C O M M U N I C A T I O N S
Scheme 3
References
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structural characterization. The X-ray derived structure of 5a is shown
in Figure 1. A hydride was located at one of the three legs of the
piano-stool geometry of 5a. The Ir-S(thiol) distance of 2.3238(17) Å
is longer than the Ir-S(thiolate) bonds of 1a (2.2617(7) Å) and 3a
(2.2095(10) Å), but it is notably shorter than that of 2a (2.4194(18)
Å), which is electronically analogous to 5a. It might be that the sulfur
atom of 5a has a sulfonium ion character. A similar M-S bond
shortening upon protonation of the thiolate sulfurs of complexes
CpFe(CO)2SPh and [Cr(StBu)(CO)5]- has been reported.13
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Figure 1. ORTEP drawings of the cationic parts of 3a (left) and 5a (right).
Selected bond distances (Å) and angles (deg): 3a: Ir-S 2.2095(10), Ir-P
2.3096(13), S-C1 1.791(3), P-Ir-S 82.80(4), Ir-S-C1 121.63(13). 5a:
Ir-S 2.3238(17), Ir-P 2.254(2), Ir-H 1.50(6), S-C1 1.791(7), P-Ir-S
94.51(8), Ir-S-C1 123.0(2).
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The deuterated compounds, [Cp*Ir(PMe3)D3](BArF ) (4-d3) and
4
D-SDmp, were generated from the reaction of 3a with D2, and their
deuterium atoms were readily replaced by hydrogen atoms under
1 atm of H2 at room temperature. Thus a facile proton exchange
between H-SDmp and 4 is occurring. A kinetic study of the
reactions of 3a with 1 atm of H2 and D2 in CD2Cl2 was conducted
by 1H NMR at -20 °C. By monitoring the decrease in the signals
of 3a, the reactions were shown to obey a pseudo-first-order
kinetics, expressed as -d[3a]/dt ) kH(D)[3a]. The rate constants
were determined to be kH ) 9.56(20) × 10-5 s-1 and kD ) 4.11(8)
× 10-5 s-1. The observed kinetic isotope effect (KIE) of 2.3 (kH/
kD) indicates that a H-H cleaving process is involved in the rate-
determining step. This KIE value may be compared with the one
(kH/kD ) 1.55 (10 °C)) estimated for the H2 activation by the [NiFe]
hydrogenase from Allochromatium Vinosum, in which the rate-
determining step was attributed to an H-H cleaving process.14
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(11) The complex cation [Cp*Ir(PMe3)H3]+ is known: Gilbert, T. M.; Bergman,
R. G. J. Am. Chem. Soc. 1985, 107, 3502–3507.
Acknowledgment. This research was financially supported by
a Grant-in-Aids for Scientific Research (No. 18GS0207 and
18064009) from the Ministry of Education, Culture, Sports, Science,
and Technology, Japan.
(12) Formation of [Cp*Rh(PMe3)(H2)H]+ was observed as a thermally unstable
complex. Taw, F. L.; Mellows, H.; White, P. S.; Hollander, F. J.; Bergman,
R. G.; Brookhart, M.; Deinekey, D. M. J. Am. Chem. Soc. 2002, 124, 5100–
5108.
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Supporting Information Available: Experimental details and
spectral data for 1-5 and information on X-ray analyses, and a CIF
file of the X-ray crystallographic data for 1a,b, 2a, 3a,b, 4, and 5a.
This material is available free of charge via the Internet at http://
pubs.acs.org.
(14) Lamle, S. E.; Vincent, K. A.; Halliwel, L. M.; Albracht, S. P. J.; Armstrong,
F. A. Dalton Trans. 2003, 4152–4157.
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