Dalton Transactions
Paper
monitor the reaction using ESI-MS. Confidence in the quality 15 D. M. Chisholm and J. Scott McIndoe, Dalton Trans., 2008,
and reliability of the data so obtained is enhanced by the excel- 3933–3945.
lent matches between experimental data and that obtained by 16 D. M. Chisholm, A. G. Oliver and J. S. McIndoe, Dalton
numerically modelling the reaction based on a well-estab- Trans., 2010, 39, 364–373.
lished mechanism. Both the model and the experimental data 17 P. Chen, Angew. Chem., Int. Ed., 2003, 42, 2832–2847.
responded in the same way to perturbations to the concen- 18 S. Torker, D. Merki and P. Chen, J. Am. Chem. Soc., 2008,
tration of free phosphine, which predictably slows the reaction
given that the turnover-limiting step involves dissociation of 19 N. Shankaraiah, W. A. da Silva, C. K. Z. Andrade and
the phosphine from Wilkinson’s catalyst to generate the un- L. S. Santos, Tetrahedron Lett., 2008, 49, 4289–4291.
saturated, 14-electron complex that rapidly oxidatively adds 20 F. Avila-Salas, C. Sandoval, J. Caballero, S. Guiñez-Molinos,
130, 4808–4814.
hydrogen.
L. S. Santos, R. E. Cachau and F. D. González-Nilo, J. Phys.
Chem. B, 2012, 116, 2031–2039.
21 L. S. Santos, Eur. J. Org. Chem., 2008, 2008, 235–253.
22 A. Kamal, N. Markandeya, N. Shankaraiah, C. R. Reddy,
S. Prabhakar, C. S. Reddy, M. N. Eberlin and L. Silva
Santos, Chem.–Eur. J., 2009, 15, 7215–7224.
23 M. Eberlin, Eur. J. Mass. Spectrom., 2007, 13, 19–28.
24 P. S. D. Robinson, G. N. Khairallah, G. da Silva, H. Lioe and
R. A. J. O’Hair, Angew. Chem., Int. Ed., 2012, 51, 3812–3817.
25 V. Ryzhov, A. Y. Lam and R. J. O’Hair, J. Am. Soc. Mass Spec-
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Acknowledgements
JSM thanks the Natural Sciences and Engineering Research
Council (NSERC) of Canada for a Discovery Grant and a Discov-
ery Accelerator Supplement, the Canada Foundation for Inno-
vation (CFI) and the British Columbia Knowledge
Development Fund (BCKDF), and the University of Victoria for
instrumentation and operational funding. We thank Dr Lisa
Rosenberg for a donation of Wilkinson’s catalyst. We also
thank Professor Peter Chen for useful discussions on the
subject of numerical modelling.
26 K. L. Vikse, Z. Ahmadi, C. C. Manning, D. A. Harrington
and J. S. McIndoe, Angew. Chem., Int. Ed., 2011, 123, 8454–
8456.
27 L. Banu, V. Blagojevic and D. K. Bohme, J. Phys. Chem. B,
2012, 116, 11791–11797.
28 D. E. Polyansky, J. T. Muckerman, J. Rochford, R. Zong,
R. P. Thummel and E. Fujita, J. Am. Chem. Soc., 2011, 133,
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