Metal&Allyl&complexes&

Types&of&metal1carbon&complexes&
C1Ligands&&
 Allyl&Complexes&

! >&10&ways&to&make&it!!&

! Equally&complex&structures&adopted&by&it&
&
! Very&complex&&in&its&reacDvity….&
 SubsDtuDon&ReacDons&

Anionic&allyl&&
Groups&can&replace&
Halide&ions&on&metals&
Palladium&Sandwich&structure&

Bis&allyl&palladium&complex&
TransmetallaDon&
Mono&allyl&palladium&complex&

Palladium&complex&of&allyl&triphenylphosphine&
&
&
ALPHP&&&Pd&complex&
OxidaDve&addiDon&with&a&metal&
anion&/&electron&rich&center.&
&
Only&Sigma&Allyl&&aQached&to&transiDon&metal&
&
&albppt.cif&Pt&complex&
FormaDon&of&allyl&complexes&from&alkenes!&

&
Ox.&State&of&
Pd&is&+2&

Ox&state&
Of&Pd.&is&&
+4!&
AlternaDve!&
AlternaDve!&
OxidaDve&addn.&to&Pd(0)&
Co1condensaDon&of&metals&with&ligands&
•  Benzyl&complex&of&a&transiDon&metal&

•  CPCOMO&
 OxidaDve&addiDon&with&proton!!&

Proton&is&added&to&the&ligand!&
Adding&a&metal&“hydride”&

In&this&case,&we&know&it&is&only&a&proton&
 1st&step&is&oxidaDve&addn.&
•  CpCo(CO)2&+&&C3H5I&&&&
η5 and η5" η3 and η5"
" "
20 electron&complex& 18 electron&complex&
Adding&an&alkyl&anion&to&diene&
 z&
Structure&and&bonding&
y&
x& &

4py& 3dyz&

3dxz&
4px&

4s& 4pz& 3dz2&

Allyl&complexes&fluxionality&and&
reacDvity&
Metal&Flips&
 Summary&
•  Allyl&fragment&forms&some&fascinaDng&
complexes&
•  3&carbons&almost&equally&bonded.&&
•  Formally&4&electron&donor&
•  NMR&is&the&only&spectroscopic&tool!&Could&be&
complicated.&&
Allyl$Complexes$Part$II$

Allyl$complexes$fluxionality$and$
reac7vity$
$
 Recap$
•  Ionic$method$it$is$formally$4$electron$donor$
(anionic$allyl$group):$3$carbons$almost$equally$
bonded$η3$structure!$$
•  Neutral$method:$3$electron$donor!$
•  In$equilibrium$with$η1$structure$where$only$
one$carbon$is$bonded.$2$electron$donor$in$the$
ionic$method!$$$
•  (1$electron$donor$in$the$neutral$method)$
Metal$Flips$
Allyl$Flips$
Allyl$vs.$Metal$Flips$

Both$give$the$same$result!$
3D$model$of$the$allyl$structure!$
Fluxional$Behaviour$
•  Spectroscopic$features$of$the$allyl$group$reflect$
this$fluxional$behavior.$

•  Posi7ons$1$and$3$are$equivalent$but$syn$and$an7$
are$rigid.$

•  NMR$is$the$only$spectroscopic$tool!$Could$be$
complicated.$Temperature$dependence$is$to$be$
studied.$
$
 All$4$Hydrogens$become$equivalent!$
40$deg.$DMSO$as$solvent$

4H$$$$$$$$$doublet!$
1H$$quintet$

Hc$ Ha,$Hs$

6.0$ppm$ 5.0$ppm$ 4.0$ppm$

 Room$temperature$spectrum$in$
chloroform,$$

2H$X2$$$$$$$$$doublet!$

1H$$triplet$of$triplet$

Hc$ Hs$ Ha$

6.0$ppm$ 5.0$ppm$ 4.0$ppm$ 3.0$ppm$

Pd$based$allylic$coupling$
Pd$based$allylic$coupling$
Wilke$
Cataly7c$Reac7on$
Reduc7ve$elimina7on,$subs7tu7on,$Oxida7ve$coupling,$$
inser7on,$reduc7ve$elimina7on$
Heimbach)
 t3
PE
Ni
n-C12H 26

H2
t 3
PE

Ni
PP
h3

CO

O
O Ni
 Reac7vity$
•  Is$it$[C3H5]+$or$is$it$[C3H5]*)?)

•  Depends)on)the)d)electron)count)and)charge)
on)the)total)complex.)
•  Structure$and$bonding$in$Allyl$Complexes$
 z$
Structure$and$bonding$
y$
x$ $

4py$ 3dyz$

3dxz$
4px$

4s$ 4pz$ 3dz2$

 Reac7vity$
•  Is$it$[C3H5]+$or$is$it$[C3H5]*)?)

•  Depends)on)the)d)electron)count)and)charge)
on)the)total)complex.)
CpFe(CO)2CH2]CH=CH2$

This$complex$loves$+ly$charged$centres:$Aldehydes$etc.$$
where$there$is$excess$electron$density$on$the$metal$
It$is$transferred$to$the$ligand.$
 What$is$the$electron$count$?$

• )This)complex)is)electrophilic!)

• )It)is)posi<vely)charged.)So)loves)electrons)
This)compound)is$a$mixture$of$two$isomers$
Both$metals$on$the$same$side$/$Metals$on$the$opposite$side$$
The$two$have$different$chemical$shibs$$
 Can$the$allyl$group$be$both$
electrophilic$and$nucleophilic?$
 [Ru(CO)3(C3H5)(OAC)]0)

Here$water$is$present$instead$of$OAc$

This$complex$is$a$Ru(II)$centre$and$so$expected$
to$behave$electron$rich$but$because$you$have$$
an$acetate$ligand,$it$is$ambivalent.$
 $
$Can$the$allyl$group$be$both$
electrophilic$and$nucleophilic?$$
$Yes!$$
$allylic$complex$
$a$“chem”eleon$

A$chameleon$changes$color$according$to$the$background$
Picture$taken$from$$Wikipedia$
hfp://upload.wikimedia.org/wikipedia/commons/4/45/
Bradypodion_pumilum_Cape_chameleon_female_IMG_1767_
%28cropped%29.jpg$
 Conclusion!$
•  Metal$can$control$the$reac7vity$of$the$allyl$
that$is$coordinated$to$it.$

•  The$ligand$can$modulate$its$reac7vity.$
C"C#Single#Bond#coupling#
C"C#coupling#wins#the#Nobel#Prize#2010#
#
Heck,#Suzuki#and#Neigishi!#
Sonoghashira,##SAlle,#Hiyama,#many#many#
more!#
 Synthesis#of#complex#molecules#
•  C"C#coupling#is#the#key#to#making#complex#
molecules#in#a#convergent#manner.#
 The#Problem#Defined#
•  C"C#coupling#
–  C."""Coupling#of#radicals##
–  C$"and"C+"
–  C"C#and#C"X#metathesis##
•  C=C#coupling####
–  Trimethylsilyldiazomethane#TMSCHN2##
–  WiOg####(Organophosphorus#chemistry)#
–  Metathesis#
–  ICH2ZnI##
–  Tebbe#ReacAon#
 Neghishi#C"C#coupling#Matrix#
R$CH2$X" R$CH=CH$CH2X" RCH=CHX" ArX" R$C≅C$X"
" " " "
R’"CH2"M"Y#
#
R’"CH=CH"CH2"M"Y#
#
R’CH=CH"M"Y#
#
Ar’"M"Y# Ar’"Ar#
#
R’"C≅C"M"Y# R’"CC"Ar#
#
 Historical#Development#
•  Kharasch#(Grignard)#
•  Heck#(palladium)#
•  Tamura#and#Kochi#(copper)#
•  Kumada#and#Corriu#(nickel)#
Original#ObservaAon#by#R.#Heck#

NANO?"
Heck#ReacAon#
 General#form#of#the#Heck#

• Pd#can#be#a#catalyst#in#the#presence#of#phosphines#
• Hindered#phosphines#are#good#ligands##
• TerAary#amines#are#required#to#remove#the#acid.#
Mechanism#of#Heck#
 Limits#to#the#reacAon#
•  X#should#be#a#good#leaving#group#
•  Alkene#should#have#one#hydrogen!##
•  Should#not#be#overcrowded#

•  Stereochemistry#of#the#product#is#not#fixed!###
######Both#cis#and#trans#products#can#be#obtained!#
UAlity#of#the#Heck#ReacAon#
 Neghishi#C"C#coupling#Matrix#1970"1980#
R$CH2$X" R$CH=CH$CH2X" RCH=CHX" ArX" R$C≅C$X"
" " " "
R"CH2"M"Y#
H# ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## He#
## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##

# Li# Be# ## ## ## ## ## ## ## # ## B# C# N# O# F# Ne#

## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##

R"CH=CH"CH2"M"Y# Na## Mg# ## # # ## ## ## ## ## Al# Si# P# S# Cl# Ar#

#
## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##

K## Ca# Sc# Ti# V# Cr# Mn# Fe## Co# Ni# Cu# Zn# Ga# Ge# As# Se# Br# Kr#

## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##
RCH=CH"M"Y#
# Rb# Sr# Y# Zr# Nb# Mo# Tc# Ru# Rh# Pd# Ag# Cd# In# Sn# Sb# Te# I# Xe#
## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##
Cs# Ba# Hf# Ta# W# Re# Os# Ir# Pt# Au# Hg# Tl# Pb# Bi# Po# At# Rn#

Ar"M"Y# ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##
Fr# Ra# Rf# Db# Sg# Bh# Hs# Mt# Ds# Rg# E#112# E#113# E#114# E#115# E#116# #E#117# E#118#
# ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ##

R"C≅C"M"Y# La# Ce# Pr# Nd# Pm# Sm# Eu# Gd# Tb# Dy# Ho# Er# Tm# Yb# Lu#

# Ac# Th# Pa# U# Np# Pu# Am# Cm# Bk# Cf# Es# Fm# Md# No# Lr#

Zn,"B,#Mg,#Al,#Zr,#Si,#Sn,#and#perhaps#Cu#
 Neghishi#Coupling#

RY##is#converted#to#RLi#
RLi#is##converted#with#Zn#Cl2##to#RZnCl#
Mechanism#of#Neghishi#ReacAon#
Generalized#Neghishi#
A#genealogy#of#Pd"catalyzed#cross"coupling#
Ei"ichi#Negishi#*#
#
•  Journal#of#Organometallic#Chemistry#653#(2002)#34/40#

This#paper#describes#a#very#brief#history#leading#to#the#birth#of#
the#Pd"catalyzed#cross"coupling,#its#birth#in#the#mid"1970s,#
(a)#the#development#of#the#Pd"catalyzed#cross"coupling#with#
organometals#containing#Zn,#Al,#Zr,#and#Mg#(the#‘first"
generaAon’#Pdcatalyzed#cross"coupling)#in#the#1970s,##
(b)#seeding#of#the#Pd"catalyzed#cross"coupling#with#
organometals#containing#Sn,#B,#and#Si##(the#‘second"
generaAon’#Pd"catalyzed#cross"coupling)#in#the#late"1970s,#
and##
(c)#further#developments#in#the##Negishi’s#group#in#the#1980s.#
Neghishi#Rxn#(applicaAons)#
Low#catalyst#loading#&#Hindered#
substrates#

An"Extremely"Ac>ve"Catalyst"for"the"Negishi"
Cross$Coupling"
Reac>on"
Jacqueline#E.#Milne#and#Stephen#L.#Buchwald*#
J."AM."CHEM."SOC."2004,"126,"13028$13032#
Cyano,#nitro,#ester,#alkoxy#and#amino#subsAtuents#tolerated!#
Synthesis#of#the#ligand!#
Suzuki#Coupling#
Specific#Examples#of#Suzuki#Coupling#
Pd#catalyst#and#a#base#

2002#

2002#
Mechanism#of#Suzuki#
 Suzuki#Coupling#
•  Aryl#"#Aryl#bond#formaAon.#
•  Pd(II)#or#Pd(0)#catalyst#precursor,#Phosphine#
ligand,#Pd(0)#actual#catalyst.#
•  Aryl#iodides,#and#bromides#work,#chlorides#are#
unsuitable#
•  Chlorides#can#be#used#if#ancillary#ligand#is#very#
electron#donaAng.#
Suzuki#Coupling#
Hiyama#reacAon#
SAlle#reacAon#
Kumada#reacAon#
Sonoghashira#reacAon#
Sonogashira#ReacAon#and#Alkyne#Homocoupling#
Side#ReacAons#
 SC#AcAvaAng#Aryl#Chlorides#
•  Trialkylphosphines#(most#electron#donaAng)#
•  Sterically#demanding#

•  Why??#
–  OxidaAve#addiAon#to#M(0)#centre#is#rd.#
–  low#coordinaAon#no.#supported#by#large#
phosphines#
Specialized#Ligands#for#Suzuki#
Assymetric#Suzuki#Coupling#
Gladyz:##Suzuki#Coupling#
 Simple#NiCl2#

Danilo Zim and Adriano L. Monteiro*

Tetrahedron Letters 43 (2002) 4009–4011
A.#Monterio.#Org.Let.#2001,#3049#
Mechanism#of#Suzuki#Coupling#with#Tosylates#
NiCl2.6H2O"#catalyzed#Suzuki#cross"coupling#of##
4"bromoanisole#with#phenylboronic#acid#
 Danilo Zim and Adriano L. Monteiro*
Tetrahedron Letters 43 (2002) 4009–4011
CombinaAon#of#classical#SC#&#Ni#
 Ferrocene#/Arene#Phosphines…..#
•  Shih"Yuan#Liyu,#Michael#J.#Choi#&#G.#C.Fu#
–  MIT,#USA.#
 G.#C.#Fu#et#al.#Chem.#Comm.#2408,#2001#
Suzuki reaction of an unactivated aryl chloride: triarylphosphines as ligands

Me Cl
1.5% Pd2(dba)3
Me
6% ligand
Me
(HO) 2B 2.4 equiv K3 PO4.H2O
toluene, 70 oC
Me
 How#does#FcPPh2#work?#
•  Ortho#TMS#group#is#absolutely#essenAal#
•  TwisAng#PPh2#group#such#that#it#is#more#
electron#donaAng???#
–  Preferred#posiAon,#lp#on#P#and#dz2#on#Fe#away#
from#one#another#(orthogonal)#
–  Pushing#of#lp#of#electrons#from#the#metal#into#C1#
and#C2#is#known#
–  Cf.#increased#solvolysis#of#C1"X!#
 To#Summarize#
•  C"C#coupling#is#a#key#reacAon#in#organic#
synthesis#

•  TransiAon#metals#are#essenAal#in#many#cases#

•  Pd#is#the#key#element#to#carry#out#the#key#
step.#