CHE2380 Organometallic chemistry and structure determination of inorganic materials

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Dr. U. Baisch

1995 - 1999
1999 2000

Undergraduate studies in chemistry, University of Tbingen, Germany

Erasmus research project on the synthesis of lanthanide compounds, University of Pisa, Italy Degree in chemistry and structural chemistry (MChem, Dipl.-Chem.), University of Tbingen, Germany PhD in Chemistry, University of Munich, German Postdoctoral Fellowship, CNRS Laboratoire de Chemie de Coordination (LCC), Toulouse, France

2000 - 2001

2001 - 2006

2006 - 2007
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2007 - 2008
2008 2009

Postdoctoral Fellowship, University of Bologna, Italy

Marie-Curie Fellowship Universities of Bristol (UK) and Bologna Lecturer in Chemistry Newcastle University, UK

2009 - 2013

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CHE2380 Organometallic chemistry and structure determination of inorganic materials: 1.Definition of organometallic chemistry: History, Metal to carbon bonds; types of bonding; 18 electron rule; Methods of formation of bonds; Reactivity of the metal to carbon bonds. 2.Organometallic compounds of the transition metals: preparation of carbonyls; structures of carbonyls. Interpretation of infra red spectra; reactions of carbonyls and derivatives. 3.Donor and acceptor ligands: Olefin and alkyne complexes; Allyl complexes; cyclopentadienyl metal complexes. 4.Organometallic compounds of: alkaline earths, beryllium and the magnesium group; Zinc, mercury and cadmium; aluminium, gallium, indium and thallium; Silicon, geranium, tin and lead.
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SYNOPSIS
5.Pseudo organometallic complexes: nitrosyl complexes; phospine complexes. 6.Metal -Metal bonds and clusters: Formation and criteria of metal-metal bonds; structure and bonding isolability; dinuclear and tetranuclear clusters. 7.Organometallic catalysis: Isomerisations; Oligomerisation and polymerization; Fischer - Tropsch Monsanto and Reppe processes. 8.Methods of structure determination Recommended Texts: Coates, Green, Powell & Wades, Principles of Organometallic chemistry. Methuen & Co.

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First organometallic compound

1760 Louis Claude Cadet de Gassicourt (Paris) investigates inks based on cobalt salts and isolates cacodyl from cobalt minerals containing arsenic (CoAs2 and CoAsS2) : As2O3 + 4 CH3COOK [AsMe2]2 first organometallic compound

Timeline: 1751 - Benjamin Franklin: Lightning is electrical 1767: Carbonated water: Joseph Priestley 1778 - Antoine Lavoisier (and Joseph Priestley): discovery of oxygen leading to end of Phlogiston theory
See editorial: Organometallics 2001, 20, 1488 -1498

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First transition metal organometallic compound

1827 Zeises salt is the first platinum - olefin complex

Timeline: 1827: Friction match: John Walker 1827: Fountain-pen : Petrache Poenaru 1827 - Georg Ohm: Ohm's law (Electricity) 1827 - Amedeo Avogadro: Avogadro's law (Gas laws) 1828 - Friedrich Whler synthesized urea, destroying vitalism 1829: Steam locomotive: George Stephenson See 15:49 editorial: Organometallics 2001, 20, 2-6

1900 1950
1863 Charles Friedel and James Crafts prepare organochlorosilanes 1890 Ludwig Mond discovers Ni(CO)4 1893 Alfred Werner develops the modern ideas of coordination chemistry 1899 introduction of Grignard reagents

1912 Nobel prize Victor Grignard and Paul Sabatier

1917 Schlenk prepares Li alkyls via transalkylation from R2Hg 1930 Ziegler and Gilman simplify organolithium preparation, using ether cleavage and alkyl halide metallation, respectively

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1950 1960
1951 1952 Discovery of ferrocene, Fe(h5-C5H5)2
Keally, Pauson, and Miller report the synthesis Wilkinson and Woodward report the correct structure

1973 Nobel prize Geoffrey Wilkinson and Ernst Otto Fischer on sandwich compounds 1955 Ziegler and Natta develop olefin polymerization at low pressure using mixed metal catalysts (transition metal halide / AlR3)

Transition Metal
R2Al-R + n

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Catalyst

Ziegler/Natta polymerization
Giulio Natta: Italian chemist, Nobel prize 1963 Learned of Zieglers research, and applied findings to other a-olefins
such as propylene and styrene. Resulting polypropylene was made up of two fractions: amorphous (atactic) and crystalline (tactic). Polypropylene is not produced in radical initiated reactions.
n propylene polypropylene

Control of polymer tacticity:

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1963 Nobel prize for Karl Ziegler and Giulio Natta on Ziegler-Natta catalysts

1960 1980: catalysis

1962: Vaskas complex

1964: Fischer reports the first metal carbene.

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olefin metathesis
1964: Banks reports the first example of olefin metathesis.

1971: Yves Chauvin proposes mechanism.

1974: Schrock synthesizes first metal alkylidene complex.

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2005 Nobel prize in chemistry

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2010 Nobel prize in chemistry

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2010 Nobel prize in chemistry

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Ligands in organometallic chemistry

Neutral 2e donors: PR3 (phosphines), CO (carbonyl), R2C=CR2 (alkenes), RCCR (alkynes, can also donate 4e), NCR (nitriles) Anionic 2e donors: X- (halide), CH3- (methyl), CR3- (alkyl), Ph- (phenyl), H- (hydride) The following can also donate 4e if needed, but initially count them as 2e donors (unless they are acting as bridging ligands): OR(alkoxide), SR- (thiolate), NR2- (inorganic amide), PR2- (phosphide) Anionic 4e donors: C3H5- (allyl), O2- (oxide), S2- (sulfide), NR2(imide), CR22- (alkylidene) and from the previous list: OR- (alkoxide), SR- (thiolate), NR2(inorganic amide), PR2- (phosphide) Anionic 6e donors: Cp- (cyclopentadienyl), O2- (oxide) Z ligands: do not bring e to the metal: BR3, AlR3

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Nomenclature

x
M

M M

h5-Cp

h3-Cp

h3-allyl

h1-allyl

kx mx
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PPh2

PPh2

h1-dppe / k1-dppe

- bridging ligand

Common organometallic ligands

M H M C M C C CNR NO M M N2 PR3 M H H M H X M

M M

CO CS

M M

M M M

M C C

Ordering in nomenclature
1. In formulas with Cp (cyclopentadienyl) ligands, the Cp usually comes first, followed by the metal center: Cp2TiCl2
Other anionic multi-electron donating ligands are also often listed in front of the metal.

2. In formulas with hydride ligands, the hydride is sometimes listed first.

Rule # 1, however, takes precedence over this rule: HRh(CO)(PPh3)2 and Cp2TiH2

3. Bridging ligands are usually placed next to the metals in question, then followed by the other ligands
Note that rules 1 & 2 take precedence: Co2(m-CO)2(CO)6, Rh2(mCl)2(CO)4, Cp2Fe2(m-CO)2(CO)2
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Coordination geometries
CN 2 Geometry Example [NCAgCN]

3, trigonal
3, T shape

Pt(PPh3)3
[Rh(PPh3)3]+

4, tetrahedron

Ti(CH2Ph)4

4, square planar

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Coordination geometries
CN Geometry Example 5, trigonal bipyramid

5, square pyramid

[Co(CNPh)5]2+

6, octahedron

W(CO)6

6, pseudo-octahedron
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FeCp2

Coordination geometries
CN Geometry Example

6, antiprism

WMe6

7, capped octahedron

[ReH(PR3)3(MeCN)3]+

7, pentagonal biprism

[IrH5(PPh3)2]

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Reactivity of the Organometallic Bond

Strong preference for s-donor groups but Cp is often p-bound (deceptively like with transition metals)

Cp2Mg

Cp2Fe

Electropositive metals: often 3c-2e or 4c-2e hydrides/alkyls

(Me3Al)2

(MeLi)4

Reactivity of the Organometallic Bond

As a Nucleophile Addition to polar C=X bonds (C=O, C=N, CN)

R M

+ O

R OM

Substitution at sp2 carbon (often via addition)

R M

+ O

OR'

OR' OM

R O

- MOR'

Reactivity of the Organometallic Bond

Substitution at sp3 carbon does occur, but is far less easy and often has a multistep mechanism

Substitution at other elements: often easy for polar M-X bonds (Si-Cl, B-OMe)
Me MeMgBr + B(OMe)3 BrMg B(OMe)2 OMe MeOMgBr + MeB(OMe)2 Me3B

Reactivity of the Organometallic Bond

As a base More prominent in polar solvents (think of free R- acting as base) H

Elimination

R M X

+ RH + MX

mechanism can be more complex than this

Metallation

H R M Me2N

M + RH Me2N

Chelate effect more important than inductive effect!

Reactivity of the Organometallic Bond

b-hydrogen transfer

Al O

Al O

mainly for Al: for more electropositive elements, deprotonation and nucleophilic attack are faster for less electropositive elements, often no reaction

Some compounds do not contain metal-carbon bond, but they are usually included in the field of organometallic chemistry. They include: Metal hydride complexes

Phosphine complexes

N2-complexes

Exercise: Which of the following compounds is an organometallic compound?

OCH3 a) CH3O Ti b) OCH3 OCH3 O CH2 CH2 d) O Pt O Ph OC e) Me Li Me Me Li P CO CO O Co C Co CO CO O H3 N NH3 Cu 2+

NH3 NH3

Cl c) Cl Pt Cl

In general, metals in organometallic compounds include: main group metals transition metals f-block metals

Li

Me

Li

f) OC Co O C Co OC OC P Ph

Why organometallic chemistry ?

From practical point of view: A) OMC are useful for chemical synthesis, especially catalytic processes, In production of fine chemicals

In production of chemicals which, in large-scale reactions, could not

be achieved traditionally

B) Organometallic chemistry is related to material sciences. e.g. Organometallic Polymers

PBu3 Pt C C C C n PBu3 PBu3 Pt C C C C n PBu3

Small organometallic compounds: Precursors to films for coating (MOCVD) (h3-C3H5)2Pd -----> Pd film CH3CC-Au-CNMe -----> Au film Luminescent materials (see later)

C) Biological Science. Organometallic chemistry may help us to understand some enzyme-catalyzed reactions.
e.g. B12 catalyzed reactions.

From academic point of view: Organometallic compounds display many unexpected behaviors- discover new chemistry- new structures
M M C M C C C M C C M M H M H M H SiR3

H3N:

New reactions, reagents, catalysts, e.g. Ziegler-Natta catalyst, Wilkinson catalyst

Reppe reaction, Schwartz's reagent

Sharpless epoxidation, Tebbe's reagent

Organometallic Bonds
Language: All bonds are coordination or coordinative Remember that all of these bonds are weaker than normal organic bonds (they are dative bonds)! Simple ligands e.g. CH3-, Cl-, H2 give s bonds p systems are different e.g. CO is a s donor and p acceptor Bridging ligands can occur two metals Metal-metal bonds occur and are called d bonds they are weak and are a result of d-d orbital overlap

18 Electron Rule (Sidgwick, 1927)

OM chemistry gives rise to many stable complexes - how can we tell by a simple method Every element has a certain number of valence orbitals: 1 { 1s } for H 4 { ns, 3np } for main group elements 9 { ns, 3np, 5(n-1)d } for transition metals

px

py

pz

dxy

dxz

dyz

dx2-y2

dz2

 Therefore, every element wants to be surrounded by 2/8/18 electrons - For main-group metals (8-e), this leads to the standard Lewis structure rules - For transition metals, we get the 18-electron rule Structures which have this preferred count are called electron-precise Every orbital wants to be used", i.e. contribute to binding an electron pair The strength of the preference for electron-precise structures depends on the position of the element in the periodic table For early transition metals, 18-e is often unattainable for steric reasons the required number of ligands would not fit For later transition metals, 16-e is often quite stable (square-planar d8 complexes) Addition of 2e- from 5th ligand converts complex to 5 CN 18e- which is marginally more stable

Predicting reactivity
14 e

- C2H4 (C2H4)2PdCl2
16 e

dissociative (C2H4)PdCl2

CO (C2H4)(CO)PdCl2 - C2H4
16 e

?
(C2H4)2(CO)PdCl2 associative
18 e

CO

Most likely associative

Predicting reactivity
16 e

- CO
18 e

dissociative Cr(CO)5

MeCN Cr(CO)5(MeCN) 18 e - CO

Cr(CO)6

?
20 e (Sterics!)

MeCN

Cr(CO)6(MeCN) associative

Most likely dissociative

N.B. How do you know a fragment forms a covalent or a dative bond?

Chemists are "sloppy" in writing structures. A "line" can mean a covalent bond, a dative bond, recognise/understand the bonding first Use analogies ("PPh3 is similar to NH3"). Rewrite the structure properly before you start counting.

Cl Pd
covalent bond

PPh3
1e dative bond

Cl Pd

PPh3
2e

Pd = Cl- = PR3 = allyl =

10 1 2 3 ------e-count 16

"bond" to the allyl fragment

3e

"Covalent" count: (ionic method also useful) 1. Number of valence electrons of central atom. 2. Correct for charge, if any (only if the charge belongs to that atom!) 3. Count 1 e for every covalent bond to another atom. 4. Count 2 e for every dative bond from another atom. no electrons for dative bonds to another atom! 5. Delocalized carbon fragments: usually 1 e per C (hapticity) 6. Three- and four-center bonds need special treatment 7. Add everything
N.B. Covalent Model: 18 = (# metal electrons + # ligand electrons) - complex charge The number of metal electrons equals it's row number (i.e., Ti = 4e, Cr = 6 e, Ni = 10 e)

Hapto (h) Number (hapticity) For some molecules the molecular formula provides insufficient information with which to classify the metal carbon interactions The hapto number h gives the number of carbon (conjugated) atoms bound to the metal It normally, but not necessarily, gives the number of electrons contributed by the ligand We will describe to methods of counting electrons but we will employ only one for the duration of this module

The two methods compared:

N.B. like oxidation state assignments, electron counting is a formalism and does not necessarily reflect the distribution of electrons in the molecule
Some ligands donate the same number of electrons Number of d-electrons and donation of the other ligands can differ

Does it look reasonable ?

Remember when counting: Odd electron counts are rare In reactions you nearly always go from even to even (or odd to odd), and from n to n-2, n or n+2. Electrons dont just appear or disappear The optimal count is 2/8/18 e. 16-e also occurs frequently, other counts are much more rare.

Exceptions to the 18 Electron Rule ZrCl2(C5H5)2 TaCl2Me3 WMe6 Pt(PPh3)3 IrCl(CO)(PPh3)2 Ir(9) + Cl(1) + CO(2) + [2 x PPh3(2)] =16 What features do these complexes possess? Zr(4) + [2 x Cl(1)] + [2 x C5H5(5)] =16 Ta(5) + [2+ x Cl(1)] + [3 x M(1)] =10 W(6) + [6 x Me(1)] =12 Pt(10) + [3 x PPh3(2)] =16

Early transition metals (Zr, Ta, W) Several bulky ligands (PPh3) Square planar d8 e.g. Pt(II), Ir(I) -donor ligands (Me)

Alkyl ligands: Transition metal alkyl complexes are important for catalysts e.g. olefin polymerization and hydroformylation Problem is their weak kinetic stability (Thermally fine: M-C bond dissociation energies are typically 40-60 kcal/mol) Simple alkyls are sigma donors, that can be considered to donate one or two electrons to the metal center depending on which electron counting formalism you use

Synthesis of Metal Alkyl Complexes 1. Metathetical exchange using a carbon nucleophile (R-). Common reagents are RLi, RMgX (or R2Mg), ZnR2, AlR3, BR3, and PbR4. Much of this alkylation chemistry can be understood with Pearson's "hard-soft" principles

Synthesis of Metal Alkyl Complexes 1. Metathetical exchange using a carbon nucleophile (R-). Common reagents are RLi, RMgX (or R2Mg), ZnR2, AlR3, BR3, and PbR4. Much of this alkylation chemistry can be understood with Pearson's "hard-soft" principles

2. Metal-centered nucleophiles (i.e. using R+ as a reagent) Typical examples are a metal anion and alkyl halide (or pseudohalogen). for example: NaFp + RX Fp-R + NaX [Fp = Cp(CO)2Fe]

3. Oxidative Addition. This requires a covalently unsaturated, low-valent complex (16 e- or less). A classic example:

4. Insertion- To form an alkyl, this usually involves an olefin insertion. The simplest generic example is the insertion of ethylene into an M-X bond, i.e. M-X + CH2CH2 M-CH2CH2-X

Carbonyl Complexes Bonding of CO

Electron donation of the lone pair on carbon s This electron donation makes the metal more electron rich - compensate for this increased electron density, a filled metal d-orbital may interact with the empty p* orbital on the carbonyl ligand
p-backbonding or pbackdonation or synergistic bonding Similar for alkenes, acetylenes, phosphines, and dihydrogen.

What stabilizes CO complexes is MC bonding The lower the formal charge on the metal ion the more willing it is to donate electrons to the orbitals of the CO Thus, metal ions with higher formal charges, e.g. Fe(II) form CO complexes with much greater difficulty than do zero-valent metal ions For example Cr(O) and Ni(O), or negatively charged metal ions such as V(-I) In general to get a feeling for stability examine the charges on the metals

Syntheses of metal carbonyls Metal carbonyls can be made in a variety of ways. For Ni and Fe, the homoleptic or binary metal carbonyls can be made by the direct interaction with the metal. In other cases, a reduction of a metal precursor in the presence of CO (or using CO as the reductant) is used. Carbon monoxide also reacts with various metal complexes, most typically filling a vacant coordination site or performing a ligand substitution reactions. Occasionally, CO ligands are derived from the reaction of a coordinated ligand through a deinsertion reaction

Synthesis of carbonyl complexes

Direct reaction of the metal

Not practical for all metals due to need for harsh conditions (high P and T)

Ni + 4CO Ni(CO)4 Fe + 5CO Fe(CO)5

Reductive carbonylation Useful when very aggressive conditions would be required for direct reaction of metal and CO Wide variety of reducing agents can be used CrCl3+ Al + 6CO AlCl3 + Cr(CO)6 3Ru(acac)3 + H2 + 12CO Ru3(CO)12 + H2acac

IR spectra and metal-carbon bonds The nCO stretching frequency of the coordinated CO is very informative Recall that the stronger a bond gets, the higher its stretching frequency M=C=O (C=O is a double bond) canonical structure nCO stretching frequency is lower as compared to the M-CO structure (triple bond) Note: nCO for free CO is 2041 cm-1) [Ti(CO)6]2- [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ [Fe(CO)6]2+ nCO 1748 1858 1984 2094 2204 cm-1

increasing M=C double bonding

decreasing M=C double bonding

Bridging versus terminal carbonyls

Bridging CO groups can be regarded as having a double bond C=O group, as compared to a terminal CO, which is more like a triple bond:
~ triple bond ~ double bond

M-CO
M terminal carbonyl (~ 1850-2125 cm-1)

C=O

the C=O group in a bridging carbonyl is more like the C=O in a ketone, which typically has nCO = 1750 cm-1

bridging carbonyl (~1700-1860 cm-1)

Bridging CO between 1700 and 2200 cm-1

Bridging versus terminal carbonyls in [Fe2(CO)9]

O OC OC Fe OC CO C Fe C C O O CO

CO

terminal carbonyls

bridging carbonyls

Summary

1. As the CO bridges more metal centers its stretching frequency drops same for all p ligands More back donation

2. As the metal center becomes increasingly electron rich the stretching frequency drops

Alkene ligands Dewar-Chatt-Duncanson model The greater the electron density back-donated into the p* orbital on the alkene, the greater the reduction in the C=C bond order Stability of alkene complexes also depends on steric factors as well An empirical ordering of relative stability would be: tetrasubstituted < trisubstituted < trans-disubstituted < cisdisubstituted < monosubstituted < ethylene

Alkyne ligands:

Similar to alkenes Alkynes tend to bind more tightly to a transition metal than alkenes -alkynes will often displace alkenes
Difference is 2 or 4 electron donor sigma-type fashion (A) as we did for alkenes, including a pi-backbond (B) The orthogonal set can also bind in a pi-type fashion using an orthogonal metal dorbital (C)

The back-donation to the antibonding orbital (D) is a delta-bond-the degree of overlap is quite small - contribution of D to the bonding of alkynes is minimal The net effect p-donation - alkynes are usually nonlinear in TM complexes Resonance depict the bonding of an alkyne. I is the metallacyclopropene resonance form Support for this versus a simple two electron donor, II, can be inferred from the C-C bond distance as well the R-C-C-R angles III generally does not contribute to the bonding of alkyne complexes.

Ally ligands: Allyl ligands are ambidentate ligands that can bind in both a monohapto and trihapto form The trihapto form can be expressed as a number of difference resonance forms as shown here for an unsubstituted allyl ligand: Important applications

Dihydrogen Ligands: Metal is more electropositive than hydrogen. Hydrogen acts as a two electron sigma donor to the metal center. The complex is an arrested intermediate in the oxidative addition of dihydrogen

How does this affect the oxidation state of the metal?

Dihydrogen complexes Bonding is simple a 3C-2electron bond.

H2 - neutral two electron sigma donor One could also describe a back-donation of electrons from a filled metal orbital to the sigma* orbital on the dihydrogen

Electronic Attributes of Phosphines Like that of carbonyls

Electron-withdrawing sigma-donating capacity decreases

At the same time, the energy of the p-acceptor (sigma-*) on phosphorous is lowered in energy, providing an increase in backbonding ability.

Therefore, range of each capabilities tuning rough ordering -CO stretching frequency indicator- low CO stretching frequency- greater backbonding to M
Experiments such as this permit us to come up with the following empirical ordering:

Cone Angle (Tolman) Steric hindrance: A cone angle of 180 degrees effectively protects (or covers) one half of the coordination sphere of the metal complex Phosphine Ligand Cone Angle

PH3 PF3

87o 104o

P(OMe)3
PMe3 PMe2Ph PEt3 PPh3

107o
118o 122o 132o 145o

PCy3
P(t-Bu)3 P(mesityl)3

170o
182o 212o

You would expect a dissociation event to occur first before any other reaction Steric hindrance (rate is first order towards increasing size) This will also have an effect on activity for catalysts

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Engineering the Crystalline State - Crystal Engineering

Crystal Engineering
Sapphire watch crystal

Garnet structural motif for Nd-YAG

Melamine fire retardants / polymers

Building blocks derived from structural motifs of mineral and synthetic structures are recombined (engineered) in accordance with their connectivity and physical properties to synthesise crystals with new 15:49 physical properties

Intermolecular Interactions versus Optical Properties Lanthanide Crystal Engineering

Triboluminesence and Alexandrite Effect
[Cp3Gd] (UV-light, lexc = 366 nm) [Cp3Nd] (cold light source) [Cp3Ho] (cold light source)

[Cp3Nd] (sunlight)

[Cp3Ho] (sunlight)

Cyclopentadienyl-Lanthanide

[1] U. Baisch, S. Pagano, M. Zeuner, W. Schnick, Eur. J. Inorg. Chem. 2006, 3517. [2] U. Baisch, S. Pagano, M. Zeuner, N. Barros, L. Maron, W. Schnick, 15:49 Chem. Eur. J. 2006, 12, 4785.

Intermolecular Interactions versus Optical Properties Lanthanide Crystal Engineering

[Cp3YbNH3]
Crystalline powder

Two crystals of the same compound viewed under planepolarized light and in three different orientations towards the light source.
15:49 S. Pagano, M. Zeuner, N. Barros, L. Maron, W.Schnick, U. Baisch, Chem. Eur. J., 2006, 12, 4785.

Melamine and Lanthanide (Ln) Oxalates as Building Blocks in Crystal Engineering

NH2 N H2N N N NH2

LnCl3 Ln(NO3)3
HO OH

Melamine

Lanthanide Salt

Oxalic acid

Synthetic pathways: 1. Dissolve all components and make them react with each other 2. Mix all components together and heat them up 3. Combine 1. + 2. and use Solvent-drop assisted grinding
U. Baisch, D. Braga, CrystEngComm 2008, 11, 40.

Solvent-drop assisted grinding = Kneading

Advantages: Green Chemistry, less solvent = reduction of environmental pollution High Yield (close to 100%) One pot synthesis = low production costs

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Hexamelaminium tetraoxalato lanthanides

O O 5H2N + 6 N N N NH2 NH2 H + NO3OO O O OH H2N N NH2 "Kneading" O O O + 6N N Ln(NO3)3x nH2O + 4 O Ln O OO O O HO O NH2 O O

[C3H7N6]6[Ln(C2O4)4][NO3](H2O)n

U. Baisch, D. Braga, CrystEngComm 2008, 10, 40. 15:49

Hexamelaminium tetraoxalato lanthanides

Optical or magnetic properties?

Sunlight 15:49

UV-light

15:49

Reaction chemistry of complexes

Three general forms: 1. Reactions involving the gain and loss of ligands a. Ligand Dissoc. and Assoc. (Bala) b. Oxidative Addition c. Reductive Elimination d. Nucleophillic displacement

2. Reactions involving modifications of the ligand a. Insertion b. Carbonyl insertion (alkyl migration) c. Hydride elimination (equilibrium) 3. Catalytic processes by the complexes Wilkinson, Monsanto Carbon-carbon bond formation (Heck etc.)

a) Ligand dissociation/association (Bala)

Electron count changes by -/+ 2 No change in oxidation state Dissociation easiest if ligand stable on its own (CO, olefin, phosphine, Cl-, ...) Steric factors important

Br

+ Br-

b) Oxidative Addition
Basic reaction:

LnM +

X Y

X LnM Y

Electron count changes by +/- 2 (assuming the reactant was not yet coordinated) Oxidation state changes by +/- 2 Mechanism may be complicated The new M-X and M-Y bonds are formed using: the electron pair of the X-Y bond one metal-centered lone pair

One reaction multiple mechanisms

Concerted addition, mostly with non-polar X-Y bonds H2, silanes, alkanes, O2, ...

Arene C-H bonds more reactive than alkane C-H bonds (!)

LnM

X Y

LnM A

X Y

X LnM Y

Intermediate A is a s-complex Reaction may stop here if metal-centered lone pairs are not readily available Final product expected to have cis X,Y groups

Stepwise addition, with polar X-Y bonds HX, R3SnX, acyl and allyl halides, ...
low-valent, electron-rich metal fragment (IrI, Pd(0), ...)

X LnM X Y LnM X Y B
Metal initially acts as nucleophile Coordinative unsaturation less important Ionic intermediate (B) Final geometry (cis or trans) not easy to predict Radical mechanism is also possible

LnM Y

Cis or trans products depends on the mechanism

H H2 OC Et3P Cl Ir PEt3 H cis Ir(III)

H OC Et3P PEt3 Ir Cl Ir(I) HI OC Et3P Cl Ir

PEt3 I cis Ir(III)

CH3 PEt3 CH3Br OC Et3P Br trans Ir Cl Ir(III)

c) Reductive elimination This is the reverse of oxidative addition - Expect cis elimination Rate depends strongly on types of groups to be eliminated. Usually easy for: H + alkyl / aryl / acyl H 1s orbital shape, c.f. insertion alkyl + acyl participation of acyl p-system SiR3 + alkyl etc Often slow for: alkoxide + alkyl halide + alkyl thermodynamic reasons? We will do a number of examples of this reaction

Relative rates of reductive elimination

L Pd L CH3 CH3 + solv -L solv L Pd CH3 CH3 RE LPd(solv) + CH3 CH3

Complex Ph3P Pd Ph3P MePh2P Pd MePh2P Ph Ph Pd Ph P Ph CH3 CH3 CH3 CH3 CH3

Rate Constant (s-1) 1.04 x 10-3

T(oC)

60

9.62 x 10-5

60

CH3 4.78 x 10-7 80

Most crowded is the fastest reaction

Special case: Nucleophilic Attack on a Coordinated CO acyl anion

Fisher carbene

This is Fischer carbene It has a metal carbon double bond Such species can be made for relatively electronegative metal centers N.B. mid to late TMs Fischer carbenes are susceptible to nucleophilic attack at the carbon

Fischer carbenes act effectively as donors and p acceptors The empty antibonding M=C p orbital is primarily on the carbon making it susceptible to attack by nucleophiles Other type is called a Shrock carbene (alkylidene)

Characteristic Typical metal (Ox. State) Substituents attached to carbene carbon Typical other ligands Electron count

Fischer-type Middle to late T.M. Fe(0), Mo(0) Cr(0) At least one highly electronegative heteroatom Good p acceptors 18

Schrock-type Early T.M. Ti(IV), Ta(V) H or alkyl

Good s and p donors 10-18

Nucleophilic displacement Ligand displacement can be described as nucleophilic substitutions O.M. complexes with negative charges can behave as nucleophiles in displacement reactions Iron tetracarbonyl (anion) is very useful
O R R'X [Fe(CO)4 ]2RX [ R Fe(CO)4]X2

R' O

O2

R O R X

OH

H+ R O X O [ R Fe(CO)4 ]R CO R H

H+

O H

Modifications of the ligand a) Insertion reactions Migratory insertion! The ligands involved must be cis - Electron count changes by -/+ 2 No change in oxidation state

If at a metal centre you have a s-bound group (hydride, alkyl, aryl)

a ligand containing a p-system (olefin, alkyne, CO) the s-bound group can migrate to the p-system 1. CO, RNC (isonitriles): 1,1-insertion 2. Olefins: 1,2-insertion, b-elimination

R M CO
1,1

R M O R M
1,2

M R

1,1 Insertion

The s-bound group migrates to the p-system if you only see the result, it looks like the p-system has inserted into the M-X bond, hence the name insertion To emphasize that it is actually (mostly) the X group that moves, we use the term migratory insertion (Both possible tutorial) The reverse of insertion is called elimination Insertion reduces the electron count, elimination increases it

Neither insertion nor elimination causes a change in oxidation state

a- elimination can release the new substrate or compound

In a 1,1-insertion, metal and X group "move" to the same atom of the inserting substrate. The metal-bound substrate atom increases its valence

Me M CO

M O

Me

Me M SO2

S Me

O O

CO, isonitriles (RNC) and SO2 often undergo 1,1-insertion 1,2 insertion (olefins)

Insertion of an olefin in a metal-alkyl bond produces a new alkyl

Thus, the reaction leads to oligomers or polymers of the olefin polyethene (polythene) polypropene

Standard Cossee mechanism

R M R M R M R M

Why do olefins polymerise? Driving force: conversion of a p-bond into a s-bond One C=C bond: 150 kcal/mol Two C-C bonds: 285 = 170 kcal/mol Energy release: about 20 kcal per mole of monomer (independent of mechanism)

Many polymerization mechanisms Radical (ethene, dienes, styrene, acrylates) Cationic (styrene, isobutene) Anionic (styrene, dienes, acrylates) Transition-metal catalyzed (a-olefins, dienes, styrene)

b Hydride elimination (usually by b hydrogens)

Many transition metal alkyls are unstable (the reverse of insertion) the metal carbon bond is weak compared to a metal hydrogen Bond Alkyl groups with hydrogen tend to undergo elimination

M -CH2-CH3 M - H + CH2=CH2
Two examples

A four-center transition state in which the hydride is transferred to the metal An important prerequisite for beta-hydride elimination is the presence of an open coordination site on the metal complex - no open site is available - displace a ligand metal complex will usually have less than 18 electrons, otherwise a 20 electron olefin-hydride would be the immediate product.

To prevent beta-elimination from taking place, one can use alkyls that: Do not contain beta-hydrogens Are oriented so that the beta position can not access the metal center Would give an unstable alkene as the product

Catalysis (homogeneous) Reduction of alkenes etc.

The size of the substrate has an effect on the rate of reaction

Same reaction different catalyst

Alternative starting material

The Monsanto acetic acid process Methanol - reacted with carbon monoxide in the presence of a catalyst to afford acetic acid Insertion of carbon monoxide into the C-O bond of methanol The catalyst system - iodide and rhodium Iodide promotes the conversion of methanol to methyl iodide, Methyl iodide - the catalytic cycle begins: 1. Oxidative addition of methyl iodide to [Rh(CO)2I2]2. Coordination and insertion of CO - intermediate 18-electron acyl complex 3. Can then undergo reductive elimination to yield acetyl iodide and regenerate our catalyst

Catvia Process

Wacker process (identify the steps)

Identify the steps