Brugia Malayi - Clark Science Center - Smith College
Brugia Malayi - Clark Science Center - Smith College
Brugia Malayi - Clark Science Center - Smith College
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Energetic Comparison of S N<br />
2 Self-Exchange Reactions on<br />
Pentacoordinate Carbon, Silicon, and Tin<br />
Sarah Kay<br />
Though carbons structures have been extensively studied in organic chemistry, relatively little is known about the analogous<br />
silicon or tin structures and whether these elements will behave similarly, given differences in size and nuclear charge. This project<br />
investigated the resultant energy changes when a ligand, XH n-<br />
, displaces an identical ligand from a methyl, silyl, or stannyl center<br />
via an S N<br />
2 mechanism. Using ADF2012 1 many such systems were investigated, in which X is an element from rows 2-5, groups<br />
14-17 of the periodic table. In each system, three structures were examined: the XH n<br />
-<br />
anion, the CH 3<br />
XH n<br />
molecule (or Si or<br />
Sn), and the trigonal bipyramid [XH n<br />
—CH 3<br />
—XH n<br />
] - . The sum of total bonding energies (TBE) for the anion and molecule was<br />
subtracted from the TBE of the overall system, giving the reaction energy from infinite separation of the starting fragments.<br />
The most significant finding is that while the energy change for the methyl-centric system is nearly always positive (a barrier),<br />
the change in both silyl-centric and stannyl-centric systems is consistently negative (energy wells). I.e. the trigonal bipyramid for<br />
SiH 3<br />
and SnHs self-exchange reactions (SER) are stabilizing, while the same structure for CH 3<br />
SER’s is destabilizing. These results<br />
support a paper 2 published by Hoz; starting from a dipole attraction of the initial fragments (rather than infinite separation), Hoz<br />
found that the CH 3<br />
systems are always uphill in energy.<br />
The trends observed show that elements farther to the right in the periodic table (i.e. halides) form the most stable<br />
pentacoordinate systems (for C, Si, and Sn). However, while silicon and tin favor the upper rows (C, N, O, F are best), carbon<br />
shows the smallest barriers with the largest elements (Sn, Sb, Te, I) as ligands. (Supported by <strong>Smith</strong> <strong>College</strong> Committee on Faculty<br />
Compensation and Development)<br />
Advisor: Robert Linck<br />
References:<br />
1 ADF2012, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands, http://www.scm.com. E.J. Baerends, T. Ziegler, J. Autschbach, et al.<br />
2 S. Hoz, H. Basch, J. L. Wolk, T. Hoz, E. Rozental, J. Am. Chem. Soc. 1999. 121, 7724-7725.<br />
2012<br />
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