Title
The synthesis and characterization of new metallaborane and carborane derivatives on the way to novel nonlinear optical materials and molecular nanosystems
Date of Award
2001
Degree Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
Advisor(s)
James T. Spencer
Keywords
Metallaborane, Carborane, Nonlinear optical, Molecular nanosystems
Subject Categories
Chemistry | Organic Chemistry | Physical Sciences and Mathematics
Abstract
The work described here consists of the synthesis and characterization of new borane cluster compounds, including large metallaboranes and substituted carboranes that are intermediates to new nonlinear optical materials and molecular nanosystems.
The first chapter of this work describes the synthesis of two new nineteen-vertex metallaborane compounds, [(CH 3 ) 4 N][B 18 H 20 Ni(η 5 -C 5 H 5 )] ( 1.4b ) and [B 18 H 19 (2-THF)Ni(η 5 -C 5 H 5 )] ( 1.5 ). The reaction of anti -B 18 H 22 with nickelocene affords the new compounds 1.4b and 1.5 . Complete spectroscopic analysis and a single crystal X-ray study are reported and discussed for both compounds. This chapter also contains a discussion of the synthesis and spectroscopic characterization of the first exo -bound organometallic fragment to an anti -B 18 H 22 cluster, [9-(Fe(CO) 2 (η 5 -C 5 H 5 )) anti -B 18 H 21 ] ( 1.3 ). Also presented are some photochemical reactions of these non- closo macropolyhedral metallaborane clusters.
The synthesis and complete characterization of a new linked bis- ortho -carborane species, 1,1 ' -bis( ortho -carborane)-3-fluorenol ( 2.3 ), is reported in the second chapter of this work. The synthesis of compound 2.3 begins with bis- ortho -carborane, which is first deprotonated and then reacted with methyl formate to afford 1,1 ' -bis( ortho -carborane)-3-fluorenol ( 2.3 ). The complete spectroscopic characterization and the X-ray crystal structure of 2.3 are reported here. This new compound contains a five-membered ring that is comprised completely of carbon atoms.
The third chapter of this work discusses the synthesis and characterization of a series of compounds that should lead to the preparation of new boron-based nonlinear optical materials with para -carborane as the primary structural unit. Complete spectroscopic characterization is presented for six previously unknown substituted para -carborane compounds, including: [1-(1-C 7 H 7 )-12-(H)-C 2 B 10 H 10 ] ( 3.3 ), [1-(1-C 7 H 7 )-12-(C 5 H 4 -1-(OH)-3,4-(CH 3 ) 2 )-C 2 B 10 H 10 ] ( 3.5 ), [1-(1-C 7 H 7 )-12-(C 5 H 3 -3,4-(CH 3 ) 2 )-C 2 B 10 H 10 ] ( 3.6 ), [1-(4-C 7 H 7 )-12-(C 5 H 3 -3,4-(CH 3 ) 2 )-C 2 B 10 H 10 ] ( 3.7 ) [1-(4-C 7 H 7 )-12-(C 5 H 2 -3-(CN)-3,4-(CH 3 ) 2 )-C 2 B 10 H 10 ] ( 3.10 ), and [1-(4-C 7 H 7 )-12-(C 5 H-3,5-(CN) 2 -3,4-(CH 3 ) 2 )-C 2 B 10 H 10 ] ( 3.11 ). The X-ray crystal structure analyses of compounds 3.3 , 3.7 , and 3.10 , are also provided in this chapter.
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Recommended Citation
Taylor, Jesse W., "The synthesis and characterization of new metallaborane and carborane derivatives on the way to novel nonlinear optical materials and molecular nanosystems" (2001). Chemistry - Dissertations. 83.
https://surface.syr.edu/che_etd/83
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