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(a) Sketch the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) on the basis of the calculation (b) Assuming that 1 were to react with an electrophile, where is the most likely site of attack Compare the Lewis basicity of 1 to that of ethylene (c) Assuming that 1 were to react with a nucleophile, where is the most likely site of attack Compare the Lewis acidity of 1 to that of ethylene (d) In terms of j j, estimate the energy of the lowest p p electronic excitation of 1 Is the p p state likely to be higher or lower than the n p state Explain in less than three lines (e) Calculate the p bond order of the C2 C3 bond of 1.



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What is the net charge on O1 (f ) Show the most likely product from a Diels Alder reaction of 1 with 1,3butadiene Pay attention to all relevant aspects of stereo- and regioselectivity Answer There are a number of questions of this type which are primarily concerned with the interpretation of the results of MO calculations and their relationship with the ideas of orbital interaction theory The data are derived from a calculation using SHMO (a) Pentadienone 1 has six p electrons A ``sketch'' of the frontier MOs is shown in Figure B51 The relative sizes of the atomic orbital are proportional to the sizes of the MO coe cients and the relatives phases are shown by shading.





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The convention is adopted that a positive signed coe cient corresponds to a p orbital with the unshaded lobe up and a negative coe cient is portrayed by a p orbital with the shaded lobe up The actual convention you use is unimportant, but you must be consistent (b) Attack by an electrophile will be directed to the part of the HOMO which has the largest coe cient, in this case, atom 3 Atom 6 is a close second Basicity relative to ethylene is governed by the relative energy of the HOMO and by the relative magnitudes of the largest coe cients The HOMO is substantially higher, suggesting greater basicity, but the largest coe cient (055) is smaller.

Figure 12-2

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(a) Discuss the electronic structure of each intermediate in terms of the orbitals involved. (b) Show a plausible geometry for the transition state for the disproportionation step, according to orbital interaction theory. (c) What additional features emerge from the study by Rautenstrauch et al. (Rau tenstrauch, V.; Megard, P.; Bourdin, B.; Furrer, A., J. Am. Chem. Soc., 1992, 114, 1418) on the reduction of camphors with potassium in liquid ammonia (d) Present a brief summary of stereochemical considerations in metal reductions of carbonyls as deduced in the theoretical study of Wu and Houk (Wu, Y.-D.; Houk, K. N., J. Am. Chem. Soc., 1992, 114, 1656). 9. Hahn and le Noble have discovered strongly enhanced stereoselectivity in the reduction of 5-substituted adamantanones where the substitution at C5 is by positive nitrogen (Hahn, J. M.; le Noble, W. J., J. Am. Chem. Soc., 1992, 114, 1916). Thus EaZ ratios for borohydride reduction of compounds 1 3 were in the range 20 25. Suggest a possible reason for these observations on the basis of orbital interaction theory.

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1. List in order from highest to lowest the upper layers of the OSI model, also indicating their layer number. Application Layer Layer 7 Presentation Layer Layer 6 Session Layer Layer 5 2. An application that runs on a user s workstation and communicates over a network with an appropriate application that is running on a server is considered to be what type of application Client/server 3. Which protocol is considered to be a connection-based protocol TCP (Transmission Control Protocol) 4. What functionality can be used to disguise addresses from a private address space to be seen on the Internet NAT (Network Address Translation) 5. List the three private address spaces that may be used and are considered to be not routable over the Internet. 10.X.X.X 172.16.X.X 192.168.X.X 6. Name an Application layer protocol that can be used to perform le transfers over the network. FTP (File Transfer Protocol) 7. What is the protocol that resolves IP addresses to hardware addresses ARP (Address Resolution Protocol)

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