Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book.The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper understanding of the underlying reaction mechanism and correlation between molecular structure and reactivity. The contributions represent a wealth of first-hand information from renowned experts working in these disciplines, covering such topics as activation of small molecules, C-C and C-Heteroatom bonds formation, cross-coupling reactions, carbon dioxide converison, homogeneous and heterogeneous transition metal catalysis and metal-graphene systems. With the knowledge gained, the reader will be able to improve existing reaction protocols and rationally design more efficient catalysts or selective reactions.An indispensable source of information for synthetic, analytical, and theoretical chemists in academia and industry.

PrefaceMECHANISMS OF METAL-MEDIATED C-N COUPLING PROCESSES: A SYNERGEISTIC RELATIONSHIP BETWEEN GAS-PHASE EXPERIMENTS AND COMPUTATIONAL CHEMISTRYIntroductionFrom Metal-Carbon to Carbon-Nitrogen BondsFrom Metal-Nitrogen to Carbon-Nitrogen BondsConclusion and PerspectivesFUNDAMENTAL ASPECTS OF THE METAL-CATALYZED C-H BOND FUNCTIONALIZATION BY DIAZOCARBENES: GUIDING PRINCIPLES FOR DESIGN OF CATALYST WITH NON-REDOX-ACTIVE METAL (SUCH AS CA) AND NON-INNOVENT LIGANDIntroductionTheoretical Models and MethodsDesign of Catalyst with Non-Redox-Active Metal and Non-Innocent LigandConclusions and PerspectivesUSING METAL VINYLIDENE COMPLEXES TO PROBE THE PARTNERSHIP BETWEEN THEORY AND EXPERIMENTIntroductionProcect Planning in Organometallic ChemistryCase StudiesThe Benefits of Synergy and PartnershipsLIGAND, ADDITIVE, AND SOLVENT EFFECTS IN PALLADIUM CATALYSIS - MECHANISTIC STUDIES EN ROUTE TO CATALYST DESIGNIntroductionThe Effect of Solvent in Palladium-Catalyzed Cross Coupling and on the Nature of the Catalytically Active SpeciesCommon Additives in Palladium-Catalyzed Cross-Coupling Reactions - Effect on (Pre)catalyst and Active Catalytic SpeciesPd(I) Dimer: Only Precatalyst or Also Catalyst?Investigation of Key Catalytic Intermediates in High-Oxidation-State Palladium ChemistryConcluding RemarksCOMPUTATIONAL STUDIES ON SIGMATROPIC REARRANGEMENTS VIA PI-ACTIVATION BY PALLADIUM AND GOLD CATALYSTSIntroductionPalladium as a CatalystGold as a CatalystConcluding RemarksTHEORETICAL INSIGHTS INTO TRANSITION METAL-CATALYZED REACTIONS OF CARBON DIOXIDEIntroductionTheoretical MethodsHydrogenation of CO2 with H2Coupling Reactions of CO2 and EpoxidesReduction of CO2 with OrganoboronsCarboxylation of Olefins with CO2SummaryCATALYTICALLY ENHANCED NMR OF HETEROGENEOUSLY CATALYZED HYDROGENATIONSIntroductionParahydrogen and PHIP BasicsPHIP as a Mechanistic Tool in Homogeneous CatalysisPHIP-Enhanced NMR of Reaction ProductsPHIP-Enhanced NMR and Heterogeneous CatalysisSummary and ConclusionsCOMBINED USE OF BOTH EXPERIMENTAL AND THEORETICAL METHODS IN THE EXPLORATION OF REACTION MECHANISMS IN CATALYSIS BY TRANSITION METALSIntroductionRecent DFT Developments of Relevance to Transition Metal CatalysisCase StudiesConclusionsIS THERE SOMETHING NEW UNDER THE SUN? MYTHS AND FACTS IN THE ANALYSIS OF CATALYTIC CYCLESIntroductionKinetics Based on Rate Constants or EnergiesApplication: Cross-Coupling with a Bidentate Pd ComplexA Century of Sabatier's Genius IdeaTheory and Practice of Catalysis, Including Concentration EffectsRDStep, RDStatesConclusionCOMPUTATIONAL TOOLS FOR STRUCTURE, SPECTROSCOPY AND THERMOCHEMISTRYIntroductionBasic ConceptsSpectroscopic TechniquesApplications and Case StudiesConclusions and Future DevelopmentsCOMPUTATIONAL MODELING OF GRAPHENE SYSTEMS CONTAINING TRANSITION METAL ATOMS AND CLUSTERSIntroductionQuantum Chemical Modeling and BenchmarkingRepresentative Studies of Graphene Systems with Transition MetalsConclusions Index