PracticeExam2_Fall2010 - Chem 103 Midterm 2 Prof Chris...

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Chem 103 Midterm 2 Prof. Chris Chang November 4, 2010 Name ____________________________________ SID ____________________________________ Signature ____________________________________ Problem 1: ____________ (42 pts) Problem 2: ____________ (44 pts) Problem 3: ____________ (44 pts) Problem 4: ____________ (44 pts) Problem 5: ____________ (31 pts) Problem 6: ____________ (45 pts) Total: ____________ (250 pts)
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1) MO Theory . (42 points) N 2 O (NNO) is a potent greenhouse gas in the atmosphere that can damage the ozone layer. Methods to sequester and use this potentially toxic molecule are of great interest. Fe- and Cu-containing enzymes bind and reduce N 2 O in plants and bacteria, but chemists have recently found alternative ways to bind this molecule. a) Here is a vanadium tris-pyrrole complex. Assuming all four nitrogens are equivalent in terms of crystal field shape, draw the crystal field, give the oxidation state, and fill in the d electrons. V(tpa Mes ) b) Draw the MO for N 2 O and fill in its electrons. Please label and draw the orbitals.
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c) Using a) and b), construct a partial MO diagram for a linear N-bound V(tpa Mes )(N 2 O) complex. Fill in the electrons. Please label and draw the orbitals. d) Give the total electron count for this N 2 O-bound complex.
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2) Electrochemistry. (44 pts) The electron transfer protein Azurin has been recently modified by Prof. Yi Lu at University of Illinois to change its oxidation-reduction potentials outside the physiological range ( Nature , 2009 ). Here are wildtype (WT) and 2 variants where the Met is changed to two different amino acids, M121Q and M121L. WT M121Q M121L a) What type of copper centers are these (Type I, II, or III)?
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