Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M
- Award ID(s):
- 1664580
- NSF-PAR ID:
- 10035606
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Israel Journal of Chemistry
- Volume:
- 57
- Issue:
- 10-11
- ISSN:
- 0021-2148
- Page Range / eLocation ID:
- 982 to 989
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The RSSH + H 2 S → RSH + HSSH reaction has been suggested by numerous labs to be important in H 2 S-mediated biological processes. Seven different mechanisms for this reaction (R = CH 3 , as a model) have been studied using the DFT methods (M06-2X and ωB97X-D) with the Dunning aug-cc-pV(T+d)Z basis sets. The reaction of CH 3 SSH with gas phase H 2 S has a very high energy barrier (>45 kcal mol −1 ), consistent with the available experimental observations. A series of substitution reactions R 1 –S–S–H + − S–R 2 (R 1 = Me, t Bu, Ad, R 2 = H, S–Me, S– t Bu, S–Ad) have been studied. The regioselectivity is largely affected by the steric bulkiness of R 1 , but is much less sensitive to R 2 . Thus, when R 1 is Me, all − S–R 2 favorably attack the internal S atom, leading to R 1 –S–S–R 2 . While for R 1 = t Bu, Ad, all − S–R 2 significantly prefer to attack the external S atom to form − S–S–R 2 . These results are in good agreement with the experimental observations.more » « less
