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An alternative mechanism of BH2SH formation in the reaction of B2H6 with SH2: concerted elimination of BH3 and H2 from H2S ·B2H6. Ab initio MO study

✍ Scribed by Alexander M. Mebel; Djamaladdin G. Musaev; Keiji Morokuma

Publisher
Elsevier Science
Year
1993
Tongue
English
Weight
411 KB
Volume
216
Category
Article
ISSN
0009-2614

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✦ Synopsis

An alternative mechanism of mercaptoborane, BH,SH, formation is proposed for the reaction of BzHs with SH2. It involves concerted elimination of BH3 and H2 from the H2SB2Hs complex and the highest energy on the pathway relative to SH, + B2H6 is 27.4 kcal/mol at MP4(SDTQ)/6-31 +G(2d, p)//MP2(FULL)/6_3lG(d) level with zero-point energy corrections, which is lower than those for the reaction pathways involving H2 elimination from SH,(BH,), and BH$HI and makes it the most favorable path for BH,SH formation at lower temperatures. At high temperatures ( > 200°C) the entropy factor destabilizes the new transition structure, and the mechanism with BHs.SH2 formation followed by Hz elimination is more favorable according to the Gibbs free energy criterion.

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