Transition Metal Triple bond to Carbon

Introduction:
Transition metal carbyne are the compounds with a triple bond between carbon and the transition
metal. This triple bond consists of a σ-bond and two π-bonds. The HOMO of the carbyne ligand
interacts with the LUMO of the metal to create the σ-bond.
The two π-bonds are formed when the two HOMO orbitals of the metal back-donate to the
LUMO of the carbyne. They are also called metal alkylidynes—the carbon is a carbyne ligand.

Example:
The first example of a metal carbyne complex was prepared by the Fischer school by treatment
of Cr(CO)5(C(OMe)Ph) with boron trichloride:

Cr(CO)5(C(OMe)Ph) + BCl3 → ClCr(CO)4(CPh) + CO + BCl2(OMe)

Classification:
There are two main classifications of the carbines:
 Fischer-type Carbynes
 Schrock-type cabynes

Fischer Carbynes:

Fischer carbynes were first made in 1973 by Fischer himself. He produced them via electrophilic
abstraction of methoxide from a methoxide methyl carbene.

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Fischer carbynes are classified by being able to be stabilized by heteroatoms and found typically
bonded with low oxidation state transition metals (usually later transition metals).
Fischer carbynes usually other have π–acceptor ligands on the metal making the carbyne
essentially electrophilic.
A Fischer carbyne can be looked at as a doublet carbyne in the way it bonds. The lone pair of
electrons on the carbon atom covalently bond to the metal; it also forms a covalent π bond with
the metal, and has an empty orbital ready to accept electrons from a filled metal orbital.
Therefore the ligand is an LX type ligand using the covalent method:

The carbyne complexes that are formed are usually 18 electrons because the CR bond is mostly
covalent. Tungsten is a very common metal used to make Fischer carbynes.
Fischer is very famous in the organometallic field, winning the Nobel Prize in 1973 for his work.

Schrock Carbynes:

On the other hand, Schrock carbynes have no heteroatoms, and are found with high oxidation
state metals (early transition metals).
The other ligands on the metal are usually strong σ-donors, which makes the carbon
essentially nucleophilic.
The Schrock carbyne is an example of a quartet carbyne. It forms 3 covalent bonds to the metal
because it has 3 unpaired electrons. The ligand is of the X3 type.
They usually form complexes with less than 18 electrons and the metals tend to be d0.

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A very common metal for Schrock carbynes is Molybdenum. Schrock Carbynes can be made
from reducing a Fischer carbyne or by α-elimination.
Schrock also won the Nobel Prize in 2005, but not for this type of chemistry specifically,
for olefin metathesis which commonly uses Schrock type catalysts. Commercial scale alkyne
metathesis nearly exclusively uses a Schrock type alkylidyne catalyst.

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Similar to what has been observed earlier in the case of the Fischer carbenes and Schrock
carbenes, the Fischer carbyne complexes are formed with metal centers in lower oxidation states
for e.g. as in Br(CO)4W≡CMe,
while the Schrock carbyne complexes are formed with metals in higher oxidation state, e.g. as in
(t−BuO)3W≡Ct−Bu.

Synthesis:
Transition metal carbyne complexes are most common for the early transition metals,
especially niobium, tantalum, molybdenum, tungsten, and rhenium. They can also have low-
valence metals as well as high-. valence metals.

Carbyne complexes can be prepared by the following methods.

The Fischer carbyne complexes can be prepared by the electrophilic abstraction of a methoxy
group from a methoxy methyl substituted Fischer carbene complex.

Schrock carbynes can be prepared by the deprotonation of a α−CH bond of a metal−carbene

complex.

1. by an α−elimination reaction on a metal−carbene complex

2. by metathesis reaction

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The reactivities of Fischer and the Schrock carbynes mirror that of the Fischer and Schrock
carbenes. For example, the Fischer carbyne undergo nucleophilic attack at the carbyne−C atom
while the Schrock carbyne undergo electrophilic attack at the carbyne−C atom.

Reactions:
Various Reactions of carbynes have been extensively studied such as nucleophilic attack at the
carbon centre, electrophilic attack at the carbyne carbon, substitution of the spectator ligands by
nucleophilic attack at the metal centre, oxidation and reduction at the metal centre, modification
or substitution of the ligand on the carbyne or transfer of the carbyne ligands.

Nucleophilic Addition:
NucleophilicAddition is common for Fischer carbyne complexes that carry a δ+ charge on either
the central metal atom or at the carbyne carbon atom.

Nucleophilic Addition at Carbyne C:

In cationic carbynes, the addition of the nucleophile will proceed exclusively at the carbyne
carbon. This is because the LUMO is located on the carbyne C and it has a sufficiently large gap
between this molecular orbital and the next highest LUMO located on the metal centre. There
are many examples of nucleophiles that show this type of reactivity (mostly anionic) such as:
phosphines, Grignards, halogens, CN-, OR-, and SR- 1.

General Reaction Scheme:

LnM≡CR+ + Nu- → LnM=C(R)(Nu)

Example:
Cp(CO)2M(≡C-Ph)+ + Nu- → Cp(CO)2M[=C(Nu)(Ph)]

M = Mn, Re

Nu = F, Cl, Br, I, C10H7Se, Bu

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Nucleophilic Addition at Metal Centre:
When the carbyne is neutral, the metal centre is now a good candidate for the nucleophilic attack
depending of the other ligands attached and the nucleophilicity of the nucleophile. For
comparison, consider the cationic compound [(CO)5Cr-(≡CH)]+ and the neutral Cl(CO)4Cr-
(≡CH).
For the carbyne complex, the LUMO lies on the metal and the energy gap between this
molecular orbital level and the N-LUMO on the carbyne C is small. This means that a
strong nucleophile will attack at either the metal centre or the carbyne C because both are
accessible because of the small gap between the levels, but a weaknucleophile will only attack
the metal centre. This is a good way to improve selectivity of a nucleophilic reaction with a
carbyne complex.

General Reaction Scheme:

LnM≡CR + Nu → Ln-1(Nu)M ≡CR

Example (reversible halide exchange):

X(CO)4W(≡C-R) + Y- → Y(CO)4W(≡C-R) + X-

Electrophilic Addition:
Electrophilic Addition is possible in Schrock-type carbynes which carry a δ- charge on the
central metal atom.

Reactions with Protonic Acids:

H+ can add to electron-rich carbyne ligands to yield a hydridocarbene compound8. The final
product will differ depending on the strength of the acid.
For a strong acid, the H+ will add to the carbyne carbon to produce a carbene; and the counter ion
will add to the metal centre producing a neutral product.
However, if the acid is has a weakly coordinating anion, then a cationic hydriodcarbene will be
produced.

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Example 1, using a strong acid:
Cp(CO)2W(≡CR) + HCl → Cp(CO)2(I)W[=C(H)(R)]

2, using an acid with a weakly coordinating anion:

(Cl)(L4)W≡C-R + CF3SO3H → [(Cl)(L4)W=(CHR)]+[CF3SO3]-

Reactions with Lewis Acids:

Similar to addition of H+, other Lewis acids (such as AlMe3) can add to a metal-carbyne
complex.

Coupling of Carbyne Ligands:

Coupling reactions in carbyne complexes leads to either an alkyne or alkyne complex. Coupling
can be induced in carbyne complexes by three methods:

 Reductive coupling – occurs when a dimeric carbene is formed with reduction at both
metal centres.
 Oxidative coupling – occurs when a dimeric carbene is formed with oxidation at both
metal centres.
 Coupling at Terminal Carbynes – terminal carbynes will combine to form a bridging
ligand between the two metal centres.

Applications:

 Transition metal carbyne complexes can also react with electrophiles. The electrophile
reacts with the C-carbyne to form a transition metal carbene complex.
 These complexes can also undergo photochemical reactions. This means that the
transition metal carbyne complexes react with light.
 One example of a photochemical reaction of a carbyne complex is the formation of
a cyclopropenyl complex by an addition of an alkyne. This is also known
as photooxidation. Generally when a transition metal carbyne complex undergoes
photooxidation a new organic ring structure is formed.

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  There are other photochemical reactions with carbyne complexes as well. Some of these
include coupling of the carbyne ligand to a carbonyl, protonation of the carbyne carbon
and conversion of the carbyne ligand into a π-allyl.

 Such compounds are useful in organic synthesis of alkynes and nitriles. They have been
the focus on much fundamental research.

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