Inorganic Chemistry
Article
8
33−836. (e) Konno, T.; Taku, K.; Yamada, S.; Moriyasu, K.; Ishihara,
Chem. 2012, 51, 4300−4313. (g) Khalimon, A. Y.; Ignatov, S. K.;
Okhapkin, A. I.; Simionescu, R.; Kuzmina, L. G.; Howard, J. A. K.;
Nikonov, G. I. Chem.Eur. J. 2013, 19, 8573−8590.
T. Org. Biomol. Chem. 2009, 7, 1167−1170. (f) Inagaki, T.; Phong, L. T.;
Furuta, A.; Ito, J.; Nishiyama, H. Chem.Eur. J. 2010, 16, 3090−3096.
(
g) Yu, F.; Zhang, X.-C.; Wu, F.-F.; Zhou, J.-N.; Fang, W.; Wu, J.; Chan,
(23) (a) Arias-Ugarte, R.; Sharma, H. K.; Morris, A. L. C.; Pannell, K.
H. J. Am. Chem. Soc. 2012, 134, 848−851. (b) Sharma, H. K.; Arias-
A. S. C. Org. Biomol. Chem. 2011, 9, 5652. (h) Sauer, D. C.; Wadepohl,
H.; Gade, L. H. Inorg. Chem. 2012, 51, 12948−12958. (i) Niu, Q.; Sun,
H.; Li, X.; Klein, H.-F.; Flo
̃
Ugarte, R.; Tomlinson, D.; Gappa, R.; Metta-Magana, A. J.; Ito, H.;
̈
rke, U. Organometallics 2013, 32, 5235−5238.
Pannell, K. H. Organometallics 2013, 32, 3788−3794.
(
10) For representative Ni hydrosilylation catalysts see: (a) Tamao, K.;
(24) Chakraborty, S.; Blacque, O.; Fox, T.; Berke, H. ACS Catal. 2013,
3, 2208−2217.
Miyake, N.; Kiso, Y.; Kumada, M. J. Am. Chem. Soc. 1975, 97, 5603−
5
6
2
605. (b) Tamao, K.; Kobayashi, K.; Ito, Y. J. Am. Chem. Soc. 1989, 111,
478−6480. (c) Chakraborty, S.; Krause, J. A.; Guan, H. Organometallics
009, 28, 582−586. (d) Tran, B. L.; Pink, M.; Mindiola, D. J.
(25) Trovitch, R. J. Synlett 2014, 25, 1638−1642.
̃
(26) Chiericato, G., Jr.; Arana, C. R.; Casado, C.; Cusdrado, I.; Abruna,
H. D. Inorg. Chim. Acta 2000, 300−302, 32−42.
Organometallics 2009, 28, 2234−2243. (e) Porter, T. M.; Hall, G. B.;
(27) Zeng, D.; Hampden-Smith, M. J. Polyhedron 1992, 11, 2585−
Groy, T. L.; Trovitch, R. J. Dalton Trans. 2013, 42, 14689−14692.
2589.
2
(
f) Miller, Z. D.; Li, W.; Belderrain, T. R.; Montgomery, J. J. Am. Chem.
(28) Several complexes featuring κ -N,N-PDI coordination have been
identified. For crystallographically characterized examples see: (a) Lu,
S.; Selbin, J. Inorg. Chim. Acta 1987, 134, 229−232. (b) Heard, P. J.;
Tocher, D. A. J. Chem. Soc., Dalton Trans. 1998, 2169−2176.
Soc. 2013, 135, 15282−15285. (g) Postigo, L.; Royo, B. Adv. Synth.
Catal. 2012, 354, 2613−2618. (h) Bheeter, L. P.; Henrion, M.; Brelot,
L.; Darcel, C.; Chetcuti, M. J.; Sortais, J.-B.; Ritleng, V. Adv. Synth. Catal.
(c) Cosquer, N.; Le Gall, B.; Conan, F.; Kerbaol, J.-M.; Sala-Pala, J.;
2
012, 354, 2619−2624. (i) MacMillan, S. N.; Harman, W. H.; Peters, J.
C. Chem. Sci. 2014, 5, 590−597.
11) (a) Morris, R. H. Chem. Soc. Rev. 2009, 38, 2282−2291.
b) Bullock, R. M. Catalysis without Precious Metals; Wiley-VCH:
Kubicki, M. M.; Vigier, E. Inorg. Chim. Acta 2006, 359, 4311−4316.
29) Hiya, K.; Nakayama, Y.; Yasuda, H. Macromolecules 2003, 36,
916−7922.
30) de Bruin, B.; Bill, E.; Bothe, E.; Weyhermu
Inorg. Chem. 2000, 39, 2936−2947.
31) Knijnenberg, Q.; Gambarotta, S.; Budzelaar, P. H. M. Dalton
Trans. 2006, 5442−5448.
32) PDI redox activity has proven to be important for enabling first-
(
7
(
(
(
̈
ller, T.; Wieghardt, K.
Weinheim, Germany, 2010. (c) Junge, K.; Schroeder, K.; Beller, M.
Chem. Commun. 2011, 47, 4849−4859.
(
(
12) Molybdenum is the only second-row metal that is widely utilized
in biological systems. For a recent review see: Hille, R.; Hall, J.; Basu, P.
(
Chem. Rev. 2014, 114, 3963−4038.
row-metal-catalyzed transformations. For a leading example see: Chirik,
(
13) Haynes, W. M. CRC Handbook of Chemistry and Physics: A Ready-
P. J.; Wieghardt, K. Science 2010, 327, 794−795.
Reference Book of Chemical and Physical Data, 94th ed.; Taylor & Francis:
Boca Raton, FL, 2013−2014.
́
(33) Corn, I. R.; Astudillo-Sanchez, P. D.; Zdilla, M. J.; Fanwick, P. E.;
Shaw, M. J.; Miller, J. T.; Evans, D. H.; Abu-Omar, M. M. Inorg. Chem.
013, 52, 546657−546663.
34) Ben-Daat, H.; Hall, G. B.; Groy, T. L.; Trovitch, R. J. Eur. J. Inorg.
Chem. 2013, 4430−4442.
35) Chatt, J.; Leigh, G. J.; Neukomm, H.; Pickett, C. J.; Stanley, D. R. J.
Chem. Soc., Dalton Trans. 1980, 121−127.
36) Luo, X.-L.; Kubas, G. J.; Burns, C. J.; Butcher, R. J.; Bryan, J. C.
Inorg. Chem. 1995, 34, 6538−6545.
37) Complete delocalization would be expected if the electron(s)
(
14) Fuchikami, T.; Ubukata, Y.; Tanaka, Y. Tetrahedron Lett. 1991, 32,
2
(
1
(
199−1202.
15) Baricelli, P. J.; Melean, L. G.; Ricardes, S.; Guanipa, V.; Rodriguez,
M.; Romero, C.; Pardey, A. J.; Moya, S.; Rosales, M. J. Organomet. Chem.
009, 694, 3381−3385.
16) (a) Bullock, R. M.; Voges, M. H. J. Am. Chem. Soc. 2000, 122,
2594−12595. (b) Voges, M. H.; Bullock, R. M. J. Chem. Soc., Dalton
(
2
(
1
(
Trans. 2002, 759−770. (c) Kimmich, B. F. M.; Fagan, P. J.; Hauptman,
E.; Bullock, R. M. Chem. Commun. 2004, 1014−1015. (d) Kimmich, B.
F. M.; Fagan, P. J.; Hauptman, E.; Marshall, W. J.; Bullock, R. M.
Organometallics 2005, 24, 6220−6229.
(
3
occupy the LUMO of the κ -N,N,N-PDI chelate (see ref 31). It is also
possible that κ -N,N-PDI chelates can behave as redox non-innocent
2
ligands. For α-iminopyridine reduction see: Lu, C. C.; Weyhermu
T.; Bill, E.; Wieghardt, K. Inorg. Chem. 2009, 48, 6055−6064.
38) Morris, R. H.; Earl, K. A.; Luck, R. L.; Lazarowych, N. J.; Sella, A.
̈
ller,
(
17) Namorado, S.; Antunes, M. A.; Veiros, L. F.; Ascenso, J. R.;
Duarte, M. T.; Martins, A. M. Organometallics 2008, 27, 4589−4599.
18) (a) Adams, K. P.; Joyce, J. A.; Nile, T. A.; Patel, A. I.; Reid, C. D.;
(
(
Inorg. Chem. 1987, 26, 2674−2683.
Walters, J. M. J. Mol. Catal. 1985, 29, 201−208. (b) Keinan, E.; Perez, D.
J. Org. Chem. 1987, 52, 2576−2580. (c) Abdelquader, W.; Ozkar, S.;
Peynircioglu, N. B. Z. Naturforsch. B: Chem. Sci. 1993, 48, 539−540.
(
(
39) Lever, A. B. P. Inorg. Chem. 1990, 29, 1271−1285.
1
40) If η -substrate binding occurs, the steric hindrance of the carbonyl
substituents would be further removed from the metal center.
(
d) Schmidt, T. Tetrahedron Lett. 1994, 35, 3513−3516. (e) Kayran, C.;
Rouzi, P. Z. Naturforsch. B: Chem. Sci. 2001, 56, 1138−1142. (f) Stosur,
M.; Syman
(
41) Ojima, I.; Kogure, T. Organometallics 1982, 1, 1390−1399.
(42) Schneider, N.; Finger, M.; Haferkemper, C.; Bellemin-Laponnaz,
́
ska-Buzar, T. J. Mol. Catal. A: Chem. 2008, 286, 98−105.
19) Dioumaev, V. K.; Bullock, R. M. Nature 2003, 424, 530−532.
20) (a) Fernandes, A. C.; Fernandes, R.; Romao, C. C.; Royo, B.
, C. C.; Royo, B.
Dalton Trans. 2006, 1842−1846. (c) Pontes da Costa, A.; Reis, P. M.;
Gamelas, C.; Romao, C. C.; Royo, B. Inorg. Chim. Acta 2008, 361, 1915−
921.
21) Ziegler, J. E.; Du, G.; Fanwick, P. E.; Abu-Omar, M. M. Inorg.
Chem. 2009, 48, 11290−11296.
22) (a) Khalimon, A. Y.; Simionescu, R.; Kuzmina, L. G.; Howard, J.
A. K.; Nikonov, G. I. Angew. Chem., Int. Ed. 2008, 47, 7701−7704.
b) Oeterson, E.; Khalimon, A. Y.; Simionescu, R.; Kuzmina, L. G.;
Howard, J. A. K.; Nikonov, G. I. J. Am. Chem. Soc. 2009, 131, 908−909.
c) Shirobokov, O. G.; Gorelsky, S. I.; Simionescu, R.; Kuzmina, L. G.;
S.; Hofmann, P.; Gade, L. H. Chem.Eur. J. 2009, 15, 11515−11529.
43) Neese, F. Orca, an Ab Initio, Density Functional and Semiempirical
Electronic Structure Program Package, version 2.9.1; Max Planck Institute
for Bioinorganic Chemistry: Mulheim an der Ruhr, Germany, 2012.
44) (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648−5652. (b) Lee, C.
T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785−789.
45) (a) Klamt, A.; Schu ramann, G. J. Chem. Soc., Perkin Trans. A 2
993, 799−805. (b) Sinnecker, S.; Rajendran, A.; Klamt, A.;
(
(
(
̃
Chem. Commun. 2005, 213−214. (b) Reis, P. M.; Romao
̃
̈
(
̃
1
(
̈ ̈
u
(
1
Diedenhofen, M.; Neese, F. J. Phys. Chem. A 2006, 110, 2235−2245.
(
(46) Grimme, S. J. Comput. Chem. 2006, 27, 1787−1799.
(47) Pantazis, D. A.; Chen, X. Y.; Landis, C. R.; Neese, F. J. Chem.
(
Theory Comput. 2008, 4, 908−919.
(
(
Nikonov, G. I. Chem. Commun. 2010, 46, 7831−7833. (d) Shirobokov,
O. G.; Kuzmina, L. G.; Nikonov, G. I. J. Am. Chem. Soc. 2011, 133,
6
487−6489. (e) Khalimon, A. Y.; Ignatov, S. K.; Simionescu, R.;
Kuzmina, L. G.; Howard, J. A. K.; Nikonov, G. I. Inorg. Chem. 2012, 51,
54−756. (f) Khalimon, A. Y.; Shirobokov, O. G.; Peterson, E.;
Simionescu, R.; Kuzmina, L. G.; Howard, J. A. K.; Nikonov, G. I. Inorg.
7
9
365
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