Organometallic Chemistry

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Presentation transcript:

Organometallic Chemistry between organic and inorganic (?) 10/24/2019 Introduction to Organometallic Chemistry

Introduction to Organometallic Chemistry Organic Chemistry more or less covalent C-X bonds rigid element environments fixed oxidation states ?Organometallic Chemistry? Inorganic / Coordination Chemistry primarily ionic M-X bonds variable and often fluxional environments variable oxidation states 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry vs. Organic Chemistry Many similarities Many differences Both can be “understood" You don’t have to learn everything by heart, but some basic knowledge is required to get anywhere. 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry There are many metals ! The chemistry of Fe is not much more complicated than that of C, but after that there are 80 more metals... Generalization is important. We concentrate on the M side of the M-C bond, and on how to tune its reactivity. Applications: synthesis, catalysis, materials, pharmaceuticals. 10/24/2019 Introduction to Organometallic Chemistry

Introduction to Organometallic Chemistry 10/24/2019 Introduction to Organometallic Chemistry

Introduction to Organometallic Chemistry Organic Chemistry Chemistry of C-X bonds C-C / C-H : nearly covalent Cd+-Xd- : polar (partly ionic) SN1, SN2 and analogous additions/eliminations Electrocyclic reactions Woodward-Hoffmann rules 10/24/2019 Introduction to Organometallic Chemistry

Introduction to Organometallic Chemistry Organic Chemistry Carbon is tetrahedral, trigonal or linear Reactive intermediates / transition states: 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry: Main group metals s and p orbitals. 8-e rule, usually. Metal is the "d+" side of the M-C bond. "Umpolung" of the organic fragment. 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry: Main group metals More electropositive and larger: higher coordination numbers, regardless of the number of electrons. “Early" groups and not very electropositive: lower coordination numbers. 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry: Main group metals Multiple bonds relatively weak and reactive. C-C 85 C=C 150 N-N 40 N=N 100 P-P 50 P=P 75 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry: Transition metals s, p and d orbitals 18-e rule, sometimes 16 e other counts relatively rare 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry: Transition metals Metal is usually "d+" Metals are sterically saturated 10/24/2019 Introduction to Organometallic Chemistry

Organometallic Chemistry: Transition metals Often ligands capable of donating 2-8 electrons Preference for p-system ligands Bonds relatively weak Catalysis ! 10/24/2019 Introduction to Organometallic Chemistry

“Forbidden” reactions ? 10/24/2019 Introduction to Organometallic Chemistry

Reactivity of the M-C bond Polar Þ reactive towards e.g. Water: Me3Al explodes with water; Me4Sn does not react. Oxygen: Me2Zn inflames in air; Me4Ge does not react. Carbonyl groups: MeLi adds at -80°C, Me3Sb not even at +50°C. 10/24/2019 Introduction to Organometallic Chemistry

Oxidation and hydrolysis: large driving force Al-C 65 As-C 55 Si-C 74 Al-O 119 As-O 72 Si-O 108 Al-Cl 100 Si-Cl 91 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (1) Ligand dissociation / coordination 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (2) Metal as a ligand 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (3) Insertion b-elimination 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (4) Oxidative addition / Reductive elimination 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (5) s-bond metathesis 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (6) Redox reactions Homolysis 10/24/2019 Introduction to Organometallic Chemistry

Type of reactions in organometallic chemistry (7) Reactivity of coordinated ligands 10/24/2019 Introduction to Organometallic Chemistry

Factors governing structure and reactivity of organometallic compounds M-C, M-X bond strengths Electronegativity of M Number of (d) electrons Coordination number Steric hindrance 10/24/2019 Introduction to Organometallic Chemistry

Trends in the periodic table Main group metals: left and down: more electropositive down: higher oxidation states less stable Transition metals: middle: strongest preference for 18-e 2nd and 3rd row: strong preference for paired electrons (low-spin states) down: higher oxidation states more stable 10/24/2019 Introduction to Organometallic Chemistry

Techniques of Organometallic Chemistry Xray diffraction Þ structure Þ bonding NMR Þ structure en dynamic behaviour (calculations) IR MS EPR Not: GC LC 10/24/2019 Introduction to Organometallic Chemistry