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Organometallic
Chemistry
Lecture Notes
Prof. George G. Stanley
Department of Chemistry
Louisiana State University
614 Choppin Hall
(225)-578-3471
E-Mail: gstanley@lsu.edu
Spring, 2015
(updated 1/02/2015)
2008 update: electron density discussion, square-planar electronic effects, orbital info
added to chapter 1; bonding comparison between PCl3 and PMe3 added to phosphine
chapter. 2012 update: additional problems, minor corrections. 2014 updates: minor
corrections. 2015 updates: minor corrections, new examples of formal charge vs.
calculated charges via DFT calculations (early chapters)
Intro 2
3. Oxidation States
4. Organic line notation for drawing structures
Cl
Cl Cl
Cl
Ni
R2P
Cl
PR2
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Ni
R2P
PR2
Cl
Ni
R2P
Cl
PR2
Intro 3
Intro 4
Examples:
Fluoride anion, F: This anion has high electron density due to the
negative charge, filled octet of electrons, and small size. BUT I would
NOT consider it to be electron-rich, meaning a good electron donor.
The extremely high electronegativity of a fluorine atom means that it
desperately wants to pick up an extra electron to form the fluoride anion,
which is extremely stable. The filled valence orbitals are fairly low in
energy for F and generally poor donors. It is certainly not electrondeficient as it doesnt have any low-lying empty orbitals and does not
want to accept any more electrons. It isnt electron-rich either since it is
a very poor nucleophile and generally a poor ligand for most metals
(except those in high oxidation states). It is almost impossible to
chemically oxidize F.
Methyl anion, CH3: This anion is very electron-rich and a powerful
nucleophile. The electron-richness comes from the lower electronegativity of carbon and the high energy of the anionic sp3-hybidized
lone pair that makes it a strong donor group. It is also very easily
oxidized, pointing to the presence of a high-energy lone pair orbital.
PROBLEM: Which is more e- rich? Why?
1) Ti(+2), d2
-or-
Pt(+2), d8
2) Al(CH3)3
-or-
N(CH3)3
3) CF3
-or-
N(CH3)2
Intro 5
PMe3
HOMO = 5.03 eV
Charge on P = +0.22
P(OMe)3
HOMO = 7.40 eV
Charge on P = +0.75
MO plot of the lone pair orbital (HOMO) for PMe3. Dashed outline
indicates the spatial extent of the lone pair for P(OMe)3.
38
72
73
Niobium
89
Radium
Actinium
Ra Ac
88
Actinides
Lanthanides
Francium
87
Lanthanum
26
27
28
42
Chromium
43
Manganese
44
Iron
45
Cobalt
46
Nickel
30
47
Copper
48
Zinc
Cu Zn
29
49
Galium
31
Aluminum
59
105
75
76
Ruthenium
60
Tungsten
61
Rhenium
62
Osmium
W Re Os
74
Molybdenum Technetium
63
Iridium
Ir
77
Rhodium
79
Silver
80
Cadmium
64
Platinum
65
Gold
66
Mercury
Pt Au Hg
78
Palladium
67
Thallium
Tl
81
Indium
33
Phosphorus
15
Nitrogen
34
Sulfur
16
Oxygen
15 16
51
Arsenic
52
Selenium
83
Antimony
84
Tellurium
85
Iodine
53
Bromine
35
Chlorine
Cl
17
Fluorine
17
91
Thorium
Protactinium
Uranium
92
Praseodymium Neodymium
Th Pa
90
Cerium
94
Samarium
95
Europium
96
Gadolinium
97
Terbium
98
Dysprosium
Neptunium
Plutonium
Americium
Curium
Berkelium
Californium
Np Pu Am Cm Bk Cf
93
Promethium
68
Lead
69
Bismuth
70
Polonium
71
Astatine
100
Erbium
101
Thulium
Lutetium
102 103
Ytterbium
Einsteinium
Fermium
Mendelevium
Nobelium
Lawrencium
Es Fm Md No Lr
99
Holmium
86
Xenon
Xe
54
Krypton
Kr
36
Argon
Ar
18
Neon
Ne
10
Helium
He
18
Radon
Pb Bi Po At Rn
82
Tin
Sn Sb Te
50
Germanium
Ge As Se
32
Silicon
Si
14
Carbon
14
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
58
104
Tantalum
Hf Ta
Barium
25
10
Cr Mn Fe Co Ni
24
Zr Nb Mo Tc Ru Rh Pd Ag Cd In
Zirconium
Hafnium
57
Yttrium
41
Cesium
56
Strontium
40
Vanadium
23
Cs Ba La
55
Rubidium
39
Titanium
Ti
Scandium
Ca Sc
Calcium
22
21
20
Magnesium
Rb Sr
37
Potassium
19
Sodium
11 12 Al
B
Boron
Na Mg
Group 8
13
Berylium
13
12
11
Lithium
Li Be
Hydrogen
Intro 6
Intro 7
low electronegativities
higher electronegativities
OXOPHILLIC!!
Intro 8
A + B
Ea
Ea
catalyzed
G
Reactants
G
Products
Reaction Coordinate
Intro 9
SiMe3
+ HSiMe3
Hydrosilylation
Me
Me
ligand addition
1. oxidative addition
2. ligand dissociation
Pt
+ propene
Me
+ HSiMe3
- alkene
Pt
Pt
SiMe3
H
Pt
SiMe3
SiMe3
+ propene
1. migratory insertion
2. ligand addition
reductive elimination
Note that there are different numbers of ligands (a generic name for
anything that bonds to a metal center) on the metal. Too many is
bad, too few is bad. How can you tell how many to use?? Electron
counting is the key, which is presented later in this chapter.
Intro 10
L
M
L
L
L
L
The second metal complex is much less likely to lose one of the ligands
due to the bridging group that holds the ligands in proximity to the metal
center. From a kinetic viewpoint, if one of the ligands dissociates, it will
remain close enough to the metal center to have a high probability of recoordinating before another ligand can get in an bind. From a
thermodynamic viewpoint, by tethering two donor ligands together, one
removes the entropic driving force for dissociating a ligand and thus
making more particles in solution (more disorder).
The chelate effect can be extremely dramatic. There are cases known
where the presence of a chelate will change the equilibrium constant by a
factor of 1010 favoring the coordinated form of the ligand to the metal
over the dissociated form. Naturally, the longer and more flexible the
bridging group in a chelating ligand, the less dramatic the chelating effect.
It is possible to design ligands with sterically enforced chelates.
Intro 11
Intro 12
M
5-Cp
M
M
3-Cp
M
3-allyl
1-allyl
Intro 13
Intro 14
Ta2(-t-Bu-CC-t-Bu)(-Cl)2Cl2(THF)2
This complex has three bridging ligands:
two single atom chlorides & an alkyne.
Hydrogen atoms not shown.
Mo2(-CH2P(Me)2CH2)4
This complex has four bridging
diylide ligands (see page intro 36
for more info). Hydrogen atoms not
shown.
A)
B)
Me2P
PMe2
Me2P
C)
PMe2
D)
Me2P
PMe2
Me2P
PMe2
Intro 15
Intro 16
L
L
L
L
M
L
L
L
axial
L
equitorial
apical
basal
L
4-Coordinate: Square Planar or Tetrahedral
(90 & 180)
(109)
L
L
M
L
L
L
Intro 17
a) CpRuCl(=CHCO2Et)(PPh3)
e) Cp2TiCl2
Intro 18
s
x
y
z
z
x
z
x
py
px
pz
z
x
d z2
dx2 - y 2
d yz
z
x
d xz
d xy
Intro 19
Intro 20
The p- orbital is higher in energy (& the HOMO) than the -bonding
orbitals. Bringing two p- orbitals together to the NN bond distance
leads to anti-bonding interactions due to the p-lobe extending over into
the other phased orbital region as shown qualitatively below:
Intro 21
Square Planar
Square planar complexes typically have d8 (sometimes d9)
electronic configurations and are usually limited to the following
elements: Rh, Ir, Ni, Pd, Pt, Cu, & Au.
Of these the first and second-row metals add a fifth ligand more
readily than the third-row analogs. The reason that Ir, Pt, and Au
are less likely to add a fifth ligand is due to the blocking effect of
the filled 5dz2 orbital that is more spatially extended than the 3 or
4dz2 orbitals. The 6pz orbital is also more contracted than one
would expect due to relativistic effects that allow better
penetration of the s and p orbitals to the highly charged nucleus
lowering their energy. The d and f orbitals are shielded better,
which raises their energies relative to the s and p orbitals. This
effect really turns on for Pt and Au, less so for Ir that does have
more of a tendency to pick up a fifth ligand.
The relative orbital extents of the filled dz2 and empty pz orbitals
from DFT calculations on MH2(NH3)2 model complexes for Ni,
Pd, and Pt are shown below.
Intro 22
Intro 23
18 Electron "Rule"
Organic compounds, of course, follow the 8 electron rule: there can
only be a maximum of 8 valence electrons around a carbon center.
The vast majority of stable diamagnetic organometallic compounds
have 16 or 18 valence electrons due to the presence of the five d
orbitals which can hold 10 more electrons relative to C, O, N, etc.
Electron counting is the process of determining the number of
valence electrons about a metal center in a given transition metal
complex.
To determine the electron count for a metal complex:
1) Determine the oxidation state of the transition metal center(s)
and the metal centers resulting d-electron count. To do this one
must:
a) note any overall charge on the metal complex
b) know the charges of the ligands bound to the metal
center (ionic ligand method)
c) know the number of electrons being donated to the metal
center from each ligand (ionic ligand method)
2) Add up the electron counts for the metal center and ligands
Complexes with 18 e- counts are referred to as saturated, because
there are no empty low-lying orbitals to which another incoming
ligand can coordinate. Complexes with counts lower than 18e- are
called unsaturated and can electronically bind additional ligands if
they are sterically allowed.
Intro 24
Early Transition
Metals
Middle Transition
Metals
Late Transition
Metals
18e- configurations
are common
Coordination
geometries higher
than 6 relatively
common
Coordination
geometries of 6 are
common
Coordination
geometries of 5 and
lower are common:
d8 = square planar
d6
Intro 25
Bonding Type
Formal
Charge
Electrons
Donated
-1
-1
-1
Halide: X
bridging
-1
4
(2 to
each M)
Halide: X
3 bridging
-1
6
(2 to
each M)
Molecular Hydrogen: H2
Hydride: H
M-H
Hydride: H
Halide: X
M-X
M- OR
-1
2 or 4
-1
4
(2 to
each M)
-1
6
(2 to
each M)
-2
-2
4
(2 to
each M)
O
M
M
R
O
M
O
Peroxide: O22
2
M
O
Peroxide: O22
2 bridging
O
M
O
M
O
M
Intro 26
M O
-2
4
6
-2
4
(2 to
each M)
-2
6
(2 to
each M)
-1
M O
Oxide, sulfide: O2, S2
bridging
O
M
O
M
M
Amine, phosphine, arsine:
NR3, PR3, AsR3
Amide, phosphide:
NR2, PR2
M-NR3
M-PR3
M N
M P
R
M N
Amide, phosphide:
NR2, PR2 bridging:
RR
-1
4
(2 to
each M)
-2
4 (bent)
P
M
Imido: NR2
M N
6 (linear)
M N R
Imido: NR2
bridging
R
N
N
M
M
R
N
Imido: NR2
3 bridging
M
-2
4 or 6
(2 or 3 to
each M)
-2
6
(2 to
each M)
-3
M
Nitride, phosphide:
N3, P3
MN:
Intro 27
Nitride, phosphide:
N3, P3, bridging
N
M
M M
Nitride, phosphide:
N3, P3, 3 bridging
4 or 6
(2 or 3 to
each M)
-3
N
M
-3
M
Nitrosyl: NO+
linear form
M N O
+1
Nitrosyl: NO
bent form
M N
-1
+1
1 to each
metal
+1
1 to each
metal
2 to each
metal
1 to each
metal
1 to each
metal
Nitrosyl: NO+
bridging
O
N
M
Nitrosyl: NO+
3 bridging
O
N
M
M
Carbonyl: CO
M C O
Carbonyl: CO
,2 mode
C
M
M
O
Carbonyl: CO
bridging
C
M
Carbonyl: CO
3 bridging
C
M
Intro 28
Isocyanide: CN-R
1 to each
metal
C R
2 or 4
2 to each
metal
2 to each
metal
-1
M C N R
Isocyanide: CN-R
bridging
N
C
M
Alkene: R2C=CR2
2 bonding mode
M
Alkyne: RCCR
2 bonding mode
R C
M
Alkyne: RCCR
bridging
Dienes: R2C=CH-CH=CR2
4 bonding mode
M
Dienes: R2C=CH-CH=CR2
bridging
Benzene: C6H6
6 bonding mode
M
Ketones, aldehydes:
2 bonding mode
R
R
O
M
M CR 3
Intro 29
-1
C
M
Aryl: C6H5
1 terminal
Alkenyl (vinyl), alkynyl:
CH=CH2, CCH
1 terminal
-1
-1
-1
-1
4
(2 to
each M)
+1
-1
-1
-1
-1
-1
M
M
R
M
Cyclopropenyl: C3H3
3 terminal
Allyl: C3H5
3 terminal
Allyl: C3H5
1 terminal
assuming no
agostic M-H
interactions
Alkenyl (vinyl):
CH=CH2
2 terminal
Alkenyl (vinyl), alkynyl:
CH=CH2, CCH
,2 terminal
2
(1 to
each M)
Pentadienyl: C5H7
5 terminal
M
Pentadienyl: C5H7
3 terminal
Intro 30
Pentadienyl: C5H7
1 terminal
Cyclopentadienyl: C5H5
5
-1
-1
-1
-2
-2
2 to each
metal
M
M
Cyclopentadienyl: C5H5
3
M
Carbene: =CYR
where Y is a substituent
capable of interaction with
the carbene carbon atom
Alkylidene: =CR22
where no substituents capable
of bonding to the carbene
carbon atom are present
R
M C
Y
R
M C
R
C
M
Carbyne or Alkyidyne:
CR3
M C R
-3
Carbyne or Alkyidyne:
CR33 bridging
-3
2 to each
metal
C
M
Intro 31
First, you should learn the charges and donor # for the common
ligands (this will significantly speed up your counting):
Cationic 2e- donor: NO (nitrosyl), cyclopropyl (or anionic 4e-)
Neutral 2e- donors: PR3 (phosphines), CO (carbonyl), R2C=CR2
(alkenes), RCCR (alkynes, can also donate
4 e-), NCR (nitriles), CNR (isocyanides)
Anionic 2e- donors: Cl (chloride), Br (bromide), I (iodide), CH3
(methyl), CR3 (alkyl), Ph (phenyl), H
(hydride)
The following can also donate 4 e- 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
(imido), CR22 (alkylidene)
and from the previous list: OR (alkoxide), SR
(thiolate), NR2 (inorganic amide), PR2
Anionic 6e- donors: Cp (cyclopentadienyl), Tp (trispyrazolylborate), N3 (nitride), CR3 (carbyne)
Intro 32
And H2O:
Intro 33
Formal Charges
Calculated Charges
Co(+1)
= + 1.0
Co(+1)
= + 0.468
= 1.0
= 0.252
CO
= 0
CO
= 0.332
PMe3
= 0
PMe3
= + 0.149
PF3
= 0
P only
= + 0.266
PF3
= + 0.023
P only
= + 1.000
Ir(+3)
= + 3.0
Ir(+3)
= + 1.550
3 C
= 1.0
3 C
= 0.464
3N
= 0
3N
= 0.539
Rh(+1)
= + 1.0
Rh(+1)
= 0.419
CO
= 0
CO
= + 0.041
3 PH3
= 0
PH3
= + 0.447
dhpe
= + 0.929
Intro 34
Simple Example:
CH3
R3P
Re
CO
CO
PR3
Intro 35
H3CNC
H3CNC
H3CNC
CNCH3
Mo
2+
CNCH3
CNCH3
CNCH3
NCH3
d4
14eTotal: 18e-
Intro 36
H2C
R2P
H2C
How do we figure out the charge and electron donor ability of this
weird ligand (a phosphorus diylide)??
1) Remove the metal atoms and examine the ligand by itself:
H
H
H2C
R2P
R2P
H2C
H
Phosphorus is trivalent and since it has four bonds to it, there is a
formal positive charge assigned to the atom. Each carbon is
currently neutral and has an odd electron.
Intro 37
+2eR2P
R2P
H
Intro 38
Me
Rh
PPh3
1) There is no overall charge on the complex
2) There is one anionic ligand (3-C3H5, allyl).
H
H
H
H
H
+e-
H
H
H
H
H
H
H
H
+e-
H
H
Intro 39
Me
H
If you work out the Lewis Dot structure for this ligand you get an
even # of electrons so there is no need to add an electron to get an
anionic ligand. Note that it is EASY to forget that there is a H on
the Cp carbon that has the methyl group attached if you are not
thinking about organic line notation.
3) Because the complex is neutral and there is one anionic ligand
present, the Rh atom must have a +1 charge to compensate for
the one negatively charged ligand. So the Rh atom is in the +1
oxidation state.
Now we can electron-count:
Rh(+1)
d8
PR3
2e4e4-C5H5Me
4e3-C3H5
Total: 18e-
Intro 40
R2
P
P
R2
Mo
Cl
Mo
Cl
C
R2
P
P
R2
Intro 41
Mo(+1)
d5
2PR3
4e4eCO
4e2-Cl
Sub-total: 17eMo-Mo 1eTOTAL: 18e-
Intro 42
Me
H2
C
N
Pd
N
Me
N
Pd
C
H3
N
Me
d8
4e1e-
2e-CH22
Sub-total: 15ePd-Pd 1eTOTAL: 16eNote that Pd(+2) is generally happy with a 16e- configuration.
Intro 43
Re
5 -Cp
d6
6
6
18
Cl
Cl
Ta
Mo
(MeO)3P
(MeO)3P
Ni
PR3
PR3
O
N
NMe2
Mo
Me2N
Cr
NMe2
NMe2
PMe3
Ti
Br
OC
Br
OC
CO
CO
PMe3
Intro 44
Ni
Pd
N
O
Mo
Mn
Ph3P
C
O
N
O
Sc
C
O
OMe
Co
OMe
Me 3 P
Me 3 P
PMe 3
PMe 3
CO
OC
Cr
OC
Ph2
OR
PMe 3
Ph2
CH 2t-Bu
CH
Intro 45
O
C
Fe
O
C
O
C
O
C
Fe
Fe
OC
OC
Os
H
O
C
Os
CO
C
O
O
C
CO
Os
O
C
C
O
O
C
O
C
Fe
C
O
C
O
O
OC C
O
C
Co
CO
Co
C
O
C
O
Br
Au
Au
Au
Au
CH 3
RO
OR
OR
Mo
Mo
RO
OR
OR
Rh
?
Rh
O
R
R
O
Intro 46