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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 />

76

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