η5-ring)MCl = (η5-Me4C5R)Rh(III)Cl or (η5-Me4C5R)Ir(III)Cl) was developed. A modular design for the substituted cyclopentadienes HC5Me4R was based on Grignard reactions of 2,3,4,5-tetramethylcyclopent-2-en-1-one (R = alkyl, 12 examples; R = aryl, 3 examples) or by SNAr reactions of potassium tetramethylcyclopentadienide with perfluoroarenes (R = perfluoroaryl, 3 examples). Reaction of the Me4CpHR ligands with [M(COD)](μ2-Cl)2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) produced the dimeric complexes [Cp*RMCl]2(μ2-Cl)2 in moderate to excellent yield. The resulting dimers were characterized by nuclear magnetic resonance (NMR) spectroscopy, single-crystal X-ray diffraction (XRD), high-resolution mass spectrometry (HRMS), elemental analysis, and examined as catalysts for oxidative lactonization of 1,4- and 1,5-diols. Oxidative lactonization of 1,4-butanediol to afford γ-butyrolactone proceeded selectively and efficiently using [(η5-Me4C5R)IrCl]2(μ2-Cl)2 as the catalyst. Several R substituents were tested to assess electronic substituent effects. The most active complex contained an electron donating group, R = CHMe2 and successfully catalyzed the formation of diols to lactones across a range of 1,4- and 1,5-diols, generally in high yield. Computational analysis of the rate-determining b-hydrogen elimination reactions provided an atomistic account of observed trends in reaction yield and selectivity as a function of substrate structure, while accounting neatly for the observed selective formation of lactones (vs. succinaldehyde) in the transfer dehydrogenation of 1,4-butyrolactone.ETDIn Copyrightiridiumrhodiumlactoneoxidative lactonizationtransfer dehydrogenationmicrowave synthesisligand effectsDissertation