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Chem 321

March 2012 Tutorial Questions on Catalysis and Organometallic Chemistry

1. A new chromium diphosphine catalyst for the selective trimerization of ethylene to make 1hexene was reported recently (Chem. Commun., 2002, 858): a) For the four-coordinate Cr cation shown below, what is: i) ii) the oxidation state of the metal, and the electron count at the metal.

b) Based on the following information sketch out a catalytic cycle for this process starting with the catalyst shown below (there is excess ethylene in solution): 1) two ethylene ligand additions (show as one step), 2) oxidative coupling to make a metallacyclopentane, 3) ligand addition, 4) migratory insertion, 5) -hydride elimination, 6) reductive elimination and ligand dissociation.
Ph2 Cl P Me N P Ph2 Cr Cl

2. (a)

Assuming some similarity between the mechanism of hydroformation using HCo(CO)4 and

HRh(CO)(PPh3)3 as catalysts, propose a mechanism for the conversion of RCH=CH2 to RCH2CH2CHO and explain what is happening in each step. (b) The regioselectivity of the hydroformation of RCH=CH2 catalyzed by HRh(CO)(PPh3)3 drops when the temperature is increased. Explain what is meant by this statement. (c) The addition of PPh3 to a solution of Wilkinsons catalyst reduces the turnover frequency for olefin hydrogenation. Give a plausible mechanistic explanation for this effect.

3. (a) Analyze the catalytic cycle shown below and identify the types of reactions occurring. For each Pd centre, show the d-electron count, the valence electron count (EAN), and the oxidation state.

b) Why does this process work best for R = vinyl, benzyl, or aryl groups? When R is vinyl, benzyl, or aryl, there is no -hydrogen present in the R group

4.

The

catalyst

[Rh(Ph2PCH2CH2PPh2)]+

can

be

prepared

by

the

reaction

of

[Rh(nbd)(Ph2PCH2CH2PPh2)]+ with two equivalents of H2 (the structure of nbd is shown at right). In coordinating solvents, [Rh(Ph2PCH2CH2PPh2)]+, in the form of a solvated complex [Rh(Ph2PCH2CH2PPh2)(solv)2]+, catalyzes the hydrogenation of RCH=CH2. a) Draw the structure of [Rh(Ph2PCH2CH2PPh2)]+ and suggest what happens when this complex reacts with H2. b) Draw the structure of [Rh(Ph2PCH2CH2PPh2)(solv)2]+, paying attention to the expected coordination environment of the Rh atom. c) Given that the first step in the mechanism is the substitution of one solvent molecule for the alkene, draw a catalytic cycle that accounts for the conversion of RCH=CH2 to RCH2CH3. Include a structure for each intermediate complex and give the electron count at the Rh center in each complex.

5. Compared to other classes of elements, the d-transition metals are particularly adept in functioning as homogeneous catalysts for a wide range of transformations. Discuss the characteristics of these metals that render them so useful. 6. The original publication on the synthesis and structure of Cp2Fe, ferrocene, showed a 2coordinate Fe centre with two -bonded Cp ligands. With reference to the physical and chemical properties of the molecule, provide an explanation of why Wilkinson and Fischer suspected that this formulation could not be correct? Why did their re-formulated (and correct) interpretation change the way we think about organometallic chemistry? 7. One accepted catalytic cycle for the Monsanto acetic acid process for the production of acetic acid is shown below. (i) Write the overall balanced equation for the synthesis of acetic acid using this process. (ii) For each Rh species, indicate the oxidation state, d-electron count on the metal, and the valence electron count (EAN). (iii) Label each of the steps 14.
CH3COOH MeI

MeOH
Me O I

RhI2(CO)2

CO OC I I Rh

O OC Me
I

CO Rh I Me I

3
CO

O Rh Me CO I I

8. For the molecules dihydrogen (H2), carbon monoxide (CO) and ethene (H2C=CH2), draw the molecular orbitals that are important for the binding of these molecules to a transition metal and illustrate how these orbitals interact with suitable valence orbitals on the metal centre.
9. For the following five metal-ligand combinations, propose a reasonable complex,

consistent with the following: Each complex must contain all specified ligands at least once. The overall charge on the complexes must be neutral. Ligands are shown without charges, so indicate the proper ligand charge in your electron counting. Draw a reasonable structure showing the geometry about the metal center. Clearly show your electron counting. a) Tc, CO c) V, O, Cl e) W, CMe, CH2, CH2SiMe3 10. Olefin hydrogenation catalyzed by transition metal complexes is a tremendously important industrial-scale reaction. a) Draw an accepted catalytic cycle for the hydrogenation of ethylene using Wilkinsons catalyst, indicating the important general classes of reactions seen in each step. b) Indicate a structure, oxidation state, and valence electron count for each metal species in your cycle. c) The rates of H2 gas absorption (in L mol-1 s-1) by alkenes catalyzed by [RhCl(PPh3)3] are: hexane, 2910; cis-methyl-2-pentene, 990; cyclohexene, 3160; 1-methylcyclohexene, 60. Suggest the origin of the trends and identify the reaction step responsible in the cycle. d) 11. Briefly describe what you understand the following common terms to mean: a) The Dewar-Chatt model of olefin bonding to transition metals b) Homogeneous catalyst c) Turnover Frequency d) Agostic interaction b) Fe, Cp, CO d) Ta, NMe, Cl

11. Draw a cycle showing how a metal alkyl species such as Cp2ZrMe2 functions as a catalyst for polymerization of ethylene when treated with the initiator [Ph3C][B(C6F5)4]. Label each step in the cycle. Are there any competing side reactions and, if so, what effect do they have on the properties of the polymer produced?

12. The following interesting reaction was reported in the journal Angewandte Chemie (DOI: 10.1002/anie.200900521).

a) For all three complexes, indicate the oxidation state of the Pt and the valence electron count. b) The Pt starting material is 2-coordinate, yet it is stable. Account for this fact. The bonding interaction between Pt and Be is not the typical one we talked about in class and is not well-described by the simple line drawn between the two. Provide a brief statement describing the nature of this interaction with a particular emphasis on the origin of the bonding electrons. 13. (a) Phosphines are weaker bases than amines. Why then do phosphines (PR3) cause larger crystal field splittings than amines? (b) [W(NMe3)(CO)5] reacts with PF3 to provide [W(PF3)(CO)5]. What is the driving force for this reaction?

14. Provide plausible formulae for the products formed in boxes A-F below, indicating stereochemistry where necessary.
cis-IrCl(CO)(PPh3)2 + H2

(A)

Hf

Cl CH3

+ CO

(B)

CO OC Mn OC CO (Indicate location of labeled (13C) carbon) Me CO +


13CO

(C)

TaCl5 +
(D)

TaCl2Me3 +

(E)

+ 2 MeLi

(F)