Organometallic Chemistry
an overview reactions
Peter H.M. Budzelaar
Between organic and inorganic...
Organic chemistry: more or less covalent C-X bonds rigid element environments fixed oxidation states (better: valencies)
??Organometallic chemistry??
Inorganic chemistry: primarily ionic M-X bonds, dative M-L bonds variable and often fluxional environments variable oxidation states
Overview of Organometallic Chemistry
Organometallic reactivity
Since most organometallics are intermediates, the focus in organometallic chemistry is usually on understanding and tuning reactivity This starts with analyzing reaction mechanisms in terms of elementary steps The number of possible elementary steps is larger than in "pure organic" chemistry, but the ideas are similar
Overview of Organometallic Chemistry
Organometallic structures
Knowledge of inorganic and coordination chemistry is useful to understand geometries, electron counts and oxidation states of organometallic compounds Organometallics are more covalent and often less symmetric than coordination compounds, so orbital symmetry arguments are not as important
Overview of Organometallic Chemistry
Trends in organometallic chemistry
Organometallic chemistry is concerned with all metals, in combination with all "organic" elements.
there are many metals !
Generalization is important
the chemistry of e.g. Fe is not much more complicated than that of C, but after that there are 80 more metals... we divide reactions in broader categories than organic chemists do
We concentrate on the M side of the M-C bond, and on how to tune its reactivity
Overview of Organometallic Chemistry
Elements of interest
Organic elements Main group metals Transition metals
Overview of Organometallic Chemistry
Organic vs organometallic reactivity
Organic chemistry:
C-C / C-H : nearly covalent Cd+-Xd- : polar (partly ionic) reactivity dominated by nucleophilic attack at C SN2 and SN1 like reactivity
-X X SN1 int (6-e) X Y -X Y SN2 TS (10-e ?) Y Y
Organometallic chemistry:
C is the negative end of the M-C bond ("umpolung") reactivity dominated by electrophilic attack at C or nucleophilic attack at M associative and dissociative substitution at M - C2H4
dissociative (C2H4)PdCl2
CO (C2H4)(CO)PdCl2 - C2H4
(C2H4)2PdCl2 CO
?
(C2H4)2(CO)PdCl2 associative
Overview of Organometallic Chemistry
Main-group organometallics
s and p orbitals.
Me Al Me Me Al Me Me Me
8-e rule, usually. with a lot of exceptions
8-e
Cl
10-e
Cl Sn Me Me More electropositive and larger: O higher coordination numbers, N regardless of the number of electrons.
Early" groups and not very electropositive: lower coordination numbers. Me Zn Me
4-e
8
Overview of Organometallic Chemistry
Main-group organometallics
Metal is the "d+" side of the M-C bond. Chemistry dominated by nucleophilic attack of Cd- at electrophiles.
this is also the main application in organic synthesis
MeMgBr + Me2CO
Me3COMgBr
note: this is a simplified picture of the Grignard reaction
Overview of Organometallic Chemistry
Main-group organometallics
M-M multiple bonds are fairly weak and rather reactive
they are a curiosity and relatively unimportant, certainly compared to C-C multiple bonds
Bond strengths in kcal/mol: C-C 85 C=C 150 N-N 40 N=N 100 P-P 50 P=P 75 Multiple-bonded compounds often have unusual geometries
"Me4Sn2"
Me4C2
10
Overview of Organometallic Chemistry
Transition-metal organometallics
s, p and d orbitals 18-e rule, sometimes 16-e
other counts relatively rare
Ni
CO OC OC Cr CO CO CO
Fe
18-e 18-e
Et3P Et3P Pt Me Cl
18-e
16-e
11
Overview of Organometallic Chemistry
Transition-metal organometallics
Lower electron counts if metals are sterically saturated:
nor Co nor nor = nor nor
Me Me Me Me W Me Me
12-e
13-e
Ti Me Me
16-e
12
Overview of Organometallic Chemistry
Transition-metal organometallics
Often ligands capable of donating 2-8 electrons
Preference for p-system ligands (good overlap with d-orbitals)
olefin
O C
carbene C
cyclopentadienyl allyl
2e
2e
2e
3e
5e
Bonding to neutral ligands (olefin/diene/CO/phosphine) relatively weak
Important for catalysis!
13
Overview of Organometallic Chemistry
Transition-metal organometallics
An olefin complex: (Acac)Ir(NCMe)(C2H4)
donation
backdonation
14
Overview of Organometallic Chemistry
Transition-metal organometallics
Forbidden reactions ?
+ ?
Mo
Mo
No symmetry Very fast
Symmetry-forbidden Does not happen
15
Overview of Organometallic Chemistry
Reactivity of the M-C bond
Polar reactive towards e.g. Water:
M-OH + H-C
Me3Al explodes with water; Me4Sn does not react.
Oxygen:
M-O-O-C
Me2Zn inflames in air; Me4Ge does not react.
Carbonyl groups:
M-O-C C
MeLi adds at -80C, Me3Sb not even at +50C.
16
Overview of Organometallic Chemistry
Reactivity of the M-C bond
Oxidation and hydrolysis: large driving force Bond strengths in kcal/mol: Al-C 65 As-C 55 Al-O 119 As-O 72 Al-Cl 100
Si-C 74 Si-O 108 Si-Cl 91
17
Overview of Organometallic Chemistry
Organometallic reaction steps
Ligand dissociation / coordination
Me3Al + NMe3 6e
Me3Al-NMe3 8e
note: free Me3Al dimerizes to Me6Al2
Mo(CO)6 18e
18
Mo(CO)5 + CO 16e
Overview of Organometallic Chemistry
Organometallic reaction steps
Insertion and b-elimination
MeMgBr + MeC N Me2C=NMgBr
N N Fe Me N
N N Fe Me N
N Fe N
N Me
N N Fe Me = N N Ar = N Ar Fe N Ar
19
Overview of Organometallic Chemistry
Organometallic reaction steps
Insertion and b-elimination
P Pd P P Pd H P
H
P P = Ph2P PPh2
20
Overview of Organometallic Chemistry
Organometallic reaction steps
Oxidative addition / Reductive elimination
P P Rh Cl P H2 P P H Rh Cl H P "P" = PPh3
21
Overview of Organometallic Chemistry
Organometallic reaction steps
Oxidative addition / Reductive elimination
Me O O Rh L L MeI O Rh L I L O I Rh O Me L L = PPh3 L L = P(OPh)3
22
Overview of Organometallic Chemistry
Organometallic reaction steps
s-bond metathesis
Lu CH3 *CH4 H3 *C H Lu C H3
Lu
*CH3
14 e
23
Overview of Organometallic Chemistry
Organometallic reaction steps
Redox reactions
Fe
- e-
Fe
Homolysis
Et Hg Et Et Hg + Et
24
Overview of Organometallic Chemistry
Organometallic reaction steps
Reactivity of coordinated ligands
25
Overview of Organometallic Chemistry
Factors governing structure and reactivity of organometallic compounds
M-C, M-X bond strengths Electronegativity of M (polarity of M-C etc bonds) Number of (d) electrons Coordination number Steric hindrance
26
Overview of 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
27
Overview of Organometallic Chemistry
Working with organometallics
Synthesis and reactivity studies (inert atmosphere!): Glove box Schlenk line, specialized glassware Characterization: Xray diffraction structure bonding NMR structure en dynamic behaviour (calculations) IR MS EPR Not: GC LC
28
Overview of Organometallic Chemistry