Oxidative Addis in OM

chemistry
Critical in for example hydrogenation s C If carbo
functiona ization
s and C X couplings

Opposite RE key bond making step in synthesis

via om mediated catalysis

Some general considerations

Need 7 d system for process at a singlemetal

Low valent E rich systems are tommon

Thermodyamic considerations Ha R X often facile

R it C C tendtowards RE

keg

kegI 104

1018
KegI

Non Polar substrates

sd
Hz as a simple but very importantsubstrate
Hydrogenation via Wilkinson'scatalyst

AN R

HOWDOESTHIS
STEPOCCUR

Reactionsproceed via T adduct Hz complex

followed by OA to dihydride

M Ha's MIA
often in rapid
equilibrium

Low e Goddard 1984

Ears longer

Ere EARLY
TS

In manysystems the Hzadduct is not observed

Thermodynamic
or

kinetic
 Consider the stereochemistry of the
above OA

Vast pet A is favored

Kinefflly
B is thermodyn

w
EEE s
Compare
PETITE

EEIIJ.CIE Ij
Eat
CO in equat plane
better it bonding

For Wilkinson's Catalyst

Hydrogenation
there are two competing pathways

PRE EQUIL
IS DISFAVORED 4 48m s
s
o

ratez rate k CBRhICHi

g4tf
kg.gg h Him s

my ox ADDN Is
10,000 Faster at
rate rate rate
3 coord species
 OXIDATIVE ADDI OF HEVIA METAL CENTERS
Z
00

ClassicHalpernstudy preferred path

y Fitz
rate k Collen
termolecularts
SHE 0.7kcal not
Ask 55cal mol k
Eseems
Cocenters are unlikely Also see work by
18e etrivalent d4 B Wayland on
TPP Bh Cil

Related more recentexample Bimolecular TS

Other PATHS To Az CLEAVAGE 8

NOT OXID ADD NS

f bond metath Bifunctional Bifunctional

F
of F
r
Bercaw MILSTEIN SAVO
Bifunctional is key
to some Hydrogenation's
OXIDATIVE ADD N OF GH BONDS
ARE HIGHLY
S
C H ACTIVATION FUNCTIONALIZATION
DESIRABLE BUT SUFFER FROM CHALLENGES
TYPICALLY THERMODYNAMICALLY UNFAVORABLE
RE IS MOST OFTEN FAVORED
ALKANES ARE POOR LIGANDS
CHEMOSELECTIVITY
USE OF REACTIVE ELECTROPHILE PROMOTED
HETERITIC CLEAVAGE HAS EMERGED AS
APPROACH
VERY VERSATILE IN SYNTHESIS

EARLY EXAMPLES OF INTERMOLECULAR ALKANE ACTIVATION

BERGMAN

GRAHAM
1982
MECHAN
CONCERTEDPATHWAYS ARE
ANALOGOUS TO Az

A COMMON SUB VARIANT OF THE CONCERTED

PATHWAY IS TERMED
CONCERTED METALLATIONDEPROTONATION CMD
F BOND METATHESIS
 sat 1st kit
Example
Low Aft
LARGE NEGATIVE 1St
SMALL KIE

III'atiation

FAGNOU STUDIES

CMD
PATHWAY

BACK TO CONCERTED GH ACTIVATION

NOEXCHANGE
FORCOD AT
10 C

Rh Art DOES
NOT DISSOC

COORDINATION
ARENE
FFS
60 C DOMINATES SELECT
PREF
AT
DATA HELP EXPLAIN FAVORED REACTIVITY
OF Ar H us R H ALMOST UNIVERSALLY
KIE STUDIES ALSO POINT TO MCARH COMPLEX

s s EE e

aad
JEE.EE
J

PICTURE OF SCENARIO

IFJdeterminingstep
m selectivity

A
 OXID ADDN OF POLAR C X H X BONDS

Ze processes

Nucleophilic
substitutions

I E COMMON FOR ALKYL X

ONDA DONS VEII

fast

As WELL AS m't X R e Mnt R

x
R Xanthe x MAIR
00 RADICALPATHWAY ON D ADDN VIA ET CAN GO VIA
INNER OR OUTER SPHEREPATHWAY

A BOT NOT
RELIABLE

I
FIInnerspher

I THERMODYNAMIC
Mnt In
g REDOX

8 Eve

Common TOOLS TO DISTINGUISH PATHWAYS

CONCERTED US HETERO US IE ET

UNLIKE LIGAND SO BST KINETIC STUDIES CAN

BE OF LIMITED VALUE TO RESOLVE
BOTH CONCERTED
RATE
Roy CMJ sub
HETERO

ALTHREE TOPES GIVE NEG Dst VALUES

SUBSTRATE REACTIVITY STUDIES CAN BE

DISCRIMINATING
HETERO LYTIC AND CONCERTED

CHz X FRITZ RX 73 RX
RADICAL
30 RX 20 RX TRX CAR
 EXAMPLES

Solvent
IMPACTS HETERO LYTIC PATHWAY HEAVILY

STEREO CHEM

CONCERTED RETENTION

HETERO LYTIC S NZ like Inversion

RADICAL_ LOSS OF STEREOCHEM
onless radical recomb is
faster than racem rate
 INVERSION
CONSISTENT
W HETERO
PATH SNL

RADICAL CLOCKS

what if you
Fp't
onlyhadthis
result
CpFelcoÉ Fp
or
Ham met studies have been commonly used
to distinguish ionic from concerted path
al aryl halides
PETTIE

P Value INDICATES SOME TRANSFER

22
Of E Density IN TS BUT LIKELY TOO
SMALL FOR ION I C PATH
 nie
Al
3 in 9in
Rit Mo remix E x D
It

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Éi

EEEE.E
oÉ

metorrelatiosn oftenusedtostudyOxidAddns
logkg p II.IE
IF IIctenIconstan
y
it Hot
y7eto
Is Fekete ly41 Etiity
f
Y KA pka logKA T
resat rent
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I
of ci
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bagnostii

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as
get Y T KIM's
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eptible

on no
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act
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giggtrgywithdrawinggroups o
y ie s I
E Electron donatinggroups
are T