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423/523 Organometallic Chemistry Problem Set 4: C C PH PH

This document contains a problem set with questions about organometallic chemistry. It includes questions about: 1) Why strained alkenes bind strongly to metals. 2) The product and hybridization of carbon atoms in the reaction of an alkyne with cobalt. 3) Possible bonding modes for cyclooctatetraene. 4) π-MOs of the allyl anion and interacting metal d-orbitals. 5) Changes in metal-phosphine and phosphorus-carbon distances upon oxidation of a metal complex. The responses provide explanations for each question addressing concepts like rehybridization, bonding modes, molecular orbitals, and effects of oxidation.

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226 views

423/523 Organometallic Chemistry Problem Set 4: C C PH PH

This document contains a problem set with questions about organometallic chemistry. It includes questions about: 1) Why strained alkenes bind strongly to metals. 2) The product and hybridization of carbon atoms in the reaction of an alkyne with cobalt. 3) Possible bonding modes for cyclooctatetraene. 4) π-MOs of the allyl anion and interacting metal d-orbitals. 5) Changes in metal-phosphine and phosphorus-carbon distances upon oxidation of a metal complex. The responses provide explanations for each question addressing concepts like rehybridization, bonding modes, molecular orbitals, and effects of oxidation.

Uploaded by

estefanimagdiel
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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423/523 Organometallic Chemistry

Problem set 4

1. Strained alkenes such as cyclopropene or norbornene bind unusually strongly to metals. Suggest a
reason why.

Rehybridisation (sp2 → sp3) upon binding leads to relief of strain.

2. Alkynes readily bridge M-M bonds, in which case they act as 2e donors to each metal. Sketch the
product of the reaction below, indicating the hybridization of the C atoms.

PhCCPh + Co2(CO)8 → (µ2-PhCCPh)Co2(CO)6 + 2CO

sp3
Ph Ph
C C

Co(CO)3
(OC)3Co

3. Draw as many bonding modes for cyclooctatetraene as you can think of.

Lots! Don’t forget bridging modes…

4. Sketch the three π-MOs of the allyl anion, [C3H5]–. Draw metal d-orbitals that can interact with
these MOs, and name the type of bonding (e.g. M→L π-acceptor).

M to L
π-acceptor
L to M L to M
π-donor σ-donor

5. The M-P distance in (η5-C5H5)Co(PEt3)2 is 221.8 pm and the P-C distance is 184.6 pm. The
corresponding distances in [(η5-C5H5)Co(PEt3)2]+ are 223 pm and 182.9 pm. Account for the changes
in these distances as the former complex is oxidised.

The oxidised complex is less able to donate electron density into σ* PEt3 antibonding orbitals,
so P-C bonds become shorter. Weakening of π-back bonding will also lengthen the Co-P bond.
However... the better energy match between metal and ligand orbitals upon oxidation of the
metal would make the M-P bond become shorter due to stronger σ-bonding, and given that σ-
bonding is much more important for phosphines than π-back bonding, I would have thought it
would be the more important effect. Apparently not…

6. Predict the product of the reactions between: Work out the structures and then use DGM rules.
(a) [Ru(η5-C7H9)(η6-C7H8)]+ and H–. Ru(η5-C7H9)2
(b) [W(η5-C5H5)2(η3-C3H5)]+ and H–. W(η5-C5H5)2(η2-cyclo-CH2CH2CH2)
We’ll cover this material later in the term.

7. Ligands of type X–Y only give 3c-2e “agostic” bonds to transition metals if X = H and Y lacks lone
pairs. Why do you think this is so (consider alternative structures if X and Y are not H)?

Lone pairs always compete better than an agostic bond (both donate a pair of electrons to the
metal). If X ≠ H, the σ* orbital is no longer spherical (it is, for example, a combination of two
sp3 orbitals out of phase rather than an sp3 and a H 1s) and is much less accessible to a metal d-
orbital.

8. [IrH2(H2O)2(PPh3)2]+ reacts with indene to give [Ir(C9H10)(PPh3)2]+ (A). On heating, this species
rearranges with H2 loss to give [IrH(C9H7)(PPh3)2]+ (B). Only A reacts with ligands such as CO to
displace C9H7. What do you think are the structures of A and B?

indene

+ +

Ir Ir
H
Ph3P PPh3 Ph3P
PPh3

A B
These structures obey the 18e rule and fit the empirical data. The reactivity described should
probably read “Only A reacts with ligands such as CO to displace C9H10; B does not react to
displace C9H7”. However, you don’t really need this to solve the structural question.
The Cp-like indenyl ligand is difficult to displace as it is formally anionic, whereas the neutral
arene can be replaced relatively easily by 3 COs.

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