Organometallics
Article
(KBr pellet, cm−1): ν(C−O) 2012 (bs); 1939 (bm); 1871(bm). UV−
vis: λmax 557 nm, 0.05 M in CH2Cl2. Anal. (C12H16S6O4Re2) Calcd: C
18.24; S 24.38; H 2.04. Found: C 18.42; S 24.37; H 2.05.
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Computational Methods. Computations were performed on
clusters provided by NC State Office of Information Technology High
Performance Computing. Theoretical calculations have been carried
out using the Gaussian 0928 implementation of the M0619 density
functional theory. All geometry optimizations were carried out in the
gas phase using tight convergence criteria (“opt = tight”) and pruned
ultrafine grids (“Int = ultrafine”). The basis set for rhenium was the
small-core (311111,22111,411) → [6s5p3d] Stuttgart−Dresden basis
set and RECP combination (SDD)29 with an additional f polarization
function.30 The 6-31G(d,p) basis set was used for all other atoms.20
Cartesian d functions were used throughout; that is, there are six
angular basis functions per d function. All structures were fully
optimized and analytical frequency calculations were performed on all
structures to ensure either a zeroth-order saddle point (a local
minimum) or a first-order saddle point (transition state: TS) was
achieved. The minimum associated with each transition state was
determined by animation of the imaginary frequency and, if necessary,
with intrinsic reaction coordinate calculations.
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Energetics were calculated at 298.15 K with the 6-311++G(d,p)23
basis set for C, H, N, O, and F atoms and the SDD basis set with an
added f polarization function on Re. Reported energies utilized
analytical frequencies and the zero-point corrections from the gas
phase optimized geometries and included solvation corrections that
were computed using the SMD model,24 with benzene as the solvent
as implemented in Gaussian 09.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
X-ray experimental data for 2, 3, 4, 6, and 7; full Gaussian
Text file of all computed molecule Cartesian coordinates
in a format for convenient visualization (XYZ)
Crystallographic data (CIF)
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2003, 42, 2362−2367.
(15) See Experimental Section and the Supporting Information for
details on the characterization and isolation of 9.
AUTHOR INFORMATION
Corresponding Author
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We acknowledge North Carolina State University and the
National Science Foundation via the CAREER Award (CHE-
0955636) for funding.
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