Electronic Theses and Dissertations

Identifier

1192

Date

2014

Document Type

Thesis

Degree Name

Master of Science

Major

Chemistry

Concentration

Organic Chemistry

Committee Chair

Theodore Johnathan Burkey

Committee Member

Charles Edwin Webster

Committee Member

Xuan Zhao

Abstract

Two alkylated cymantrene derivatives, one disubstituted Mn[η5-C5H3(β-{CH2}6CH3)CH2CO(C5H4N)](CO)3, (4) and one monosubstitutedMn[η5-C5H4CH({CH2}6CH3)CO(C5H4N)](CO)3 (10) have been synthesized and characterized spectroscopically. UV photolysis of 4 and 10 in n-heptane resulted in the formation of chelatesMn[η1:η5-C5H3(β-{CH2}6CH3)CH2CO(2-py- κ-N)](CO)2 (14) andMn[η1:η5-C5H4CH({CH2}6CH3)CO(2-py- κ-N)](CO)2 (16), respectively. Both resultant purple chelates exhibit an N-chelate spectroscopically based on previous analysis ofMn[η1:η5-C5H4CH2CO(2-py- κ-N)](CO)2 (3). TRIR experiments with UV photolyzing (4) in n-heptane yielded a mixture ofMn[η1:η5-C5H3(β-{CH2}6CH3)CH2(CO- κ-O)(2-py)](CO)2 (13) and 14 (O- and N-chelate, respectively) with a greater abundance of 13 within the ns timescale. The opposite is noticed within the ns timescale when 10 is UV-photolyzed in n-heptane (greater abundance of 16 than Mn[η1:η5-C5H4CH({CH2}6CH3)(CO- κ-O)(2-py)](CO)2 15). The rate of conversion of O-chelate 13 to N-chelate 14 (k = 1.6 x 10-2 s-1) is slower than the conversion of O-chelate 15 to 16 (k = 1.2 x 10-3s-1).

Comments

Data is provided by the student.

Library Comment

Dissertation or thesis originally submitted to the local University of Memphis Electronic Theses & dissertation (ETD) Repository.

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