Chem 634. Introduction to Transition Metal Catalysis. Reading: Heg Ch 1 2 CS-B 7.1, , 11.3 Grossman Ch 6

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1 Chem 634 Introduction to Transition etal Catalysis eading: eg Ch 1 2 CS-B 7.1, , 11.3 Grossman Ch 6

2 Announcements Problem Set 1 due Thurs, 9/24 at beginning of class ffice our: Wed, 10:30-12, 220 B

3 Announcements

4 rganometallic Complexes PPh 3 Ph 3 P h Cl Cl Pd PPh PPh 3 PPh3 PPh3 Cl Pt Cl PPh 3 3 Cl 2 Ph 2 2 P Cl u P Cl Ph 2 2 Ph Ph otol 2 P Ir Ph B CF 3 CF III IV V VI VII VIII IX X XI XII d 3 d 4 d 5 d 6 d 7 d 8 d 9 d 10 d 10 s 1 d 10 s 2 1 st row Sc Ti V Cr n Fe Co i Cu Zn 2 nd row Y Zr b o Tc u h Pd Ag Cd 3 rd row a f Ta W e s Ir Pt Au g early dividing line late

5 ow any Valence Electrons? Consider C 4 ecall the ctet ule 2p x 3 E CA's of 4 1s orbitals 2s Bonding orbitals filled... stable configuration. C C 4 4 x

6 ow any Valence Electrons? Transition metals have 5 d orbitals (plus s & 3 p s)! x antibonding orbitals (n+1)p x 3 E (n+1)s nd x 5 (9 x) nonbonding orbitals Bonding and nonbonding orbitals filled... stable configuration. x x bonding orbitals x

7 Determining Electron Count of T Complex Ionic ethod: All ligands are dissociated with their electrons. -type ligands = neutral, 2 e - donor X-type ligands = anionic 2 e - donor X X n X X n+y where y = number of x-type ligands mnemonic: X X + X X Electron counting is a formalism.

8 Example of Ionic ethod Electron Counting C C Fe C C C C Fe 2+ C C 4 X C 4 X 2e - 8e - 2 X 2 X 2e - 4e - Fe(2+) (d 6 ) 6e - 18e - ote: Both Ionic and eutral ethods give the same electron count, but differ in how they treat the metal center.

9 Charged Complexes Cl Cl Pd 2 2K + Cl Cl 4 X Cl - 4 X 2e - 8e - Pd(2+) (d8) 8e - 16e -

10 xidation State Formalism to account for oxidation state of metal center. This is only a formalism, in reality electrons (and thus charge) are shared over both the ligand and metal. onetheless, oxidation state guides understanding of metal reactivity. Using ionic method of electron counting arrives directly at metal oxidation state. Example: C Fe C C C xidation State = Fe(II) 4 X C 4 X 2e - 8e - 2 X 2 X 2e - 4e - Fe(2+) (d 6 ) 6e - 18e -

11 Examples of X-type igands igand Complex Disconnection ligand charge ligand e - hydride halide Cl + + Cl -1 2 alkyl C C aryl (σ bound) acetylide silane Si Si amido alkoxide

12 Examples of X-type igands (ore Complex) igand Complex Disconnection ligand charge ligand e - acetate (η1) e + + e -1 2 acetate (η3) e + + e -1 4 allyl (η1) allyl (η3) cyclopentadienyl (Cp) η (eta) denotes hapticity = how many atoms of ligand are bond to metal from single donor site.

13 Examples of 2e Donor -type igands igand Complex Disconnection ligand charge ligand e - phopshine PPh 3 + PPh amine Et 3 + Et nitrile C + C 0 2 sigma bond ( ) sigma bond (C ) C 3 C 3 alkene carbonyl C + C 0 2 ether

14 -type igands Donating ore than 2e igand Complex Disconnection ligand charge ligand e - diene arene (η6) arene (η2) bisphosphine (κ 2 ) Ph Ph P P Ph Ph + Ph Ph P P Ph Ph X 2e -type ligands diamine (κ 2 ) P X 2e -type ligands κ (kappa) denotes denticity = how many binding sites of a polydentate ligand are bound.

15 X 2 igands igand Complex Disconnection ligand charge ligand e - triplet carbenes (alkylidines) oxo C C imido (bent)

16 C-igands igand Complex Disconnection ligand charge ligand e - -heterocyclic carbenes Sigma Bond Pi-Backbond C C

17 18 Electron ule any, but not all, stable, isolatable T complexes are 18e complexes. Ph 3 P PPh 3 Pd PPh3 PPh 3 Ph 2 P P Ph 2 Cl u Cl 2 2 Pd = group 10 10e- + 8e- = 18e- u = group 8 +2 = d = 18 TE: 18e rule is more of a suggestion. any of the most interesting, i.e. reactive, complexes do not follow this rule.

18 Basic rganometallic echanisms To understand transition metal catalysis, we need to understand something about the mechanisms by which the catalysts operate. any T catalyzed reactions proceed via a series of elementary steps.

19 Dissociative igand Substitution - ' ' common with: coordinately saturated 18e- complexes

20 Associative igand Substitution ' equatorial ligand w/ strongest pi-interactions ' ' common with: 16 e- complexes requires open coordination site ' Y* Y* trans effect '

21 xidative Addition [ n ] X [ n+2 ] X formal oxidation state of metal center increases by two favored by electron-rich metal centers Example: Ph 3 P Pd 0 Ph 3 P Ph I Ph 3 P Pd II Ph 3 P Ph I

22 eductive Elimination [ n ] [ n-2 ] + formal oxidation state of metal center decreases by two promoted by electron poor metal centers large ligands accelerate process microscopic reverse of oxidative addition Example: i II Ph i 0 + Ph

23 Transmetallation [ n ] X ' ' [ n ] ' + ' X Exchange of ligands between different metal centers o change in oxidation state at metals Exact mechanisms are complex, some are still unknown. Example: Ph 3 P Pd II Ph 3 P Ph I Bu 3 Sn Ph Ph 3 P Pd II Ph 3 P Ph Ph + Bu 3 SnI

24 igratory Insertion [ n ] X [ n ] X igand inserts into adjacent metal-ligand bond o net change of oxidation state at the metal Examples: C PPh 3 h I C C PPh 3 h I PPh 3 PPh 3 Ar + + Ph 3 P Pd II PPh 3 Ph 3 P Pd II PPh 3 Ar

25 β-elimination [ n ] [ n ] icroscopic reverse of migratory insertion o net change of oxidation state at the metal ost often observed as β-hydride elimination from alkyl ligand equires open coordination site on the metal center Example: PPh 3 + PPh 3 + Ph 3 P Pd II Ar Ph 3 P Pd II note open coordination site

26 β-elimination ote: most of the time, β-hydride elimination is superfacial. This is because the mechanism is inner-sphere, involving formation of a metal-hydride bond. [Pd] Ph 3 Ph 3 PPh 3 + PPh 3 + Ph 3 P Pd II Ar Ph 3 P Pd II note open coordination site

27 α-elimination ' [ n ] [ n ] + ' Via: ' [ n ] or: [ n ] ' not common in organic synthesis

28 xidative Coupling/Cyclization [ n ] [ n+2 ] [ n ]

29 σ Bond etathesis [] ' '' [] ' + '' Via: [] [] ' '' ' '' Common mechanism of C- bond activation.

30 π Bond etathesis [] X Y [] X + Y via: [] X Y [2+2] [] [retro 2+2] [] X Y X Y Common in alkene metathesis.

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