Inorganic Chemistry
Communication
Scheme 1. Proposed Pathway for Hydrolysis of Silanes
Catalyzed by [RhCl(CO)2]2
rate of H2 evolution by a Hiden Analytic HPR20 mass
spectrometer.
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(
Figure 4S in the SI). The second-order kinetics and large
⧧
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(
(
THF)RhCl(CO) with silane to form (THF)(CO) ClRhH-
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silyl) might be the rate-determining step in the catalytic cycle.
An alternate pathway has been proposed for alcoholysis of
+
silanes by Crabtree’s group in which [Et SiOHMe] was formed
and the step of formation of final products was supposed to be
the rate-determining step. In our system, if the analogous
3
16
+
(6) (a) Jeon, M.; Han, J.; Park, J. ACS Catal. 2012, 2, 1539−1549.
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H OR Si] was formed through internal water attack, it should
2 3
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6
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2
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2 2
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(
2
ASSOCIATED CONTENT
(
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*
S
Supporting Information
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AUTHOR INFORMATION
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2578−2592.
(12) The Si−H coupling constant is 370 Hz in free HSiCl .
3
*
(13) Schubert, U. Adv. Organomet. Chem. 1990, 30, 151−187.
̈
̈
(14) Schubert, U.; Scholz, G.; Muller, J.; Ackermann, K.; Worle, B.;
Notes
Stansfield, R. F. D. J. Organomet. Chem. 1986, 306, 303−326.
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The authors declare no competing financial interest.
(
2
ACKNOWLEDGMENTS
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(
This work was suppored by the Natural Science Foundation of
China (Grants 21171012 and J1030413). We thank Prof.
Haichao Liu and Xiaohui He for their help in monitoring the
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dx.doi.org/10.1021/ic402022v | Inorg. Chem. 2013, 52, 10741−10743