ACS Catalysis
Page 10 of 12
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publications dealing with Co-catalyzed hydrosilylations have since
appeared (ref 2a-d).
ACKNOWLEDGMENT
(9) PDI and related redox-active ligands have a long history in
cobalt-mediated polymerization and hydrofunctionalization
reactions: (a) Small, B. L.; Brookhart, M.; Bennett, A. M. A. J. Am.
Chem. Soc. 1998, 120, 4049-4050. (b) Britovsek, G. J. P.; Bruce,
M.; Gibson, V. C.; Kimberley, B. S.; Maddox, P. J.; Mastroianni,
S.; McTavish, S. J.; Redshaw, C.; Solan, G. A.; Strömberg, S.;
White, A. J. P.; Williams, D. J. J. Am. Chem. Soc. 1999, 121, 8728-
8740.
(10) For reactivity and applications of PDI ligands in
hydrofunctionalization reactions, see: (a) Zhu, D.; Thapa, I.;
Korobkov, I.; Gambarotta, S.; Budzelaar, P. H. M. Inorg. Chem.
2011, 50, 9879-9887. (b) Bart, S. C.; Chłopek, K.; Bill, E.;
Bouwkamp, M. W.; Lobkovsky, E.; Neese, F.; Wieghardt, K.;
Chirik, P. J. J. Am. Chem. Soc. 2006, 128, 13901-13912. (c)
Tondreau, A. M.; Atienza, C. C. H.; Weller, K. J.; Nye, S. A.;
Lewis, K. M.; Delis, J. G. P.; Chirik, P. J. Science 2012, 335, 567-
570. (d) Obligacion, J. V.; Chirik, P. J. J. Am. Chem. Soc. 2013,
135, 19107-19110. See also ref 2c and 2f.
(11) See Supporting Information for details. Data for full
characterization of the products and gas chromatographic analysis
of products of key reactions are included there.
(12) See Supporting Information for the effect of various
activators on the selectivity of hydrosilyaltion of 1,3-dienes (Table
S1).
(13) For the effect of solvents, the counter ions and experimental
parameters, see Supporting Information for details (Tables S2 and
S3).
(14) Raya, B.; Biswas, S.; RajanBabu, T. V. ACS Catal. 2016, 6,
6318-6323.
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Authors thank Vagulejan Balasanthiran of this department for
providing some of the (PDI)CoCl complexes and for some
early NMR experiments using these complexes. Financial
assistance for this research provided by US National Science
Foundation CHE-1362095 and NIH (R01 GM108762).
References
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(1) For recent reviews, see: (a) Sun, J.; Deng, L. ACS Catalysis
2016, 6, 290-300. (b) Nakajima, Y.; Shimada, S. RSC Adv. 2015, 5,
20603-20616. (c) Greenhalgh, M. D.; Jones, A. S.; Thomas, S. P.
ChemCatChem 2015, 7, 190-222. (d) Chirik, P. J. In Catalysis
without Precious Metals; Bullock, R. M., Ed.; Wiley-VCH:
Weinheim, Germany, : 2010, pp 83-110. (e) Hydrosilylation: A
Comprehensive Review on Recent Advances; Marciniec, B., Ed.;
Springer: Berlin, 2009.
(2) For representative examples of recent contributions from
various research groups, see the following references and others
cited there in: Cobalt-catalysis: (a) Du, X.; Zhang, Y.; Peng, D.;
Huang, Z. Angew. Chem. Int. Ed. 2016, 55, 6671-6675. (b)
Ibrahim, A. D.; Entsminger, S. W.; Zhu, L. Y.; Fout, A. R. ACS
Catal. 2016, 6, 3589-3593. (c) Schuster, C. H.; Diao, T.; Pappas, I.;
Chirik, P. J. ACS Catal. 2016, 6, 2632-2636. (d) Noda, D.; Tahara,
A.; Sunada, Y.; Nagashima, H. J. Am. Chem. Soc. 2016, 138, 2480-
2483. (e) Chen, C.; Hecht, M. B.; Kavara, A.; Brennessel, W. W.;
Mercado, B. Q.; Weix, D. J.; Holland, P. L. J. Am. Chem. Soc.
2015, 137, 13244-13247. (f) Atienza, C. C. H.; Diao, T.; Weller, K.
J.; Nye, S. A.; Lewis, K. M.; Delis, J. G. P.; Boyer, J. L.; Roy, A.
K.; Chirik, P. J. J. Am. Chem. Soc. 2014, 136, 12108-12118. (g)
Mo, Z.; Liu, Y.; Deng, L. Angew. Chem. Int. Ed. 2013, 52, 10845-
10849. (h) Brookhart, M.; Grant, B. E. J. Am. Chem. Soc. 1993,
115, 2151-2156. Iron: (i) Sunada, Y.; Noda, D.; Soejima, H.;
Tsutsumi, H.; Nagashima, H. Organometallics 2015, 34, 2896-
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(o) Tondreau, A. M.; Atienza, C. C. H.; Weller, K. J.; Nye, S. A.;
Lewis, K. M.; Delis, J. G. P.; Chirik, P. J. Science 2012, 335, 567-
570. Nickel: (p) Srinivas, V.; Nakajima, Y.; Ando, W.; Sato, K.;
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(3) (a) Lappert, M. F.; Nile, T. A.; Takahashi, S. J. Organomet.
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(15) See ref 2f, esepcially, Supporting Information of this
reference, p S8. We have repeated these experiments and looked at
ligand effects in the reactions of (TMSO)2Si(Me)H with alkenes.
As reported2f only dehydrogenative hydrosilylation and reduction
were observed under these conditions. See Table S4 and pages
S143-S145 in the Supporting Information for details. However, in
sharp contrast, a 1:1 mixture of PhSiH3 and 1-octene in toluene
i-
mixed in the presence of 15 (Z = Me) [or the corresponding
Pr(PDI)Co-Me] and subsequently stirred to room temperature gives
exclusive hydrosilylation giving 17a and 18a in a ratio of 10:90 in ~
85% yield (See Supporting Information
p S138-S142). No
dehydrogenative silylation was observed under these conditions for
PhSiH3. This unusual dependence on silane in these reactions on
hydrosilylation vs dehydrogenative silylation, and, the reversal in
regioselectivity in hydrosilylation are currently under investigation.
(16) These studies were originally done with 1-octene and 4-
methylstyrene as model substrates. See supporting Information for
detailed Tables showing the effect of various parameters on the
selctivity of this reaction.
(17) (a) Tellmann, K. P.; Humphries, M. J.; Rzepa, H. S.;
Gibson, V. C. Organometallics 2004, 23, 5503-5513.
(b)
Knijnenburg, Q.; Horton, A. D.; Heijden, H. v. d.; Kooistra, T. M.;
Hetterscheid, D. G. H.; Smits, J. M. M.; Bruin, B. d.; Budzelaar, P.
H. M.; Gal, A. W. J. Mol. Catal. A. Chem. 2005, 232, 151-159.
(18) See Supporting Information (Table S5) for the effect of
temperature, stoichiometry of reagents and reaction conditions on
the distribution of products (dehydrogenative silylation,
hydrosilylation and reduction) in the reactions of (TMSO)2Si(Me)H
with 1-octene. .
(19) Gibson, V. C.; Humphries, M. J.; Tellmann, K. P.; Wass, D.
F.; White, A. J. P.; Williams, D. J. Chem. Commun. 2001, 2001,
2252-2253.
(20) This catalyst facilitates the anti-Markovnikov addition of
PhSiH3, Ph(Me)SiH2, Ph2SiH2 and Et3SiH to various alkenes in
>95% yield. These results will be reported separately. Lewis-acid-
catalyzed addition of silanes to alkenes is a well-established
reaction that requires high catalysts loading and works most
efficiently for tertiary silanes (Rubin, M.; Schweir, T.; Gevorgyan,
(5) Wu, J. Y.; Stanzl, B. N.; Ritter, T. J. Am. Chem. Soc. 2010,
132, 13214-13216.
(6) Parker, S. E.; Borgel, J.; Ritter, T. J. Am. Chem. Soc. 2014,
136, 4857-4860. A lone example of 1,2-addition of PhSiMe2H to
isoprene was published while we were preparing this manuscript.
See ref. 2b.
(7) (a) Timsina, Y. N.; Sharma, R. K.; RajanBabu, T. V. Chem.
Sci. 2015, 6, 3994-4008. (b) Biswas, S.; Page, J. P.; Dewese, K. R.;
RajanBabu, T. V. J. Am. Chem. Soc. 2015, 137, 14268-14271.
(8) These results were first reported at the 251st National ACS
Meeting in San Diego, March 2016, Abstract ORGN 427. Several
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