Organometallic Chemistry: Reactions of SO2 Ligands

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What is the final product of the reaction involving 1-butene?

1° alkyl (correct)

Terminal alkene

Internal alkene

2° alkyl

Why is the 1° alkyl thermodynamically more stable than the 2° alkyl?

Electronic reasons

Steric reasons (correct)

Kinetic reasons

Solubility reasons

What can be done with the 1° alkyl after its formation?

It can only be converted to a 2° alkyl

It cannot be functionalized

It can only be converted to a terminal alkene

It can be functionalized in a number of ways (correct)

What is the preferred position of the metal in the LnM–H insertion product for ArCH=CH2?

Benzylic position Signup and view all the answers

Why does the equilibration of the two regioisomers favor the thermodynamic product?

Due to the strength of the newly formed C–H′ bonds Signup and view all the answers

Why is the new C–H′ bond in 7.8 stronger than in 7.7?

Because it is not benzylic Signup and view all the answers

What is the result of 1e oxidation of Cp(CO)2FeIIMe at −78°C in MeCN?

The formation of a 17e, Fe(III) acyl complex Signup and view all the answers

Why is the migration of Me− to the CO carbon expected to be faster in the 17e, Fe(III) acyl complex?

Due to the increased electrophilicity of the oxidized metal Signup and view all the answers

What type of ligands do early d0 metals prefer?

O-donor ligands Signup and view all the answers

What is the role of the solvent in the oxidation of Cp(CO)2FeIIMe?

It acts as a ligand for the metal Signup and view all the answers

What is the effect of the limited back bonding in d0 Zr(IV) and Th(IV) complexes?

It makes the CO more reactive for insertion Signup and view all the answers

What is the outcome of the reaction shown in Eq. 7.17?

The formation of an η2-acyl complex Signup and view all the answers

What is the unique property of SO2 as a ligand?

It can be either an η1 (S) or η2 (S,O) ligand Signup and view all the answers

What is the typical direction of insertion reactions involving SO2?

Forward, with SO2 inserting into M–R bonds Signup and view all the answers

What is the requirement for the cis arrangement of ligands in insertion reactions?

It is required for the insertion reaction Signup and view all the answers

What is the effect of binding an external 2e ligand on the insertion product?

It traps the insertion product Signup and view all the answers

What is the requirement for the elimination reaction to occur?

A 2e vacant site Signup and view all the answers

What is the change in formal oxidation state of the metal during the insertion reaction?

It remains the same Signup and view all the answers

What is the role of the nucleophilic hydride in the reaction involving CO2?

It attacks the carbon of free CO2 to give a 16e M+ unit Signup and view all the answers

What is the difference between the kinetic and thermodynamic products of the reaction involving SO2?

The kinetic product is O-bound sulfinato complex, while the thermodynamic product is S-bound sulfinate Signup and view all the answers

Why does the reactivity of the reaction involving SO2 fall off for bulky alkyls and electron-attracting substituents?

Because the bulky alkyls and electron-attracting substituents increase the steric hindrance and decrease the reaction rate Signup and view all the answers

What is the significance of the crossover reaction of a mixture of RS and SR isomers of [CpFe(CO)L{CH2CH(Me)Ph}]?

It shows that the intermediate must stay ion-paired and the intermediate iron cation must have stereochemical stability Signup and view all the answers

What is the reason for the formation of an alkyl sulfinate ion when SO2 electrophilically attacks the α carbon of an 18e alkyl?

Because the anion has much of its negative charge on the oxygens Signup and view all the answers

What is the type of insertion that occurs when SO2 reacts with an 18e alkyl?

Both 1,1 and 1,2 insertion of SO2 can occur Signup and view all the answers

What is the likely reason why 7.8 is preferred as a product?

The M–C bond in 7.8 is stronger due to back donation from metal dπ orbitals. Signup and view all the answers

What is the outcome of insertion in simple α-olefins?

The insertion can have a mixed regiochemistry. Signup and view all the answers

What happens to the cis-vinyl complex during syn insertion?

It rearranges to the sterically less hindered trans isomer. Signup and view all the answers

Why is the radical formed in 7.8 more stable?

Because it is specially stabilized. Signup and view all the answers

What is the general principle for interpreting reactivity trends?

Considering all the bonds broken and formed. Signup and view all the answers

What type of substituents may exhibit similar trends to –Ar?

A variety of electronegative substituents, such as –CN, –F, and –CHO. Signup and view all the answers

Organometallic Chemistry: Reactions of SO2 Ligands

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Questions and Answers

What is the final product of the reaction involving 1-butene?

Why is the 1° alkyl thermodynamically more stable than the 2° alkyl?

What can be done with the 1° alkyl after its formation?

What is the preferred position of the metal in the LnM–H insertion product for ArCH=CH2?

Why does the equilibration of the two regioisomers favor the thermodynamic product?

Why is the new C–H′ bond in 7.8 stronger than in 7.7?

What is the result of 1e oxidation of Cp(CO)2FeIIMe at −78°C in MeCN?

Why is the migration of Me− to the CO carbon expected to be faster in the 17e, Fe(III) acyl complex?

What type of ligands do early d0 metals prefer?

What is the role of the solvent in the oxidation of Cp(CO)2FeIIMe?

What is the effect of the limited back bonding in d0 Zr(IV) and Th(IV) complexes?

What is the outcome of the reaction shown in Eq. 7.17?

What is the unique property of SO2 as a ligand?

What is the typical direction of insertion reactions involving SO2?

What is the requirement for the cis arrangement of ligands in insertion reactions?

What is the effect of binding an external 2e ligand on the insertion product?

What is the requirement for the elimination reaction to occur?

What is the change in formal oxidation state of the metal during the insertion reaction?

What is the role of the nucleophilic hydride in the reaction involving CO2?

What is the difference between the kinetic and thermodynamic products of the reaction involving SO2?

Why does the reactivity of the reaction involving SO2 fall off for bulky alkyls and electron-attracting substituents?

What is the significance of the crossover reaction of a mixture of RS and SR isomers of [CpFe(CO)L{CH2CH(Me)Ph}]?

What is the reason for the formation of an alkyl sulfinate ion when SO2 electrophilically attacks the α carbon of an 18e alkyl?

What is the type of insertion that occurs when SO2 reacts with an 18e alkyl?

What is the likely reason why 7.8 is preferred as a product?

What is the outcome of insertion in simple α-olefins?

What happens to the cis-vinyl complex during syn insertion?

Why is the radical formed in 7.8 more stable?

What is the general principle for interpreting reactivity trends?

What type of substituents may exhibit similar trends to –Ar?

More Quizzes Like This

Isolable Species in Organometallic Chemistry Quiz

Nomenclature of Organometallic Compounds Quiz

Organometallic Chemistry: Dewar-Chatt and Metalacyclopropane Models

Organometallic Chemistry: Vaska's Complex

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Organometallic Chemistry: Reactions of SO2 Ligands

Podcast Beta

Questions and Answers

What is the final product of the reaction involving 1-butene?

Why is the 1° alkyl thermodynamically more stable than the 2° alkyl?

What can be done with the 1° alkyl after its formation?

What is the preferred position of the metal in the LnM–H insertion product for ArCH=CH2?

Why does the equilibration of the two regioisomers favor the thermodynamic product?

Why is the new C–H′ bond in 7.8 stronger than in 7.7?

What is the result of 1e oxidation of Cp(CO)2FeIIMe at −78°C in MeCN?

Why is the migration of Me− to the CO carbon expected to be faster in the 17e, Fe(III) acyl complex?

What type of ligands do early d0 metals prefer?

What is the role of the solvent in the oxidation of Cp(CO)2FeIIMe?

What is the effect of the limited back bonding in d0 Zr(IV) and Th(IV) complexes?

What is the outcome of the reaction shown in Eq. 7.17?

What is the unique property of SO2 as a ligand?

What is the typical direction of insertion reactions involving SO2?

What is the requirement for the cis arrangement of ligands in insertion reactions?

What is the effect of binding an external 2e ligand on the insertion product?

What is the requirement for the elimination reaction to occur?

What is the change in formal oxidation state of the metal during the insertion reaction?

What is the role of the nucleophilic hydride in the reaction involving CO2?

What is the difference between the kinetic and thermodynamic products of the reaction involving SO2?

Why does the reactivity of the reaction involving SO2 fall off for bulky alkyls and electron-attracting substituents?

What is the significance of the crossover reaction of a mixture of RS and SR isomers of [CpFe*(CO)L{CH2C*H(Me)Ph}]?

What is the reason for the formation of an alkyl sulfinate ion when SO2 electrophilically attacks the α carbon of an 18e alkyl?

What is the type of insertion that occurs when SO2 reacts with an 18e alkyl?

What is the likely reason why 7.8 is preferred as a product?

What is the outcome of insertion in simple α-olefins?

What happens to the cis-vinyl complex during syn insertion?

Why is the radical formed in 7.8 more stable?

What is the general principle for interpreting reactivity trends?

What type of substituents may exhibit similar trends to –Ar?

More Quizzes Like This

Isolable Species in Organometallic Chemistry Quiz

Nomenclature of Organometallic Compounds Quiz

Organometallic Chemistry: Dewar-Chatt and Metalacyclopropane Models

Organometallic Chemistry: Vaska's Complex

What is the significance of the crossover reaction of a mixture of RS and SR isomers of [CpFe(CO)L{CH2CH(Me)Ph}]?