Organometallics
Note
Mes); 2.26 (4H, m, NCH2CH2). 13C{1H} NMR (125 MHz, CDCl3,
298 K): δ 188.7; 149.9; 148.9; 142.7; 137.9; 136.9; 136.7; 131.9; 129.6;
124.3; 55.5; 24.8; 21.0; 20.5. Anal. Calcd for C28H34N3PdCl3: C, 53.78;
H, 5.48; N, 6.72. Found: C, 53.31; H, 5.34; N, 6.24.
(8) For examples of Pd−PEPPSI systems prepared by others see:
(a) Ray, L.; Shaikh, M.; Ghosh, P. Dalton Trans. 2007, 40, 4546.
(b) Liao, C. Y.; Chan, K. T.; Zeng, J. Y.; Hu, C. H.; Tu, C. Y.; Lee, H. M.
Organometallics 2007, 26, 1692. (c) O’Keefe, B. M.; Simmons, N.;
Martin, S. F. Org. Lett. 2008, 22, 5301. (d) Larrosa, I.; Somoza, C.;
Banquy, A.; Goldup, S. M. Org. Lett. 2011, 13, 146. (e) Canseco-
ASSOCIATED CONTENT
* Supporting Information
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Gonzalez, D.; Gniewek, A.; Szulmanowicz, M.; Muller-Bunz, H.;
̈
S
Trzeciak, A. M.; Albrecht, M. Chem. Eur. J. 2012, 18, 6055. (f) Chen,
M.; Vicic, D. A.; Turner, M. L.; Navarro, O. Organometallics 2011, 30,
5052. (g) Keske, E. C.; Zenkina, O. V.; Wang, R.; Crudden, C. M.
Organometallics 2012, 31, 6215. (h) Chartoire, A.; Frogneux, X.; Boreux,
A.; Slawin, A. M. Z.; Nolan, S. P. Organometallics 2012, 31, 6947.
(9) (a) Valente, C.; Baglione, S.; Candito, D.; O’Brien, C. J.; Organ, M.
G. Chem. Commun. 2008, 735. (b) Organ, M. G.; Calimsiz, S.; Sayah, M.;
Hou Hoi, K.; Lough, A. J. Angew. Chem., Int. Ed. 2009, 48, 2383.
(c) Organ, M. G.; Avola, S.; Dubovyk, I.; Hadei, N.; Kantchev, E.A. B.;
O’Brien, C. J.; Valente, C. Chem. Eur. J. 2006, 12, 4749. (d) Valente, C.;
Belowich, M. E.; Hadei, N.; Organ, M. G. Eur. J. Org. Chem. 2010, 4343.
(e) Pompeo, M.; Froese, R. D. J.; Hadei, N.; Organ, M. G. Angew. Chem.,
Int. Ed. 2012, 51, 11354.
Text, figures, tables, and CIF files giving catalyst optimization
data, deuterium labeling/catalytic dehalogenation data, addi-
tional experimental data, and crystallographic data for 3 and 4.
This material is available free of charge via the Internet at http://
charge from the CCDC under file numbers 988948 and 988949.
AUTHOR INFORMATION
Corresponding Authors
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(10) (a) Organ, M. G.; Abdel-Hadi, M.; Avola, S.; Dubovyk, I.; Hadei,
N.; Kantchev, E. A. B.; O’Brien, C. J.; Sayah, M.; Valente, C. Chem. Eur. J.
2008, 14, 2443. (b) Hou Hoi, K.; Organ, M. G. Chem. Eur. J. 2012, 18,
804.
(11) (a) Sayah, M.; Organ, M. G. Chem. Eur. J. 2011, 17, 11719.
(b) Sayah, M.; Organ, M. G. Chem. Eur. J. 2013, 19, 16196.
(12) (a) Nasielski, J.; Hadei, N.; Achonduh, G.; Kantchev, E. A. B.;
O’Brien, C. J.; Lough, A.; Organ, M. G. Chem. Eur. J. 2010, 16, 10844.
(b) Valente, C.; Calimsiz, S.; Hou Hoi, K.; Mallik, D.; Sayah, M.; Organ,
M. G. Angew. Chem., Int. Ed. 2012, 51, 3314.
Present Address
†School of Chemistry, University of Manchester, Manchester
N13 9PL, U.K.
Author Contributions
The manuscript was written through contributions of both
authors. Both authors have given approval to the final version.
Notes
The authors declare no competing financial interest.
(13) Higgins, E. M.; Sherwood, J. A.; Lindsay, A. G.; Armstrong, J.;
Massey, R. S.; Alder, R. W.; O’Donoghue, A. C. Chem. Commun. 2011,
47, 1559.
(14) An alternate one-pot route toward expanded ring NHC Pd−
PEPPSI compounds would involve the in situ generation of the desired
free carbene species with either KHMDS or tBuOK employing
anhydrous 3-chloropyridine as solvent in the presence of PdCl2 under
inert conditions.
(15) Dunsford, J. J.; Cavell, K. J. Dalton Trans. 2011, 40, 9131.
(16) Hauwert, P.; Dunsford, J. J.; Tromp, D. S.; Weigand, J. J.; Lutz, M.;
Cavell, K. J.; Elsevier, C. J. Organometallics 2013, 32, 311.
(17) Although this method was suitable to access 6- and 7-Mes
derivatives, it did not allow access to the increasingly sterically
demanding 6- and 7-DIPP (DIPP = 2,6-diisopropylphenyl) derivatives,
as the parent Pd(0) complexes are inaccessible; see refs 15 and 16 for
further details.
(18) (a) Poater, A.; Cozenza, B.; Correa, A.; Giudice, S.; Ragone, F.;
Scarano, V.; Cavello, L. Eur. J. Inorg. Chem. 2009, 1759. (b) For a
comprehensive review of %Vbur values of NHC complexes see: Clavier,
H.; Nolan, S. P. Chem. Commun. 2010, 46, 841.
ACKNOWLEDGMENTS
We acknowledge the EPSRC for financial support and the Cardiff
Catalysis Institute for J.J.D.’s Ph.D. studentship.
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(23) See the Supporting Information.
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dx.doi.org/10.1021/om5003107 | Organometallics 2014, 33, 2902−2905