Inorganic Chemistry
ARTICLE
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(7) For ruthenium η2-B-H monoborane complexes, see: (a) Alcaraz,
G.; Chaplin, A. B.; Stevens, C. J.; Clot, E.; Vendier, L.; Weller, A. S.;
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Barthelat, J.-C.; Sabo-Etienne, S. Organometallics 2005, 24, 2935. (g)
Montiel-Palma, V.; Lumbierres, M.; Donnadieu, B.; Sabo-Etienne, S.;
Chaudret, B. J. Am. Chem. Soc. 2002, 124, 5624.
130, 149. (b) Xu, Z.; Lin, Z. Coord. Chem. Rev. 1996, 156, 139. (c) For
LnM = Cp*RuPR3þ see: Suzuki, H.; Lee, D. H.; Oshima, N.; Moro-oka,
Y. Organometallics 1987, 6, 1569.
(22) It has been established that the formulation of η2-B-H mono-
borane complexes is best ascertained on the basis of a combined X-ray
crystallographic and quantum chemical (DFT) analysis.6b
(23) For some other crystallographically characterized complexes
featuring a Ru-H-B bridging motif, see: (a) Rankin, M. A.; MacLean,
D. F.; McDonald, R.; Ferguson, M. J.; Lumsden, M. D.; Stradiotto, M.
Organometallics 2009, 28, 74. (b) Rudolf, G. C.; Hamilton, A.; Orpen,
A. G.; Owen, G. R. Chem. Commun. 2009, 553. (c) Kawano, Y.; Hashiva,
M.; Shimoi, M. Organometallics 2006, 25, 4420. (d) Saito, T.; Kuwata, S.;
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S. L.; Leong, W. K.; Goh, L. Y.; Webster, R. D. Organometallics 2005, 24,
4639. (g) Merle, N.; Frost, C. G.; Koicok-K€ohn, G.; Willis, M. C.; Weller,
A. S. J. Organomet. Chem. 2005, 690, 2829. (h) Merle, N.; Koicok-K€ohn,
G.; Mahon, M. F.; Frost, C. G.; Ruggerio, G. D.; Weller, A. S.; Willis,
M. C. Dalton Trans. 2004, 3883. (i) Foreman, M. R. St.-J.; Hill, A. F.;
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4446. (j) Baker, R. T.; Calabrese, J. C.; Westcott, S. A.; Marder, T. B.
J. Am. Chem. Soc. 1995, 117, 8777.(k) Ref 7 herein.
(8) For non-ruthenium η2-B-H monoborane complexes, see: (a)
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P. M. B.; Koetzle, T. F.; Schultz, A. J.; Kaminsky, W.; Goldberg, K. I.;
Heinekey, D. M. J. Am. Chem. Soc. 2008, 130, 10812. (d) Crestani, M. G.;
Mu~noz-Hernꢀandez, M.; Arꢀevalo, A.; Acosta-Ramírez, A.; García, J. J. J.
Am. Chem. Soc. 2005, 127, 18066. (e) Schlecht, S.; Hartwig, J. F. J. Am.
Chem. Soc. 2000, 122, 9435. (f) Muhoro, C. N.; He., X.; Hartwig,
J. F. J. Am. Chem. Soc. 1999, 121, 5033. (g) Douglas, T. M.; Chaplin,
A. B.; Weller, A. S.; Yang, X.; Hall, M. B. J. Am. Chem. Soc. 2009, 131,
15440.
(24) A related cationic iron-borylene complex [Cp*(CO)2-
FedBMes]þX- has been reported: (a) Coombs, D. L.; Aldridge,
S.; Rossin, A.; Jones, C.; Willock, D. J. Organometallics 2004, 23,
2911. (b) Coombs, D. L.; Aldridge, S.; Jones, C.; Willock, D. J. J. Am.
Chem. Soc. 2003, 125, 6356.
(25) By comparison, while NMR spectroscopic data for both
(9) M(BHX) (X = OR, NR2) complexes featuring η2-B-H ligands
have recently been reported: (a) Esteruelas, M. A.; Fernꢀandez-Alvarez,
F. J.; Lꢀopez, A. M.; Mora, M.; O~nate, E. J. Am. Chem. Soc. 2010, 132,
5600.(b) Ref 8a herein.
(10) (a) Szymczak, N. K.; Tyler, D. R. Coord. Chem. Rev. 2008, 252,
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(c) Jessop, P. G.; Morris, R. H. Coord. Chem. Rev. 1992, 121, 155.
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Chem. Soc. Rev. 2002, 31, 239. (d) Corey, J. Y.; Braddock-Wilking, J.
Chem. Rev. 1999, 99, 175.(e) Refs6b and 6d herein.
[Cp*(PR3)(H)2RudSiHR]þX- and [Cp*(μ-2-NMe2-3-PiPr2-indene)-
(H)2RudSiHR]þX- complexes14,16 revealed minimal Ru-H SiHR
3 3 3
interactions in solution, an unsymmetrical Ru-H-Si bridging motif was
observed in a quantum chemical analysis of the former complexes,17b as
well as in solid state structures of the latter base-stabilized complexes.16
(26) (a) Crossley, I. R.; Foreman, M. R. St.-J.; Hill, A. F.; Owen,
G. R.; White, A. J. P.; Williams, D. J.; Willis, A. C. Organometallics 2008,
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Angew. Chem., Int. Ed. 1999, 38, 2759.
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(13) (a) Jimꢀenez-Tenorio, M.; Puerta, M. C.; Valerga, P. Eur. J. Inorg.
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(14) Glaser, P. B.; Tilley, T. D. J. Am. Chem. Soc. 2003, 125,
13640.
(30) The related transformation of coordinatively unsaturated
M-SiHRX species into (H)MdSiRX complexes (X = H, R) now
represents an established route to metal-silylene complexes.15a
(31) No evidence for chemical exchange involving the alkenyl C-H
and the Ru-H environments in 7 was obtained by use of 1H-1H EXSY
NMR techniques (300 K) employing a range of mixing times.
(32) (a) While our investigations were underway, the decomposi-
tion of Cp*(PiPr3)RuCl in the presence of various benzylating agents
leading to intractable reaction mixtures was reported: (b) Hayes, P. G.;
Waterman, R.; Glaser, P. B.; Tilley, T. D. Organometallics 2009, 28,
5082. (c) The formation of the osmium analogue of 7 has been reported
in the reaction of Cp*(PiPr3)OsBr with KB(C6F5)4, followed by
treatment with KN(SiMe3)2: Glaser, P. B.; Tilley, T. D. Organometallics
2004, 23, 5799.
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Ogino, H. Chem. Rec. 2002, 2, 291. (d) Ogino, H.; Tobita, H. Adv.
Organomet. Chem. 1998, 42, 223. (e) Zybill, C.; Handwerker, H.;
Friedrich, H. Adv. Organomet. Chem. 1994, 36, 229.
(16) While crystallographically characterized [Cp*(PR3)(H)2-
RudSiHR]þX- complexes have yet to be reported, structurally
related base-stabilized variants have appeared: Rankin, M. A.; Ma-
cLean, D. F.; Schatte, G.; McDonald, R.; Stradiotto, M. J. Am. Chem.
Soc. 2007, 129, 15855.
(17) (a) Beddie, C.; Hall, M. B. J. Phys. Chem. A 2006, 110, 1416. (b)
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Wallingford, CT, 2004.
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T. D. J. Am. Chem. Soc. 2006, 128, 428.
(34) (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098. (b) Lee, C.; Yang,
W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. (c) Becke, A. D. J. Chem. Phys.
1993, 98, 5648.
(19) A portion of this synthetic work has been communicated: Hesp,
K. D.; Rankin, M. A.; McDonald, R.; Stradiotto, M. Inorg. Chem. 2008,
47, 7471.
(20) Kawano, Y.; Shimoi, M. Chem. Lett. 1998, 935.
(21) Structurally diverse complexes of the type LnM(BH4) are well-
established: (a) Besora, M.; Lledoꢀs, A. Struct. Bonding (Berlin) 2008,
(35) Ahlrichs, R.; May, K. Phys. Chem. Chem. Phys. 2000, 2, 943.
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dx.doi.org/10.1021/ic1022328 |Inorg. Chem. 2011, 50, 2431–2444