Organometallic Chemistry: Reactions of SO2 Ligands
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Questions and Answers

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?

    <p>Benzylic position</p> Signup and view all the answers

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

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

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

    <p>Because it is not benzylic</p> Signup and view all the answers

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

    <p>The formation of a 17e, Fe(III) acyl complex</p> 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?

    <p>Due to the increased electrophilicity of the oxidized metal</p> Signup and view all the answers

    What type of ligands do early d0 metals prefer?

    <p>O-donor ligands</p> Signup and view all the answers

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

    <p>It acts as a ligand for the metal</p> Signup and view all the answers

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

    <p>It makes the CO more reactive for insertion</p> Signup and view all the answers

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

    <p>The formation of an η2-acyl complex</p> Signup and view all the answers

    What is the unique property of SO2 as a ligand?

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

    What is the typical direction of insertion reactions involving SO2?

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

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

    <p>It is required for the insertion reaction</p> Signup and view all the answers

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

    <p>It traps the insertion product</p> Signup and view all the answers

    What is the requirement for the elimination reaction to occur?

    <p>A 2e vacant site</p> Signup and view all the answers

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

    <p>It remains the same</p> Signup and view all the answers

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

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

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

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

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

    <p>Because the bulky alkyls and electron-attracting substituents increase the steric hindrance and decrease the reaction rate</p> 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{CH2C*H(Me)Ph}]?

    <p>It shows that the intermediate must stay ion-paired and the intermediate iron cation must have stereochemical stability</p> 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?

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

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

    <p>Both 1,1 and 1,2 insertion of SO2 can occur</p> Signup and view all the answers

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

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

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

    <p>The insertion can have a mixed regiochemistry.</p> Signup and view all the answers

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

    <p>It rearranges to the sterically less hindered trans isomer.</p> Signup and view all the answers

    Why is the radical formed in 7.8 more stable?

    <p>Because it is specially stabilized.</p> Signup and view all the answers

    What is the general principle for interpreting reactivity trends?

    <p>Considering all the bonds broken and formed.</p> Signup and view all the answers

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

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

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