Journal of the American Chemical Society
Communication
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importantly no combustible gas was collected with a Toepler
pump (200 Torr expected).
The competency of (dppe)Co(COD) as a precatalyst for
alkene hydrogenation was evaluated with α-methylstyrene and
terpinen-4-ol as representative substrates. Complete conversion
with the former was observed in 6 h under the standard
conditions, while for the latter only 34% conversion was obtained
after 2 h likely due to the presence of coordinating diene.
Notably, a 99.1:0.9 diastereomeric ratio was observed suggesting
catalyst activation similar to that for 1 (entry 6b, Table 2).
The mechanism for alkene hydrogenation by bis(phosphine)-
cobalt(II) alkyl complexes involves initial hydrogenolysis of the
alkyl groups to form SiMe4 (observed quantitatively by NMR
spectroscopy) and a thus far unobserved cobalt(II) dihydride.
Fryzuk et al. have reported a related phosphine-ligated cobalt
hydride, [(iPr2P(CH2)3PiPr2)Co]2(H)(μ-H)3,25 from addition
of H2 to the corresponding Co(I) allyl. Subsequent olefin
insertion and reductive elimination of alkane generates a putative
Co(0) species that coordinates alkene. Support for the existence
of such a species is provided by the isolation and catalytic activity
of (dppe)Co(COD). These observations and understanding
provide a platform for future optimization of base metal alkene
hydrogenation catalysts with high diastereo- and enantioselec-
tivity.
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ASSOCIATED CONTENT
* Supporting Information
Experimental details, substrate and product characterization, and
crystallographic data for 1−4 in cif format. This material is
■
S
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AUTHOR INFORMATION
Corresponding Author
Notes
■
(18) Trovitch, R. J.; Lobkovsky, E.; Bouwkamp, M. W.; Chirik, P. J.
Organometallics 2008, 27, 6264.
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V.; Kudinov, A. R. Koord. Khim. (Russ. J. Coord. Chem.) 2010, 36, 795.
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2013, 52, 2446.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the U.S. National Science Foundation (NSF) for a
Grant Opportunities for Academic Liaison with Industry
(GOALI) grant (CHE-1265988) between Princeton and
Merck. M.R.F. thanks the NSF for a Graduate Research
Fellowship (DGE-1148900). We also thank Z. R. Turner and
S. P. Semproni for assistance with X-ray crystallography, Prof. C.
Milsmann for assistance with EPR spectroscopy, and R. P. Yu for
assistance with Toepler pump experiments.
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