Valentine Ananikov received his Ph.D. degree in 1999, Habilitation in 2003, and was appointed Professor and Laboratory Head of the ND Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences in 2005. In 2008 he was elected as a Member of Russian Academy of Sciences. In 2012 he became Professor of Chemistry, Department of Moscow State University. In 2013 he has received a Megagrant of Saint Petersburg State University and was appointed as Head of Laboratory of Cluster Catalysis. Valentine Ananikov was a recipient of the Russian State Prize for Outstanding Achievements in Science and Technology in 2004, a Science Support Foundation award in 2005, a Russian Academy of Sciences Medal in 2000. He was named a Liebig Lecturer by German Chemical Society in 2010, and was awarded the Balandin Prize for outstanding achievements in the field of catalysis in 2010. His scientific interests are focused on development of new concepts in transition metal and nanoparticle catalysis, sustainable organic synthesis and new methodology for mechanistic studies of complex chemical transformations. His research has been supported by grants of Russian Science Foundation, Russian Foundation of Basic Research and Grants of President of Russia. Valentine Ananikov is a member of the International Advisory Boards of Advanced Synthesis & Catalysis, Organometallics, Chemistry - An Asian Journal and OpenChemistry.

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.

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

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.