Olefin complexes

Synthesis of Olefin complexes

•  Ligand substitution
•  Reduction of metal salts in the presence of
an olefin
•  Metal atom synthesis
•  Ligand addition to unsat. complexes
 Very weak complexes!

AgNO3 + olefin Ag(olefin)2NO3

Cu(ClO4)2.6H2O Reduced with copper in
CH3CN gives “Cu(ClO4)”
Key to this reaction is the non-coordinating anion and the
stabilizing solvent!

Triflate instead of perchlorate also works

Reduction could be carried out electro-
chemically also!
 Reduction of a metal in the
presence of the olefin
CH2 H2C
CH2
C2H5OH / H2O Cl
H2C
RhCl3 + C2H4
Rh
Rh

H2C Cl
CH2

H2C
CH2
Cp2Co + K + C2H4 CpCo(C2H4)2+ CpK

CpK is eliminated in the reaction

Where did the electron go?
Co2+ reduced to Co+ to balance the net
charge.
 Dil HCl
K2[PtCl4] + C 2H4
60 bar
K[C2H4PtCl3].H2O + KCl

Re(CO)5Cl + C2H4 [Re(CO)5C2H4 ]AlCl4

CpFe(CO)2I + C2H4 + AgBF4 CpFe(CO)2(C2H4)]BF4 + AgI

 Simple substitution
Dil HCl
K2[PtCl4] + C 2H4
60 bar
K[C2H4PtCl3].H2O + KCl

Re(CO)5Cl + C2H4 [Re(CO)5C2H4 ]AlCl4

CpFe(CO)2I + C2H4 + AgBF4 CpFe(CO)2(C2H4)]BF4 + AgI

 Simple displacement of 2e
donors!
Cl
PdCl2(PhCN)2 + C8H12 Pd

Cl

COOEt
Fe(CO)5 + CO
COOEt
OC
COOEt
Fe
OC
COOEt
CO
 Reduction in the presence of
olefin
NiCl2 + AlR3 + C2H4
Ni

Complex is stable up to 0 oC

NiCl2 + AlR3 + 2C8H12

Ni
 Simple displacement of Olefins!

CN
Ph 3P CN
Ni(PPh3)2C2H4 +
Ni +
Ph 3P
Co-condensation of a metal
vapor
 Removing an H- from an alkyl
complex

+
H
CH3
[CPh3]BF4
H Fe
[BF 4]-
CH3 - HCPh3
Fe
H2C

H O
O
O
O H H
 Stability of metal olefin
complexes
CO can be replaced by olefins in trans
positions!

Simple ethylene can be replaced by CH2=CHCN

Ni(PPh3)2(C2H4) + AN Ni(PPh3)2(AN) + C2H4
 Stability of metal olefin
complexes
Steric effects seem to be important!
Trans < cis < mono-sub < ethylene!
 Metal Olefin complexes Structure

•  η2 bonding
•  (both C are equally bound)
•  (All H’s are equidistant from the metal)

•  Lengthening of C-C bond

•  Barrier to rotation of the olefin

 Structural Features
•  If π bonding is involved..

•  Lengthening of C-C bond

•  C-C bond length in ethylene 134 pm
•  C-C bond is 137 pm coordinated to the
metal Pt in Zeise salt!
 Spectroscopy
Frequency of C=C stretch 1623 cm-1

Coordinated to Pt: ethylene in Zeise’s salt

1516 cm-1
 Bonding
Dewar Chatt Duncanson model of Bonding

The π bond in
ethylene binds in a
σ fashion to the
Metal

2e- present in the π

bond of ehtylene.

After bonding with

metal some e-
density Electron density
is lost. from the olefin to
empty d orbital of
metal

0.24 electrons
sigma symmetry
 Bonding
Dewar Chatt Duncanson model of Bonding

π* orbitals of ethylene accept

e- density from the metal.
This gives a ‘π-bond”

π* orbitals of ethylene are

filled.

0.22 electrons
Electron density
from the metal to
empty antibonding
orbital of olefin

pi symmetry
 Bonding
Dewar Chatt Duncanson model of Bonding

The π bond
in ethylene
binds in a σ
fashion to π* orbitals of
the Metal ethylene
2e- present accept e-
in the π density from
bond of the metal.
ehtylene. This gives a
After ‘π-bond”
bonding
with metal Electron density π* orbitals of
some e- Electron density
from the olefin to from the metal to ethylene are
density empty d orbital of filled.
is lost. empty antibonding
metal orbital of olefin

sigma symmetry pi symmetry

 The bonding in Zeise salt
•  The anion of Zeise salt has a square
planar geometry with one of the
positions occupied by an ethylene.
CH2
•  The olefin is placed such that the C-C Cl Cl
bond is perpendicular to the PtCl3
plane. Assuming that the PtCl3 plane is Cl Pt
the xy plane, and that the Cl trans to
the olefin is on the x axis.
H2C
•  Then the dxz orbital is making the π
bond. This is filled and pumps in z
electron density from the metal dxy
into the olefin π * orbitals.

•  The dx2– y2 orbital is the empty orbital

in which σ donation occurs. y x
•  If we assume that the oelfin is rotated about the Pt-olefin axis such
that the two carbons are in the xy plane, we have a rotational isomer
of Zeise salt. The π bond between the olefin and the Pt can be
formed by the dxy orbital of Pt and the π * orbital of olefin!
• 
CH2 H2C
Cl Cl Cl
Pt
H2C Cl Cl Cl Pt

CH2
 H
H
H
C
H H
Cl Cl Cl
Pt
Cl Cl Cl Pt
H C
H H

In a simple bonding picture there is apparently no difference between

the two situations.

However, the in plane position leads to 5 atoms in the plane and

would lead to CH2 groups closer to Cl atoms increasing the
unfavourable steric repulsion between the ligands. This also brings
the π bond of the olefin close to the M-Cl bonds.
H3P CH2
Ni
146 pm (154 C-C and 136 C=C)
H3P CH2

H H
H H
11 to 16 deg.

H3P CH2
Pt
H3P C 142 deg. 148 pm is the dist.
CH2
Complex Frequency cm-1 Distance (pm)

C 2H 4 1623 134

(C2H4)2Ag 1584

(C2H4)Fe(CO)4 1551 146

(C2H4)2Rh(acac) 1523 141

[(C2H4) PtCl2] 2 1506

(C2H4)2Rh(Cp) 1493
 Donor / Acceptor nature of
metals also vary!
28
Atom Electrons IP EA
in eV in eV
Zero oxdn. state easy to
Ni(0) 10 1.7 1.2 Oxidize
Pd(0) 10 4.2 1.3
Pt(0) 10 3.3 2.4
Rh(I) 8 1.6 7.3
Ir(I) 8 2.4 8.0

Cu(I) 10 8.3 7.7

Ag(I) 10 9.9 7.6

Zn(II) 10 17 18
 Donor / acceptor prop. of olefins
Stability of C=C complex

cis
trans

Substituent on the olefin π* energy level

Trisub disub mono OAc COOMe CN trans dicyano
 CN, CN
Binding constant

COMe CN

Me
OAc

Me, Me

-1 -2 -3 -4
ρ Hammet substituent constant
 Barrier to rotation of the olefin

If π bond is there there will

be a barrier to rotation!
Varies widely,
Rh complex has a
rotational barrier of 15
Kcals / mol
It does not correlate with
freq. decrease!!
 F
Ph3P F
Ni PPh3 Ni
Ph3P Ph3P F F

1.36 A 1.51 A
 Differences between CO & C2H4
complexes

•  Not just η1 and η2

•  Similarities
–  Both donate e- density from HOMO
•  Difference
–  C2H4 – homo is bonding
–  CO -- homo is non-bonding ~ antibonding
•  Both accept e- density into LUMO
–  antibonding of ethylene is symmetric
–  antibonding CO is lopsided
•  For a recent, complete discussion of metal olefin
bonding and the DCD model,
•  See Chem. Eur. Journal 2000, 6, 4587
 Metal Olefin complexes
Key concepts
•  Synthesis, Structure
•  Bonding & Differences from CO
•  Synthesis of Olefin complexes
•  Ligand substitution
•  Ligand addition to unsat.complexes
•  Reduction of metal salts with olefin
•  Metal atom synthesis
Acetylenes,*cumulenes,**
•  Acetylenes*are*like*alkenes*

–  π*bond*is*a*donor*and*π *orbital*accepts*electrons***

–  Less*steric*hindrance*
Ethylene%

!0.1%

!7.5%

!7.6%
Acetylene%

0.5%

8.6%eV%

!8.1%
In*situ*reduc8on!*
 In*situ*reduc8on!*

Alkenes*do*not*interact*with*metals*in*high*oxida8on*states!*
Alkynes*appear*to*bond*well!**Here*we*have*“W”*in**+4*ox.*State!*
Dewar Chatt Duncanson model of Bonding

Electron density Electron density

from the olefin to from the metal to
empty d orbital of empty antibonding
metal orbital of olefin

sigma symmetry pi symmetry

Dicyanoacetylene%

!3.2%

6.2%eV%

!9.4%
Reduced*steric*interac8ons*
Free*acetylene*120*ppm!*

124*ppm*

132*ppm*
•  Alkynes*are*synthesized*by*subs8tu8ng*
exis8ng*ligands*with*“stable*alkynes”*
•  Subs8tu8on*can*be*carried*out*with*or*
without*reduc8on*depending*on*the*oxida8on*
state*of*the*metal.*
•  What*is*the*smallest*ring*which*can*support*a*
cycloalkyne?*
M*=*Nb,*Ta*
 Benzyne*

ppm*

ppm* ppm*
M*=*Nb,*Ta*
Abnormal*alkynes!*
•  Acetylenes*are*like*alkenes*
–  Less*steric*hindrance*
–  π*bond*is*a*donor*and*π *orbital*accepts*electrons***
–  π*bond*is*a*beTer*donor*and*π *orbital*is*lower*in*
energy*

–  Perpendicular*to*one*π*bond*there*is*another*π*
orbital*and*another*π *orbital*
–  2*metals*can*bond*to*the*same*acetylene!!*
 XWaxis* Z*axis*

• Acetylene*is*similar*to*ethylene*but*2π*bonds*
are*there*(⊥)*so*two*metals*can*be*bridged.*
Reac8on*of*acetylenes*with*Co2(CO)8*
DITXUZ*
 How*many*electrons*does*it*give?*

According*to*group*theory,*all*the*p*orbitals*on*C*cannot*interact**
with*tungsten*as*there*are*A1*+*E*+*A2*+*E*type*orbitals.**So****
RICRUR*
 combining*π*orbitals*
CWC*interac8on*greater*than*
everything*else!*
Orbitals*on*tungsten*
Mul8ple*double*bonds!*
allene%

0.02%

7.52%eV%

!7.5%
 Metal Hydrides

They are very important!

 FUELS

Methanol METALS
From CO / H2 METAL From ores
HYDRIDES
CATALYSTS

Preparation of Preparation of
Fertilizers and Plastics Foods and drugs
A PERIODIC TABLE OF HYDRIDES
 H2 and H - complexes
•  A few molecular complexes are polyhydrides
have only M and H, but are rare.
Eg. [ReH9]2-
•  These are in striking contrast with several
molecular hydrides NH3, CH4 etc..
•  There are several species with M-H bonds
usually other ligands besides “H”.
Transition Metal (TM) Hydrides
•  Tm-H is usually considered as H- because
the electronegativity (EN) of TM < H.
•  However, in a [TM(CO)n] fragment, EN of
the “TM” is > H!
 Transition Metal (Tm) Hydrides
•  If the EN of the “Tm(CO)n” is > H!
•  Heterolytic splitting of TM-H might occur!
•  TmH might behave as H+ and the metal will be
[Tm(CO)n]- .
•  But we still call [HTm(CO)n] a hydride, which
implies it is H- whereas it behaves like a
typical H+.
 Hydride or Acid
Metal Hydride! Ka Comparable acid
HCo(CO)4 1X 10-2 Like [HSO4]-
HCo(CO)3PPh3 1X 10 -7 Like water
HMn(CO)5 8 X 10 -4 acid
H2Fe(CO)4 3.6 X 10 -5 weak acid
[HFe(CO) ]
- 1X 10 -14 very weak acid
4
(Cf. 2nd ionization of oxalic acid)

pKa = -log10 Ka
 TMH
•  Hieber (1895-1976) was the first person to
make a TMH.
•  Fe(CO)5 + 3NaOH ==> Na[HFe(CO)4]
+ Na2CO3 + H2O
 Water Gas Shift Reaction
CO + H2O H2 + CO2
 Synthesis (with reduction)

•  Reduction of a Sulfide
CoS + H2 + CO ==> HCo(CO)4 + H2S
(200 deg. And 200 atm of CO + H2 is used)
Cu powder is used to remove the H2S
 Synthesis (with reduction)

•  Reaction with an oxide

OsO4 + 3 CO/H2
===> H2Os(CO)4 + H2Os2(CO)8
 Reduction of Chlorides
•  Cp2ZrCl2 + LAH/NaBH4 => Cp2ZrHCl
LAH stands for LiAlH4
•  Interestingly when cis PtCl2(P(Et)3)2 is
reduced, the trans phosphine complex is
formed.
P(Et)3 H
Pt
Cl
P(Et)3
 Reduction with hydrogen gas
•  RuCl2P4 + H2 atm ==> HRuClP3 + P
–  Where P stands for triphenyl phosphine PPh3
 Protonation
H
+ PPh2
+
PPh2 PPh2 PPh2

Co + H Cl Co
PPh2 PPh2
PPh2 PPh2

Cl

Na[Re(CO) 5] + H Cl H[Re(CO)5] + NaCl

 Oxidative cleavage of M-M bonds by H2

Mn2 (CO )10 + H 2 !80 !→ HMn(CO )5

!atm

Rh( PPh3 )3 (CO ) − Rh ( PPh 3)3 (CO ) !80 !→ 2 HRh (CO )( PPh3 )3
!atm

In both cases the M-M bond is cleaved with H

 IR spectroscopy
M-H stretch occurs at 2200 to 1900 cm-1

−1
HCo(CO) 4 − 1934cm
Same region as CO vibration −1
HMn(CO) 5 − 1783cm
Difficulty is solved by synthesizing
isotopically labelled compounds

ν M−H
= 1.44
ν M −D
 Reporter ligand for the trans
ligand!
PR 3
H
Pt
O 3N PR 3 X = NO3 Pt-H 2242 cm-1

PR 3 H

Pt X = CN Pt-H 2041 cm-1

NC
PR 3
 NMR spectroscopy
NMR – very useful.

But can be difficult to interpret!

Signals from H in M – H complexes

– can be very broad.
Usually upfield -7 to –24 ppm.

Value of chemical shift, δ, depends on

dn and the d – d separation.
 NMR & covalency of M-H bonds
103Rhand 195Pt are useful for detecting hydride complexes
Usually JM-H can be observed and is in the range 40-1400 Hz

Covalent bonding is essential for transferring the spin information

from M to H. If it was ionic bonding, no JM-H would be observed.

Observation of spin-spin interactions clearly confirm

covalent interactions

NMR is also useful for studying fluxional species.

 Structural Difficulties
M-H
•  Not located in X-ray diffraction ... Low
electron density makes it difficult to identify
the position of H.
•  “Swallowed up by the metal’s electron
density..”
•  Too close to the metal.. Neutron diffraction
studies are required.
•  Disorder or fluxional behavior
RuH(Bipy)
Hydrogen occupies a coordination
site on the metal.
Ru-H 1.54
 H2 and H - complexes

•  Interestingly, di-Hydrogen complexes are

also possible and these were structurally
characterized only in 1983 (recently).
•  Kubas G. J. Acc. Chem. Res. 1988, 27, 120-28

Mo(CO)3(CHT) + 2P(iPr)3 Mo(CO)3(PPr3) + CHT

CHT
Cycloheptatriene
 Mo(CO)3(CHT) + 2P(iPr)3 Mo(CO)3(PPr3)2 + CHT

CHT
Cycloheptatriene

Mo(CO)3(PPr3)2 + H2 Mo(CO)3(PPr3)2H2
Structure of the corresponding
W complex
WH2(CO)3(PiPr3)2

CSDS code CEJDEA

Bonding
•  Several of them exist in equilibrium with
hydrides!
OC CO

Ph3P CO Ph 3P CO

W H W
H
H PPh3 PPh3
H CO
CO
•  Proof for existence of H-H complex is difficult!
•  Contrary to expectations, the chemical shifts
are similar
•  X-ray: H-H bond length is 75(16)pm (X-ray is
not trustworthy)
•  Neutron data: 84 pm versus 74 pm in free
hydrogen!
 Distance ranges in H2 and
Hydride complexes
H H
H H2 H
M M M M
H H2 H
H H

74 80-90 100-130 > 130

True dihydrogen Elongated dihydrogen Dihydride

complex
complex complex
Easier way is to look for the H-H coupling
constant.
Problem: Magnetically equivalent hydrogens
exhibit a single resonance.
H-D coupling is what is measurable. 33.5 Hz.
For free H-D, coupling constant is 43.2 Hz.
Cf. M(H)2 complexes!
H-H coupling constant is 2 Hz!
Better way is to look for the H-H coupling
constant.
Problem: Magnetically equivalent hydrogens
exhibit a single resonance.
H-D coupling is what is measurable. 33.5 Hz.
For free H-D, coupling constant is 43.2 Hz.
Cf. M(H)2 complexes! H-H coupling constant
is 2 Hz!
Coupling is lost when the covalent bond is
broken anytime during the measurement
time.
H
H
M M
H
H

A second NMR technique is to measure the

relaxation time.
 Relaxation times depend on
distance to other hydrogen
H
H
M M

H
H

H atoms are closeby

H atoms are faraway
relaxation rate 4-100 ms
relaxation rate 150-400 ms
References:
http://pubs.acs.org/doi/pdf/10.1021/om100416w

Caveats identified by Halpern!

Distance is not the only factor, relaxation
Rates depend on the free rotation of the H2
 Factors favoring H2 complexes
(1) electron-withdrawing ancillary ligands such as
CO, particularly trans to the ligand;
(2) positively charged metal centers, i.e. cationic
rather than neutral complexes;
(3) less electron-rich first or second row M; and
(4)  orbital hybridization, i.e. octahedral
coordination and d6 metals.
 Key points to remember…
•  Hydride Complexes: the term could be misleading
•  The ambivalent behavior of hydrogen in metal
hydrides.
•  The difficulty in assigning oxidation states.
•  To understand the nature, study its chemistry.
•  Different ways to make metal hydride complexes.
•  How NMR can be used to distinguish M – H and M(H)
complexes.
•  Structure of metal-hydrides and their steric demands.
1
Mechanisms of Organotransition Metal Reactions
Classification of OM Reactions
M - C

A. Rearrangements, Isomerizations

M - L M - L'

B. Ligand Insertion Reactions

X

M L + X M X L

C. Oxidative Addition Reductive Elimination

Mn+ + L M(n+x)+ L

D. Reactivity changes on the Ligand

M L + Y M L' + X OM - 3
R O
Mg X + CO2 R
O
Mg X

O
CH3OH + CO H3C
HO

Ph4As+ [Rh(CO)2I2]- HI , 800 C / 3 atm of CO

Monsanto's acetic acid process

annual production 106 tons.
H

Co / Rh
H3C CH2
H3C O
+ H2 + CO
 O CH3

H3C
OC CO OC CO
+ CO
Mn Mn
CO OC CO
OC
CO OC

Calderazzo
Which is correct ?

O CH3

H3C
OC CO OC CO
+ CO
Mn Mn
CO OC CO
OC
CO OC
 Me O CO
OC Me CO
CO Mn
Mn 13
OC
13
CO OC CO trans
CO CO
Direct
elimination CO
OC Me
Me Mn
13
OC CO cis
OC CO CO
Mn
13
trans : cis : unlabelled
OC CO CO
CO
1 : 2 : 1 OC CO
Mn
OC Me
CO unlabelled

Methyl migrates to a vacant cis site.

Isotopic labelling

I. R.
 STEREOCHEMISTRY OF MIGRATING CARBON

•  Methyl (anionic ligand / 1 electron donor)

migrates to a cis vacant site.

•  Is it a free “methyl radical” ??

•  Or does it come out like an alkyl cation??

–  Does it undergo inversion? As if it is an SN2
process?
 The Whitesides experiment….

D D
H H
R R
CO
Fe Fe(CO)Cp
Cp
OC
O

D H
H D
R CO R
Fe Fe(CO)Cp
Cp
CO
O

R
D

H Fe(CO)Cp

O
 Stereochemistry of migrating C

D Me3C D
Me3C
C C H C C H
H H
O
D Fe(CO)2Cp D
PPh3(CO) FeCp
erythro erythro

G. Whitesides

tBu tBu
D H D
H
PPh3
D H
D H
O JH - Hcoupling measured
Fe 1. Complete retention
CO Fe 9
CO 2. No resolution necessary
CO
PPh3
 Karplus Equation
•  In the 3-bond coupling of two H atoms, Cis
has smaller coupling constants. Trans
orientation gives large coupling.
12
10

Karplus curve
5
0

0 60 120 180
Dihedral angle (deg) 10
11
 Stereochemistry of migrating C

D D
Me3C Me3C

C C H C C H
H H
O
D Fe(CO)2Cp D
PPh3(CO) FeCp
erythro Erythro coupling 9-12 Hz erythro

G. Whitesides Complete retention

tBu tBu
D H D
H
PPh3
D H
D H Only
O JH - coupling
H
couplingconstant
measured
Fe measurements
1. Complete retension
CO Fe No resolution of the complex is
CO 2. No resolution necessary
CO necessary
PPh3
12
 Electron Counting
Effect of migration

Before Insertion After insertion

2 coordination sites occupied 1 coordination site is occupied.
One cis coordination site free
Neutral method: 2 from CO Neutral method: 1 electron from R-CO-
1 from R M is M(0)
M is M(0)
Ionic method 2 from CO Ionic method 2 from R-CO-
2 from R- M is M(+1)
M is M(+1)
NEUTRAL LIGANDS Anionic Ligands
•  Olefin •  Hydrogen
•  CO •  Alkyl
•  Acetylene •  Aryl
•  NO •  Halogen
•  Phosphine •  Vinyl
•  Reactions of olefin with nucleophiles?

•  Photochemical type reactions

–  1 electron promoted from HOMO to LUMO
 Migratory insertion!
Nucleophilic attack on a coordinated olefin.
H2C
H2C
CH2
CH3

M
H M
Hydrido-zirconation
HZ (3 products expected)
Insertion-Abstraction Reaction!
End Result: formation of 1 product!
Isomerization with HCo(CO)4 an example of insertion / abstraction
 Synthesis of "Sliceable mineral oil"

Polyolefins ----- C, H

easily recycled

Combustion CO2 + H
from ethene and
propene
By 2005 ------- constitute 55% of total plastics.

New 'procedures'

100 tons polyethylene per gram of catalyst

Zr

Insertion time ~ 10-5 sec!

"Enzymatic activity"
 Acetylene + Chlorine
When R = Me When R = Ph
R
R R R R
RC CR
+ R R
PdCI2 R R
PdCI2
R
2
 R R
R R R R
R
Cl
R R PdCI
R R R
PdCI2
R R
2

CR R R
RC CR R Cl
Cl RC CR
+ RC
Pd
C C PdCl
PdCI2 2 Pd R
Cl Cl
Cl R
RC CR
 R -PdCl2 R

R Cl
PdCl R
Cl
R R PdCl
R R

R
RC CR

R R

R R
Cl Cl
PdCl
PdCl
R R R
R
R
R R R
4 H -C C-H + Ni( acac) 2

3 HC CH + L2 Ni(CO)2 C6H6
 Topological Pathways

HC CH
HC CH Zipper
Ni
CH
HC
H -C C -H

Cyclobutadiene
Ni Arene Ni

H-C C -H

CH
CH
CH Ni Carbyne
CH
CH
HC exchange
HC CH

OM - 28
 Migratory Insertion?
•  Nucleophilic attack on coordinated ligand!
•  Cis geometry
•  Anionic ligand migrates to neutral species!
•  Stereochemistry is maintained.
Diene%and%Polyene%Metal%
Complexes%
Ligands%for%Organometallic%Chemistry%
Dienes%
 butadiene%;;;;%pi%orbitals%

0.96%
LUMO+3%

Energies%in%eV%

HOMO% ;4.34%

HOMO;1% ;7.22%

HOMO;2% ;9.68%
Ethylene%

Cis!butadiene%

!0.1%
!0.9%

!7.5% 5.8%eV%

!6.7%

!7.6%
Cis!butadiene%

Compared%to%ethylene%this%%
!0.9%
MO%is%a%beLer%acceptor!%

5.8%eV%

Compared%to%ethylene%this%%
!6.7% MO%is%a%beLer%donor!%
Free%butadiene%
148%pm%and%134%
pm%
Pi%bond%order%is%
1.2%and%%1.98%
%
 s;cis;%butadiene%

singlet%

nonplanar%
•  Link%to%3d%structure%of%butadiene%iron%
tricarbonyl%
 145% 139%
Ψ4% *%
Ψ3% hυ%
Ψ2%
Ψ1%
Compare%two%extreme%descripSons.%
s;cis%or%s;trans?%
•  Structure%of%Nb%and%Zr%complexes%
Cyclobutadiene%;;;;%singlet;;;;;;;;Rectangular%

LUMO+6% 1.66%

Energies%in%eV%

LUMO% ;1.86%

HOMO% ;5.41%

HOMO;2% ;9.80%
singlet% triplet%
•  Link%to%3d%structure%
 NMR%spectra%of%M;ene%complexes?%
NMR

85 ppm 13
C NMR 65 ppm
40 ppm

Fe Fe
OC OC
CO CO
CO CO

1
H NMR 6.5 ppm
H H H H 64 ppm

H H H H
13
C NMR 123 ppm
Pd
Q.%Can%we%then%make%M;triene%
complexes?%
M;triene%are%not%aromaSc%complexes!%
•  Link%to%3d%structures%
Compare%conjugated%and%non;
conjugated%double%bonds.%
 Key%points%to%remember%
•  Synthesis%is%easy!%
–  SubsStuSon%of%ligands%
–  ReducSon%of%metals%
–  Useful%starSng%material%
•  Structure%of%complexes%
–  Explain%using%the%DCD%model%
–  Bond%delocalizaSon%is%increased!%
–  Complex%looks%like%an%excited%state%olefin%