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CHEM2009: Transition

Metal Chemistry

Topic 2: Transition Metal Chemistry and an
Introduction to Organometallic Chemistry

Professor Gill Reid

Lecture synopsis:
L1: History & relevance of organometallic chemistry; e-counting rules
L2&3: TM carbonyls, carbonylates & hydrides preparation,
bonding & spectroscopic features (NMR & IR spectroscopy);
comparison of t-acceptor ligands (CO, N
2
, RNC, NO); IR
spectroscopy as a probe of ligand pr0perties
L4&5: TM alkyls, alkenes, alkynes, arenes bonding properties, e-counting; case
studies - examples
L6&7: Reaction mechanisms in TM chemistry; kinetics vs themodynamics;
substitution reactions (A, D, I mechanisms); rates of water exchange
& CFAE
L8: Substitution in organometallic complexes
L9: Oxidative addition & reductive elimination reactions; consequences &
relevance in organometallic chemistry
L10: Migratory insertion and elimination (de-insertion) reactions CO
insertion into metal-alkyl bonds (or alkyl migration to M-CO bond)
L11: Homogeneous catalysis combining elementary steps for industrial
production of acetic acid via the Monsanto Process (BP)
Reading:
Inorganic Chemistry Shriver & Atkins, Oxford, 5th Ed, 2009, Ch 21 & 22
Advanced Inorganic Chemistry F. A. Cotton, G. Wilkinson, C. A. Murillo
and M. Bochmann, Wiley, 6th Ed,1999, aspects of Ch 16, 21, 22 and survey
chapters
Organometallics I M. Bochmann, OCP 12, 1994
The Organometallic Hypertext Book -
http://www.ilpi.com/organomet/index.html
Lectures are supported by problem solving workshops and lab practicals
which reinforce the key learning objectives and develop important skills in
interpretation of various spectroscopic and other experimental data to provide logical
rationale for the identification of the products from organometallic reactions.
These activities are fully integrated within the course, full participation is
a requirement and all the relevant material is examinable.
History of organometallic
chemistry & electron counting
rules
L1
History of Organometallic Chemistry:
1760 1
st
organometallic compound (Cadet) [(CH3)2As]O
1827 1
st
alkene complex (Zeise) Na[PtCl3(C2H4)]
1849 1
st
alkyl Zn and Hg compounds (Frankland) [(C2H5)2Zn],
[C2H5ZnI], [(CH3)2Hg]
1868 1
st
metal carbonyl complex (Schtzenberger) [Pt(CO)Cl2]2
1890 1
st
binary metal carbonyl (Mond) [Ni(CO)4]
1909 1
st
o-organotransition-metal compound (Pope) [(CH3)3PtI]
1951 1
st
sandwich complex (Pauson, Miller) [(C5H5)2Fe]

Nobel Prizes:
1963 Polymerisation catalysts (Ziegler, Natta)
1973 Sandwich complexes (Fischer, Wilkinson)
2001 Chiral catalysts (Knowles, Noyori, Sharpless)
2005 Metathesis catalysis (Chauvin, Grubbs, Schrock)
Effective Atomic Number Rule (EAN):
Also called the Inert gas rule or the 18 electron rule

Thermodynamically stable transition metal
organometallics are formed when the sum of the metal d
electrons + the electrons conventionally regarded as
being supplied by the ligands = 18"
i.e. organometallic complexes are stable when the metal has effectively the
atomic number of the next inert gas.

[Similar to the Lewis octet rule for light main group elements]

[Only useful for organometallic compounds do not attempt to
use this in coordination chemistry]
Electron counting: ligands
Consider ligands as Lewis bases: i.e. electron pair donors

e.g. H will achieve an inert gas configuration as H
-
(hydride)
- a 2 electron donor (1s
2
)
Cl will achieve a Lewis octet (inert gas config.) as Cl
-
(chloride)
- a 2 electron donor (3s
2
3p
6
; 3p
z
= o-donor)
CH
3
will achieve a Lewis octet (inert gas config.) as CH3
-
(isoelectronic with
NH: CH
3
-
NH
3
)
- a 2 electron donor (sp
3
hybrids - with lone pair)
CO is stable as neutral molecule (:C
-
O
+
)
- a 2 electron donor (sp hybrids - lone pair)

Termed MLX approach L = neutral 2e donor; X = charged 2e donor
Electron counting: complexes
E.g.1 [Cr(CO)
6
]
Ligands:
6 x neutral CO ligands - each 2 electron o-donors
6 x 2 e count
Metal: Cr(0)
Cr(g) 3d
5
4s
1
- in complexes, d-s orbital separation is increased so
we consider Co(0) in complexes as 3d
6
6 e count
Complex:
Ligand + metal electron count = 18 e total
Electron counting, MLX approach
E.g.2 [IrCl
2
(CH
3
)(CO)(PPh
3
)
2
]
Ligands:
3 anionic ligands - 2 Cl
-
, 1 CH
3
-
- each 2 e o-donors
3 neutral ligands (CO + 2 PPh
3
- each 2 electron o-donors)
12 e count
Metal: Ir(III)
Ir(g) 5d
7
6s
2
- in complexes, so lose 3 electrons and consider 5d
6
.
6 e count
Complex:
Ligand + metal electron count: 18 e total
Ligand nomenclature

n
(Greek eta) number of ligand atoms, n, coordinated to a metal;
when n is absent, all unsaturated atoms in the ligand are assumed
to be coordinated to the metal
E.g. [Cr(
6
-C
6
H
6
)
2
] i.e. dibenzenechromium


m
(Greek mu) number of metal atoms, m, the ligand is coordinated
to;
when m is absent, the ligand is assumed to be coordinated to 2
metal atoms
E.g. [Co
2
(CO)
8
] i.e. di--carbonyl-bis{(tricarbonyl)cobalt}
Electron counting: M-M bonds
E.g.3 [Rh(C
5
H
5
)(CO)
2
]
Ligands:
1 anionic ligand (6 e donor)
2 neutral ligands (CO) 10 e count
Metal: Rh(I)
Rh(g) 4d
8
5s
1
- in complexes, and loses 1 electron to get +1; consider as 4d
8
.
8 e count i.e. 18 e overall

E.g.4: [Rh
2
(C
5
H
5
)
2
(CO)
3
]
Each metal has Rh(C
5
H
5
)(CO) unit (16 electrons).
Bridging (
2
) CO donates an electron pair 1 electron per metal:
17 electrons per unit (therefore unstable)
Have a 2-centre-2-electron Rh-Rh bond to achieve the 18 electron
count
Why 18 electrons?
Organometallic compounds usually involve strong-field ligands
i.e. good -donor or -donor/t-acceptor ligands
6 Metal-ligand o-bonding orbs,
3 Metal-ligand t-bonding orbs.

So optimum bonding at 18 e

Also large gap (A
oct
) to metal-ligand
t* orbital, so rarely occupied


Exceptions:
i) when ligands are not strong t-
acceptors and
ii) at extremes of TM rows
4p
4s
5 x 3d

Ligand
o-orbs
E
Ligand
t-orbs
o-donor o-donor/t-acceptor
Metal carbonyls

(compounds containing the MCO
fragment)
L2
Coordination modes in TM carbonyls:
Always C-coordinated to TMs, and 2 e donor
O O O

C C C

M M M M M
M
terminal (
1
) doubly bridging () triply bridging (
3
)
e.g. [Cr(CO)
6
] e.g. [Co
2
(-CO)
2
(CO)
6
] e.g. [Co
6
(
3
-CO)
4
(CO)
12
]
(common form, and less common
almost always in conjunction
with M-M bonds)
Also [Fe
2
(CO)
9
]
Preparation of TM carbonyls:
1. Direct combination:
metal + CO (only works for Fe, Ni, and Ru)

2. Synthesis from a metal salt:
metal salt + reducing agent + CO

Stable binary carbonyls (i.e. TM compounds with only CO ligands)
are known for:
V Cr Mn Fe Co Ni
Mo Tc Ru Rh
W Re Os Ir
Group 6: Cr, Mo and W
Synthesis by reduction of a metal salt:




White, air stable volatile solid: octahedral:
Cr-C 1.92 ; IR: v(CO) 2000 cm
-1
(Point Group = O
h
; t
1u
is the
only IR active band expected)

[Mo(CO)
6
] and [W(CO)
6
] have very similar properties
benzene
CrCl
3
+ Al + 6 CO [Cr(CO)
6
] + AlCl
3
AlCl
3
140
o
C, 300 atm
Group 8: Fe, Ru and Os
Iron: Synthesis is by direct combination:
200 atm
Fe + 5 CO [Fe(CO)
5
]
200
o
C
[Fe(CO)
5
] is a yellow liquid, bp 103
o
C; structure: trigonal bipyramid;
UV irradiation precipitates [Fe
2
(CO)
9
] (contains one Fe-Fe bond to keep 18 e)

Ruthenium and osmium: Synthesis by reduction of a metal salt
(e.g. via RuCl
3
or OsO
4
)
[Ru(CO)
5
] and [Os(CO)
5
] are unstable, since for these metals:

[M(CO)
5
] [M
3
(CO)
12
] + 3CO

The M(CO)
4
units in the final product are 16 e species, so 2 M-M bonds are needed to
allow each metal atom to achieve an 18 electron count - triangular
Group 10: Ni, Pd and Pt
Nickel: Synthesis is by direct combination:
1 atm
Ni + 4 CO [Ni(CO)
4
]
25
o
C
(this is the basis of the Mond process for purification of Ni)

Colourless liquid: bp 43
o
C - very toxic (toxicity similar to HCN)
Tetrahedral (T
d
) complex - Ni(0) is d
10
- 18 e count; v(CO) 2058 cm
-1
(t
2

expected from Group Theory)

There are no binary carbonyls of Pd and Pt. Nearest equivalents are the
[M(PR
3
)
4
] complexes or cluster anions, e.g. [Pt
6
(CO)
12
]
2-
Group 9: Co, Rh and Ir
Synthesis is by reduction of a metal salt:

130
o
C
2CoCO
3
+ 2H
2
+ 8CO [Co(CO)
4
]
2
+ 2CO
2
+ 2H
2
O
300 atm

Co(CO)
4
is a 17 e species, so it dimerises with a Co-Co bond (2 centre, 2
electron) to achieve 18 e count.
There are 2 bridging CO groups - for e-counting purposes each bridging CO
donates 1 electron to each metal.
Heating causes loss of CO, forming [Co(CO)
3
]
4
- 15 electron metal centres,
requiring 3 Co-Co bonds - tetrahedron.

M
4
(CO)
12
is the smallest binary carbonyl for Rh and Ir also made by
reduction of a metal salt.
Group 7: Mn, Tc and Re
Synthesis by reduction of a metal salt

CO (200 atm)
MnCl
2
+ Na/Ph
2
CO [Mn(CO)
5
]
2
200
o
C, THF

(Ph
2
CO = dibenzophenone - forms a carbanion with sodium which reduces the metal)

Electron count: Each Mn(CO)
5
- with Mn(O) being d
7
has 17 electrons, forming a 2-
centre 2-electron Mn-Mn bond provides 18e count.
(c.f. 2 CH
3

H
3
C-CH
3
). d(Mn-Mn) = 2.92 . Staggered Mn(CO)
5
units

[Tc
2
(CO)
10
] and [Re
2
(CO)
10
] are also known and stable.
Group 5: V, Nb and Ta
Synthesis is by reduction of a metal salt:
diglyme/ether
VCl
3
+ 3Na + 6CO [Na(diglyme)
2
]
+
[V(CO)
6
]
-
120
o
C,200atm
(diglyme = MeOCH
2
CH
2
OCH
2
CH
2
OMe)

[V
-I
(CO)
6
]
-
= a carbonylate anion - d
6
, oct. 18 electrons. v(CO) 1859 cm
-1
Oxidation with HCl forms [V(CO)
6
] = 17 electrons, pyrophoric;
eff
= 1.71 BM
(t
2g
5
) i.e. low spin (since CO is a strong ligand field)

Nb
2
(CO)
12
and Ta
2
(CO)
12
have never been authenticated, but [M(CO)
6
]
-
are
well known for Nb and Ta
Group 11: Cu, Ag and Au
There are no stable binary carbonyls with Cu, Ag or Au
Some complexes of M(I) (d
10
) with CO are known:
H
2
O
Cu + Cu
2+
+ CO [OC-Cu-OH
2
]
+

For Ag and Au, linear complexes known:
[OC-Ag-CO]
+
v(CO) = 2198 cm
-1
(IR)
[OC-Au-Cl] v(CO) = 2152 cm
-1
(IR)
[OC-Au-CO]
+
v(CO) = 2217 cm
-1
(IR)

Virtually no t-back bonding due to low energy of the d orbitals (and
consequently high frequency IR bands, since the CO(t*) orbital ~empty)
Metal carbonylates:
(anionic metal carbonyls)
Synthesis is by reduction of M-M bonds by Na (or as amalgam in Hg)
THF
Mn
2
(CO)
10
+ Na Na[Mn
-I
(CO)
5
]

Further reduction by stronger reductant leads to:
THF
Mn
2
(CO)
10
+ (10x)Na Na
3
[Mn
-III
(CO)
4
]

Mn(-III), d
10
. v(CO) 1805w and 1670vs cm
-1

Base attack on a M-CO group:
Fe(CO)
5
+ 4 OH
-
[Fe
-II
(CO)
4
]
2-
+ CO
3
2-
+ 2 H
2
O

Fe(-II), d
10
. v(CO) 1771w and 1729vs cm
-1
Metal hydrides (M-H):
1. Synthesis is by reduction of M-M bonds using H
2
:

[Co
2
(CO)
10
] + H
2
[Co
I
H(CO)
4
] (pK
a
= 8.3)

2. Protonation of a carbonylate anion (with H
2
O or acid):
[Fe(CO)
4
]
2-
+ H
2
O [Fe
0
H(CO)
4
]
-
+ OH
-

[Fe
o
H(CO)
4
]
-
+ H
+
[Fe
II
H
2
(CO)
4
] (pK
a
= 11.4)

3. Base attack on a M-CO group:
Fe(CO)
5
+ 2 OH
-
[Fe
0
H(CO)
4
]
-
+ HCO
3
-
Spectroscopic characterisation

IR spectroscopy - Functional groups & typical ranges:

Neutral carbonyls: v(CO) for bridging groups 1650 - 1860 cm
-1
v(CO) for terminal groups 2125 - 1850 cm
-1
(strong)

Nitrosyls: Linear M-NO
+
: v(N-O) bands 1700 - 1900cm
-1

Dinitrogen complexes: v(N-N) bands 1900 - 2200cm
-1
(medium
intensity)

Metal hydrides: v(M-H) bands 2100 - 1800 cm
-1
(weak)
Spectroscopic characterisation
NMR spectroscopy - Functional groups:

Transition metal hydrides: characteristic
1
H shift range: o -5 to -30
e.g. (CO)
5
MnH -7.5
(CO)
4
FeH
2
-11.1
(CO)
4
OsH
2
-8.7

13
C Shifts (vs. TMS as o = 0):
Carbonyl ligands: Terminal: o = 180 - 220
Bridging: o = 220 - 280
Electron rich metals shift to higher o

Comparison of t-
acceptor ligands
L3
Bonding in diatomics:
Electronegativity
P
: C < N < O
N
2
CO CN
-
NO
+
; RNC is pseudo-isoelectronic (RN like O); NO has 1 extra electron in t*
2p
2s
2p
2s
N: 2s
2
2p
3
N: 2s
2
2p
3
Dinitrogen: N
2
Carbon Monoxide: CO

C: 2s
2
2p
2
O: 2s
2
2p
4
2s
2p
2p
2s
o
o
o*
o*
t
t*
t*
t
o
o
o*
o*
Energy
Energy
Dinitrogen frontier orbitals:
NN
N
2
has 2 x degenerate Lowest
Unoccupied MOs (LUMOs) = t*
(mutually orthogonal)
Highest Occupied MO
(HOMO) =
N N
Carbon monoxide frontier orbitals:
CO
C
O

2 x degenerate LUMOs =
t*
(orthogonal)

Localised on C
HOMO =

Localised on C


MeNC
12
N
2

8 CO

4 t*

eV 0

-4
NO
-8

-12 o

-16


Comparison of t-acceptor (t-acid) ligands

Interactions are strongest
when orbital is localised
on the donor atom.

Donation is stronger from
the higher energy occupied
orbitals

Acceptance is easier into
lower lying unoccupied
orbitals

Cone angles of diatomics
90-95
o

t-acceptance: MeNC < N2 < CO << NO

-donation: MeNC > NO CO > N2
Metal-CO bonding overview:
o-donation: 2 electrons from HOMO which is located mostly on C (hence M-C
bond)
t-backbonding: 2 t* orbitals per CO donation is from filled metal d
t
orbitals
Synergic bonding: i.e. the two forms of bonding are mutually enhancing
t-acceptor ligands act as electron sinks - varying the extent of back donation

In [M(CO)
6
], there are 9 M-L bonding orbitals occupied for 6 bonds bond
order of 1.5

In [M(CO)
3
L
3
] (where L is not a t-acid ligand) then 3 M-L t-bonds are localised
on 3 M-CO bonds giving a M-CO bond order of 2.
Evidence for the synergic model (1):
Predicts that with increasing t-acceptance:
The M-C bond should shorten.
The C-O bond should lengthen.
The bond strength of the M-C bond will increase and hence the force
constant of that bond might increase.
The bond strength of the C-O bond will decrease and hence the force
constant of that bond might decrease.
Evidence for the synergic model (2):
Note the following experimental constraints:
the variation in C-O bond length is small compared to experimental error
so the M-C bond length provides better evidence (X-ray crystallography)
The v(M-C ) modes mix with o(M-C-O) and so the observed frequency is a
reflection not only of the force constant K
CO
.
The frequency range of v(M-C ) is ~400 cm
-1
- below the NaCl cut-off, so
observable only with KBr or CsI windows in IR
On the positive side - the v(C-O) modes are very intense and occur in a
region (~ 2000 cm
-1
) relatively free of other vibrations (except v(M-H) )

Hence the v(CO) IR bands provide the easiest means of monitoring the
relative degree of t-backbonding into the t* orbitals of CO

The v(NN) and v(NO) bands will behave similarly in M-N
2
and M-NO
complexes.
v(CO) energies in metal carbonyls:

In free CO, v(CO) = 2143 cm
-1
For a diatomic molecule: v(Hz) = (1/2t)(K/m)
where m (reduced mass) = m
1
m
2
/(m
1
+m
2
) and K = the force constant of the bond
Consider a series of isoelectronic complexes we see an increase in nuclear charge from
V(-I) to Mn(+I), or from Fe(-II) to Ni(0) and hence increasing Z
eff
of the 3d orbitals. So
less available for t-back bonding:
Experimentally:
[Mn(CO)
6
]
+
[Cr(CO)
6
] [V(CO)
6
]
-
v(CO)

2096 2000 1859
v(MC) 416 449 460

[Ni(CO)
4
] [Co(CO
4
]
-
[Fe(CO)
4
]
2-

v(CO) 2058 1883 1729

Increasing back bonding to CO from left to right

CO bond order + and v(CO) + from left to right
MC bond order | and v(MC)| from left to right
Effect of CO substitution:
With the exception of PF
3
, phosphines
are stronger donors and weaker
acceptors than CO. So substitution of
a CO by a phosphine should increase
the electron density on a metal and
thus increase the t-back bonding to
the remaining CO groups (compare
the A1 modes across the series).
CO vibrational modes for
[Ni(CO)
4-n
L
n
], L = P(OMe)
3


The v(CO) frequencies are good
guides to the mean donor/acceptor
ability of the other ligands (L = PR
3
)
in the complex.
E.g. [Ni(CO)
3
L], A
1
modes:
[Ni(CO)]
4
[Ni(CO)
3
L] [Ni(CO)
2
L
2
] [Ni(CO)L
3
]

Point T
d
C
3v
C
2v
C
3v
group:

v(CO) A
1
2131 A
1
2082 A
1
2025 A
1
1964
T
2
2058 E 2006 B
1
1965

v(MC) A
1
368 A
1
420 A
1
458 A
1
499
T
2
423 E 455 B
1
495


R v(CO) (A
1
) o-properties t-properties
of L (PR
3
) of L (PR
3
)

C(CH
3
)
3
2056 o-donation t-acceptance
CH
3
2064 decreasing increasing

C
6
H
5
2069
OCH
3
2079
OC
6
H
5
2085
F 2111
As v(CO) increases, this indicates that PR
3

is pushing less e-density onto Ni; i.e. PR
3
is
a weaker o-donor or a better t-acceptor
Metal nitrosyls:
Sources of NO in a complex are:
NO
+
BF
4
-
, NOCl, NO
2
- all with N as N
III
; and NO with N as N
II
NO
+
+ e = NO (E
o
= 1.28 V vs SCE in MeCN)
v(NO): ~2250 cm
-1
1840 cm
-1

NO can reduce the metal formally to form NO
+
on coordination and displace CO:
[Fe(CO)
5
] + 2 NO [Fe
-II
(CO)
2
(NO)
2
] + 3 CO
d
8
, 18 e d
10
, 18e (C
2v
)
v(CO) 2087, 2038 cm
-1
;
v(NO) 1817, 1780 cm
-1
[Cr(CO)
6
] + 4 NO [Cr
-IV
(NO)
4
]
d
6
, 18 e d
10
, 18e (T
d
)
v(NO) 1726 cm
-1
Important reaction type inter-converting nitrosyls and nitrites:
[(CN)
5
Fe(NO)]
2-
+ OH
-
[(CN)
5
Fe{NO(OH)}]
3-
[(CN)
5
Fe(NO
2
)]
4-
Metal nitrosyls: alternative structure
In some complexes the M-N-O angle is highly bent:
[Ir
III
Cl(NO
-
)(CO)(PPh
3
)
2
]
+
:
5d
6
2e 2e 2e 4e = 16 electrons


the NO is now considered as a [NO]
-
with the extra 2e in a lone pair
on an sp
2
N atom.
Metal forms a -bond by donation from the N, and there is t-back-
bonding in one plane:
Ir Cl
P
OC
P
N
O
o-bonding interaction t-bonding interaction
M
N O
M
N O
NB within CHEM2009 you
should treat TM-NO
complexes as containing
NO
+
(2e donor) unless
specifically told otherwise
For background information:
Metal dinitrogen complexes:
Direct synthesis from N
2
:
[Ru
II
(NH
3
)
5
(OH
2
)]
2+
+ N
2
H
2
O + [Ru(NH
3
)
5
N
2
]
2+

d
6
, 18e d
6
, 18e
v(NN): 2331 cm
-1
(Raman) 2150 cm
-1
(IR)

Reduction in the presence of N
2
:
[FeCl
2
{Et
2
PCH
2
CH
2
PEt
2
}
2
] + N
2
+ Na(naphthalenide) [Fe(N
2
){Et
2
PCH
2
CH
2
PEt
2
}
2
]

Reaction with acids (Functional model of nitrogenase):
[WCl
4
(PMe
2
Ph)
3
] + N
2
+ Mg + PMe
2
Ph [W(N
2
)
2
(PMe
2
Ph)
4
]
+ H
+
NH
3

Metal-carbon -
bonds

L4
Synthesis of metal alkyls (1):
From substitution of anionic ligands:
the M-C bond involves alkyl acting as a 2 e donor:

metal halide + carbanion source (M = Li, Mg, Al, Zn, Hg)
ZrCl
4
+ 4 PhCH
2
MgCl [Zr(CH
2
Ph)
4
]
TiCl
4
+ Al
2
Me
6
[MeTiCl
3
]

Metal hydride + alkene: homologation of an anionic ligand (insertion)
trans-[(Et
3
P)
2
PtHCl] + C
2
H
4
trans-[(Et
3
P)
2
Pt(C
2
H
5
)Cl]

NB there is no change in oxidation state during this reaction
Synthesis of metal alkyls (2):
From alkyl electrophiles:
Carbonylate anion + alkyl halide
Na
+
[Mn
-I
(CO)
5
]
-
+ CH
3
I [CH
3
Mn
I
(CO)
5
] + NaI +

From 16e complex + alkyl halide:
[Ir
I
(CO)L
2
Br] + CH
3
Cl [Ir
III
(CO)L
2
Br(CH
3
)Cl]

Increase in oxidation state of II formally reducing a carbenium ion
(carbocation) to a carbanion (oxidative addition- see later)
Stability of metal alkyls (1):
Thermodynamic stability:
Comparable to main group alkyls
Decreases with the number of alkyl groups
Bond strength increases down the group (unlike main group alkyls)
(d orbitals become less contracted as the TM Group is descended, hence
giving better overlap with ligand orbitals)

Main Group Alkyl D(kJ/mol) TM Alkyl D (kJ/mol)
CMe
4
358 Ti(CH
2
t
Bu)
4
198
SiMe
4
311 Zr(CH
2
t
Bu)
4
249
GeMe
4
249 Hf(CH
2
t
Bu)
4
266
SnMe
4
217 TaMe
5
261
PbMe
4
152 WMe
6
160
Stability of metal alkyls (2):
Kinetic stability:
Often much lower than main group alkyls due to different decomposition mechanisms:
Main group decomposition (homolytic fission radicals) (PbEt
4
is quite stable)

PbEt
4
(100
o
C) PbEt
3
-
+ Et
-
TM alkyl decomposition (-hydride elimination) (TiEt
4
is unknown)

R
3
Ti-CH
2
CH
3
R
3
TiH + CH
2
=CH
2
(see later)

- Increase stability when no -H present (e.g. R = CH
3
, CH
2
CMe
3
, CH
2
Ph, CH
2
SiMe
3
)

- Increase stability by using more bulky ligands

More electron rich alkyls as donors and block dinuclear decomposition mechanisms
i.e. TiMe
4
is stable to 40
o
C but the much bulkier Ti(CH
2
CMe
3
)
4
is stable > 100
o
C
NMR Spectroscopic
Characterisation

Spectroscopic characterisation
of M-alkyls/alkenes/arenes:
NMR spectroscopy - Functional groups:
1
H NMR
Metal alkyls: Shifts are a function of electronegativity (oxidation state):
electron rich metals shift to lower o: Range 5 to -1 ppm
Arenes and alkenes:
Upfield (lower o) shifts on coordination ~ 0.5 to 4 ppm;
electron rich metals shift to lower o

13
C NMR
Metal alkyls: shifts function of electronegativity (oxidation state):
electron rich metals shift to lower o: Range 50 to -20
Arenes and alkenes: Upfield (lower o) shifts on coordination of ~ 5 to 80 ppm
electron rich metals shift to lower o:
13
C{
1
H} NMR Example: [Re{C(O)CH
3
}(CO)
5
]
Re
CO OC
CO OC
CO
O CH
3
o/ppm
CH
3
CO trans

4 x CO

C (acyl)

245 55 200 150 100
Metal-carbon t-
bonds
Metal alkene complexes:
Synthesis by substitution reactions of 2 e donor ligands:
K
2
[PtCl
4
] + C
2
H
4
K
+
[(q-C
2
H
4
)Pt
II
Cl
3
]
-
.H
2
O + KCl
Re(CO)
5
Cl + C
2
H
4
+ AlCl
3
[Re
I
(CO)
5
(q-C
2
H
4
)]
+
AlCl
4
-
Centre point of the double bond acts as the ligand binding point

Alkene is face-on to the metal

An extreme view would be to consider it as a
[C
2
H
4
]
2-
bidentate metal-di-alkyl, but generally
the actual bonding is more subtle than that
description.
Bonding of ethene to a transition metal (1):
Highest Occupied Molecular Orbital
(HOMO) can act as a 2-electron donor.



Lowest Unoccupied Molecular Orbital
(LUMO) can act as a t-acceptor.
Bonding of ethene to a transition metal (2)
The t orbital on ethene acts as a -donor to the metal;
the t* orbital on ethene can be a t acceptor from the
metal.
C
C
M
o-donation
(2e donor)
Back-bonding to empty
t orbital
C
C
M
Bonding of ethyne (RCCR) to a TM:
One t orbital on ethyne acts as a -donor to the metal and one t * orbital on ethene can be
a t-acceptor from the metal.

HOMO as 2 e donor HOMO with possible
weak t donation



LUMO as acceptor LUMO as acceptor
with weak o-interaction


Generally alkynes are 2 electron donors ( occasionally 4 e donors to early transition
metals with low electron density)
Alkyne bonding orbital interactions
o-donation
from filled
alkyne t-
orbital
t-acceptance
to vacant t*
alkyne orbital
t-donation
from filled
alkyne t
orbital
o-type back
bonding to
vacant t*
alkyne orbital
TM-alkyne bonding
The bonding of an alkyne to a TM complex is similar to that of an
alkene complex.
Alkynes tend to be more electropositive and therefore tend to bind
more tightly to a TM than alkenes.
In fact, alkynes will often displace alkenes.
The primary difference in bonding between alkenes and alkynes is that
an alkyne can act as either a 2 or 4 electron donor.
Alkynes have two sets of mutually orthogonal t bonds. We can bind
one of these to the TM in a o-donor fashion (A) as we did for alkenes,
including a t-backbond (B).
The orthogonal set can also bind in a t-donor fashion using an
orthogonal metal d-orbital (C).
The back-donation to the anti-bonding orbital (D) is a o-bond, and the
degree of overlap is small (the contribution of D to the bonding of
alkynes is minimal at best).

Metal-Carbon t
bonds arenes and
cyclopentadienyl
ligands
L5
Arenes as ligands (1):
The 6 t electrons in benzene can also act as a ligand as if a
delocalised tri-alkene ligand


n
Bu
2
O, THF
[Cr(CO)
6
] + C
6
H
6
[Cr(q
6
-C
6
H
6
)(CO)
3
] + 3 CO
Arene is face-on to metal so 6 t-electrons act
as donors (molecule has C3v symmetry).

Can consider as an octahedral complex with
the benzene a facially coordinating ligand
(effectively occupying 3 coordination sites).
CO
OC
CO
Cr
Arenes as ligands (2):
With 2 benzene ligands can form a sandwich complex
[M(C
6
H
6
)
2
] structures are mostly stable as 18 electron species
Both arenes are face-on to metal so
6 t-electrons act as donors.

Rings are eclipsed in the crystal
structure (D
6h
symmetry).

Can consider as an octahedral
complex with the benzenes as
facially coordinating ligand
E. O. Fischer, 1955 - rational synthesis and structure; Nobel Prize 1973
6 t electrons

3d
6

6 t electrons

= 18 electrons
Cr
0
Charged arenes as ligands (1):
The 6 t electrons in the cyclopentadienyl anion (C
5
H
5
)
-
can also act as
a strong ligand
q
5
-C
5
H
5
-
ring face-on
to metal: aromatic
anion donates 6 t-
electrons to metal
[Mo(CO)
6
]
Mo
CO OC
CO
(+ Na)
_
+ H
+
_
+ 3 CO
cyclopentadiene, C
5
H
6
cyclopentadienyl, C
5
H
5
-
Point group = C
3v
; I
CO
= a
1
+ e
-both IR active (2 CO stretches in IR)
Charged arenes as ligands (2):
Two cyclopentadienyl anions (C
5
H
5
)
-
(often abbreviated as Cp
-
) can
also form sandwich complexes: metallocenes
these exist from M = V to Ni (15 to 20 electrons) due to the stability of
the ion triplet.
Synthesis: P L Pauson, 1951.
Proposal of sandwich structure: G Wilkinson, 1951: Nobel Prize 1973
Ferrocene: [Fe(q
5
-C
5
H
5
)
2
]

Cyclopentadienyl rings
both face-on to the metal

Nearly staggered in crystal
Fe
6 t e

d
6

6 t e

= 18 e
II
Case studies/examples:
Determine the NVE associated with the following species and sketch
their structures:
[FeH
2
(CO)
4
]
1
H NMR: o = -8.4

[Ru
3
(CO)
12
]

[Pt(
t
Bu)Cl(PMe
3
)
2
]

[(q
5
-C
5
H
5
)Fe(CO)
2
I] v(CO) = 2055, 1982 cm
-1


For the reaction sequence below, use the data
provided to identify compounds A-D and sketch
their structures.
[MnCl(CO)
5
] + PMe
3
A + B
+
C + D
CH
2
Cl
2
,
reflux
(i) AgBF
4
/ Me
2
CO;
(ii) PMe
3
A: %C = 33.1; %P = 19.0; %Mn = 16.8; IR: 2028, 1959, 1917 cm
-1
; o(
31
P) = -17 (s).
B: m/z = 28
C: %C = 31.8; %P = 20.5; %Mn = 12.1; IR: 2020, 1950 cm
-1
; o(
31
P) = -10 (s).
D: white solid; %Cl = 24.8

[PMe
3
: o(
31
P) = -62]