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# PRIN OF ORGANIC CHE CHE 538

UK

GPA 3.91

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This 4 page Study Guide was uploaded by Michelle Gulgowski DVM on Friday October 23, 2015. The Study Guide belongs to CHE 538 at University of Kentucky taught by Staff in Fall. Since its upload, it has received 42 views. For similar materials see /class/228302/che-538-university-of-kentucky in Chemistry at University of Kentucky.

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Date Created: 10/23/15

Study Guide CHE538 Chapters 4 5 6 11 Chapters 45 1 By examination can you tell me how many pielectrons there are in the following systems 2 3 Why do we do molecular orbital calculations What should MO calculations be able to tell us regarding the chemistry andor the spectra of molecules ANSWER everything The occupied unoccupied occupied occupied orbital interactions are the basis of ALL observables in chemistry Are you still satisfied with your answer for 2 above Do you know how to set up the secular determinants for any pielectron LCAO linear combination of atomic orbitals in any molecule Can you solve simple secular determinants Can you use these solutions to make statem ents about the resonance energy of the molecule Resonance energy is a comparison between the energy of the system and a similar system of isolated porbitals or the gains that the system makes in bonding and stability compared to ethene depending on how the question is framed Can you use 0V or C2 to simplify the calculations of the MOs of ethene and of allyl Do you understand the use 0V or Q for S cis or Slrans conformers of butadiene to simplify the calculation of the M05 and the coefficients of butadiene We are not as much interested in the right answer here but more interested in your understanding of the role that symmetry can play in MO theory See the benzene example in the lecture notes The FrostHuckel mnemonic is rather powerful Can you use it to get the energies of linear and cyclic aromatic systems Can you calculate the Huckel coefficients from the solutions of the secular determinant What does resonance energy have to do with rule 239 electrons are more stable in bigger orbitals 1 1 Why are conjugated systems more stable HINT quot 39 39 39 of and of bonding Can you use the coef cients of the MOs to estimate barriers to rotation bond order electron density spin density and or atomic charge Can you identify nonalternate alternate even alternate and odd alternate carbon systems Can you use the properties of alternate hydrocarbons to simplify the calculation of their corresponding HOMOs See Carroll p 200204 Can you define the term stationary state in terms of atomic coordinates Can you define transition state in terms of atomic coordinates HINT perhaps a derivative of atomic coordinates with respect to energy Study Guide CHE538 Chapters 4 5 6 ll 15 21 22 23 24 25 26 27 On what do we base an operational definition of the word intermediate Is an intermediate in a reaction pathway a stationary state Why do we need an operational definition of the intermediate HINT Defined by lifetime and vibrational spectroscopy See notes How can IR spectroscopy operationally define a reactive intermediate Establishing a mechanism for a reaction involves identifying unstable stationary states on the reaction pathway and talking about the nature of the transition states that connect them Why is kinetic theory so important to this exercise Can you calculate the number of vibrational modes in any molecule HINT 3N6 or 3N5 Reactions occur along vibrational modes This limits the rate of reactions From the kinetic theoretical argument can you see that the equation connecting transition state energy to rate constant has two parts One part is derived from the stationary components of the molecule undergoing transformation The other is derived from the fact that reactions occur along vibrational modes Know the relationship between rate constant change in energy to closest stationary state and life time Know the relationship between frequency and life time and how it applies to any form of spectroscopy and tri energies of the transitions in the spectroscopies Can you calculate the molarity of water 5556 M from its density 1 gcm3 and molecular weight 18 gmol This equation is so important I think you should commit it to memory kR kThe39m QT From here you can derive similar equations that take entropy and enthalpy into account From here you can derive the relationship between energy and the equilibrium constant HINT equilibrium is the ratio of at least two rate constants The above assumes J quot quot39 and J quot quot39 stipulates the above Why httpenwikipediaorgwikiMicroscopicireversibili Often you hear people say that kinetics and thermodynamics have nothing to do with each other Or you might hear that is a kinetic argument but it is a thermodynamic problem that we are talking about How does the Hammond postulate connect thermodynamic and kinetic arguments What is the CurtinHammett principle Does it contradict the Hammond postulate If it agrees with Hammond postulate how does it agree with the Hammond postulate How are the CurtinHamm ett principle and the Hammond postulate related Why are triplet carbenes radicals and anions so configurationally stable whereas cations and singlet carbenes so prone to rearrangement Given the half life of a unimolecular process can you calculate the rate constant The product ratio re ects directly two competing rates If I give you product ratios of an intramolecular cyclization versus an intermolecular H transfer as a function of concentration of a Study Guide CHE538 Chapters 4 5 6 11 hydrogen atom donor do you think you could calculate the rate constant of the unim olecular process I would also have to give you the intermolecular H transfer rate constant 29 Do you understand the statement the nonclassical carbocation is the classical carbocation s transition state of the 12shift We calculate that the transition state is stable why should it not be an intermediate stationary Chapter 11 is very connected to chapter 4 30 The concepts of bond order and their relationship to the MO coefficient is important to keep in m ind 31 The reliance of MOs on symmetry is another common thread between the two chapters We focused on symmetry in che538 32 In chapter 4 we grouped orbitals by symmetry and mixed them to produce symmetric and asymmetric orbitals 33 In chapter ll we considered the nature of M05 as a molecule goes from reactant to transition state to product The premise was that symmetry was conserved and that the MOs could not change symmetry willy nilly on the y a Speaking of symmetry the Frost diagram resurfaces on p 783 in Carroll b At the beginning of the class we classified objects and molecules according to symmetry 34 Concerted reactions elementary steps 35 Suprafacial antarafacial conrotatory disrotatory a Know what these are and how they relate to frontier orbitals b What do these adjectives have to do with the number of electrons in the structure c How and in what context do these descriptors relate to the aromatic and antiaromatic d Can you predict and explain the stereochemical result of a sigm atropic reaction i In terms of frontier orbitals ii In terms of Tstate aromatic or antiarom atic character iii In terms of symmetry correlated M05 36 Hopefully you can appreciate the importance of a theory that globally encompasses all the reactions at the top of p 715 in Carroll a The same theory covers the photochemical processes that we did not read in Chapter 12 b The same theory covers many elemental reactions involving heteroatoms in which our first thought might not be sigm atropic rearrangement c We touched on photochemical processes in MO symmetry correlation diagrams i In the first excited state some groundstate symmetryforbidden transformations become allowed 37 Can you count the number of electrons involved in a chemical transformation a From there you predict the stereochemistry etc Study Guide CHE538 Chapters 4 5 6 11 Chapter 6 runs through a laundry list of mechanistic tools to use to probe chemical mechanism You need to think about these and when and how to possibly apply them 47 Crossover experiments Isotopic Labeling Determination of AH and AS Synthesize the intermediate under the reaction conditions Calculations Synthesis of intermediates Stereochemical labels Molecularity Kinetic Isotope Effects KIE a A rich argument needing an understanding of dynamic processes b When might you expect to see an inverse KIE Linear free energy relationship a You should look into this but it will not be on this exam

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