Inorganic Chemistry
ARTICLE
on which of the two C atoms on propene receives the H atom
formerly on the metal during alkene insertion. While it should be
possible to identify CD H on the basis of its infrared spectrum,
V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui,
Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.;
Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith,
T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.;
Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.;
Pople, J. A. Gaussian 03, revision D.01; Gaussian, Inc.: Wallingford, CT,
2
2
the complexity of the potential propane isotopomers and their
very similar spectra in the CꢀH and CꢀD absorption regions
makes the current analysis difficult at best when considered with
the wealth of propene precursor features in the same areas. Thus,
while a full mechanistic investigation involving careful isotopic
substitution should be possible, it would require a substantial
investigation in order to confirm the geometric details of the
latter part of this mechanism.
2004.
(9) We isolated CO, CO , CH , and CD in Ar as reference
2 4 4
standards in our own laboratory in this experimental system and
observed these wavenumber values using the FTIR apparatus
described here.
(
10) Gough, K. M.; Baudais, F. L.; Casal, H. L. J. Chem. Phys. 1986,
4, 549.
11) Data obtained from CRC Handbook of Chemistry and Physics,
70th ed.; Weast, R. C., Ed. in Chief; CRC Press: Boca Raton, FL,
8
’
SUMMARY AND CONCLUSIONS
(
The nature of V-atom reactivity with propene evolves as the
1
1
1
5
989ꢀ1990.
12) Andrews, D. C.; Davidson, G. J. Chem. Soc. Dalton Trans. 1972,
3, 1381.
concentration of propene is increased. Under low partial-pres-
sure conditions, a CꢀH bond insertion intermediate is observed,
which is consumed with increasing partial pressures of propene
to yield a hydrogenation product, propane. Additionally, under
high propene concentration, products consistent with CꢀC
bond cleavage appear to occur, as evidenced by the formation
(
(13) Davidson, G.; Andrews, D. C. J. Chem. Soc., Dalton Trans. 1972,
, 126.
(14) Andrews, D. C.; Davidson, G. J. Organomet. Chem. 1973,
5, 383.
of CH at high propene partial pressures. Given the current
4
(15) Andrews, D. C.; Davidson, G. J. Organomet. Chem. 1977,
results, the only viable mechanism is one in which the final
V-containing products are small, highly symmetric species that
are unobserved under the present conditions. Otherwise, the
mechanism and product distribution are very similar to pre-
viously reported observations wherein ethene is analogously
hydrogenated sacrificially.
124, 181.
(16) Chensdaya, T. B.; Leites, L. A.; Aleksanyan, V. T. J. Organomet.
Chem. 1978, 148, 85.
(
(
17) Li, X.; Wang, L.-S. J. Chem. Phys. 1999, 111, 8389.
18) Gupta, S. K.; Gingerich, K. A. J. Chem. Phys. 1981, 74, 3584.
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ASSOCIATED CONTENT
S
Supporting Information. This material is available free
b
of charge via the Internet at http://pubs.acs.org.
’
AUTHOR INFORMATION
Corresponding Author
*E-mail: mparnis@trentu.ca.
’
REFERENCES
(
1) See, for example: (a) Crabtree, R. The Organometallic Chemistry
of the Transition Metals, 4th ed.; John Wiley & Sons, Inc.: Hoboken, NJ,
005. (b) Cotton, F. A., Wilkinson, G. Advanced Inorganic Chemistry, 5th
2
ed.; Wiley: New York, 1988. (c) Gates, B. C. Catalytic Chemistry; John
Wiley & Sons, Inc.: Hoboken, NJ, 1992.
(
2) Thompson, M. G. K.; Parnis, J. M. J. Phys. Chem. A. 2005,
109, 9465.
(
(
(
3) Cho, H.-G.; Andrews, L. J. Phys. Chem. A. 2007, 111, 5201.
4) Thompson, M. G. K.; Parnis, J. M. Inorg. Chem. 2008, 47, 4045.
5) Ritter, D.; Carroll, J. J.; Weisshaar, J. C. J. Phys. Chem. 1992,
9
9
6, 10636.
(
(
6) Senba, K.; Matsui, R.; Honma, K. J. Phys. Chem. 1995, 99, 13992.
7) Song, L.; Freitas, J. E.; El-Sayed, M. A. J. Phys. Chem. 1990,
4, 1604.
8) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
(
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson,
G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda,
R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai,
H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken,
V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.;
Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski,
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dx.doi.org/10.1021/ic200934r |Inorg. Chem. 2011, 50, 7317–7323