N-Heterocyclic Carbene Stabilized Digermanium(0)†
Anastas Sidiropoulos
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597
Search for more papers by this authorCameron Jones Prof.
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597
Search for more papers by this authorAndreas Stasch Dr.
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597
Search for more papers by this authorSusanne Klein
Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg (Germany), Fax: (+49) 6421-282-5566
Search for more papers by this authorGernot Frenking Prof. Dr.
Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg (Germany), Fax: (+49) 6421-282-5566
Search for more papers by this authorAnastas Sidiropoulos
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597
Search for more papers by this authorCameron Jones Prof.
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597
Search for more papers by this authorAndreas Stasch Dr.
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597
Search for more papers by this authorSusanne Klein
Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg (Germany), Fax: (+49) 6421-282-5566
Search for more papers by this authorGernot Frenking Prof. Dr.
Fachbereich Chemie, Philipps-Universität Marburg, 35032 Marburg (Germany), Fax: (+49) 6421-282-5566
Search for more papers by this authorWe thank the Australian Research Council (fellowships for C.J. and A.S.) and the Deutsche Forschungsgemeinschaft (grant FR641/25-1 to G.F.). The EPSRC is also thanked for access to the UK National Mass Spectrometry Facility.
Graphical Abstract
Germanium und sonst nichts! Die Reduktion eines Addukts aus einem N-heterocyclischen Carben (NHC) und GeCl2 mit Magnesium(I)-Dimeren ergab eine dimere Verbindung (siehe Bild), die nach Strukturuntersuchungen und theoretischen Studien ein Singulett-Digermanium(0)-Fragment :GeGe: enthält, das dativ durch zwei NHC-Liganden koordiniert ist.
Supporting Information
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References
- 1See for example
- 1aP. de Frémont, N. Marion, S. P. Nolan, Coord. Chem. Rev. 2009, 253, 862–892;
- 1bF. E. Hahn, M. C. Jahnke, Angew. Chem. 2008, 120, 3166–3216; Angew. Chem. Int. Ed. 2008, 47, 3122–3172;
- 1cW. A. Herrmann, Angew. Chem. 2002, 114, 1342–1363;
Angew. Chem. Int. Ed. 2002, 41, 1290–1309;
10.1002/1521-3773(20020415)41:8<1290::AID-ANIE1290>3.0.CO;2-Y CAS PubMed Web of Science® Google Scholar
- 1dD. Bourissou, O. Guerret, F. P. Gabbaï, G. Bertrand, Chem. Rev. 2000, 100, 39–91, and references therein.
- 2See for example
- 2aN. Kuhn, A. Al-Sheikh, Coord. Chem. Rev. 2005, 249, 829–857;
- 2bC. J. Carmalt, A. H. Cowley, Adv. Inorg. Chem. 2000, 50, 1–32, and references therein.
- 3
- 3aY. Wang, G. H. Robinson, Chem. Commun. 2009, 5201–5213;
- 3bC. A. Dyker, G. Bertrand, Science 2008, 321, 1050–1051.
- 4Y. Wang, Y. Xie, P. Wei, R. B. King, H. F. Schaefer III, P. von R. Schleyer, G. H. Robinson, Science 2008, 321, 1069–1071.
- 5Z. Liu, J. Phys. Chem. A 2009, 113, 6410–6414.
- 6Y. Wang, Y. Xie, P. Wei, R. B. King, H. F. Schaefer III, P. von R. Schleyer, G. H. Robinson, J. Am. Chem. Soc. 2008, 130, 14970–14971.
- 7aO. Back, G. Kuchenbeiser, B. Donnadieu, G. Bertrand, Angew. Chem. 2009, 121, 5638–5641;
10.1002/ange.200902344 Google ScholarAngew. Chem. Int. Ed. 2009, 48, 5530–5533;
- 7bJ. Masuda, W. W. Schoeller, B. Donnadieu, G. Bertrand, J. Am. Chem. Soc. 2007, 129, 14180–14181;
- 7cJ. Masuda, W. W. Schoeller, B. Donnadieu, G. Bertrand, Angew. Chem. 2007, 119, 7182–71851; Angew. Chem. Int. Ed. 2007, 46, 7052–7055;
- 7dO. Back, B. Donnadieu, P. Parameswaram, G. Frenking, G. Bertrand, Nature, in press.
- 8C. A. Dyker, V. Lavallo, B. Donnadieu, G. Bertrand, Angew. Chem. 2008, 120, 3250–3253;
10.1002/ange.200705620 Google ScholarAngew. Chem. Int. Ed. 2008, 47, 3206–3209.
- 9A related acyclic “carbodicarbene” complex was simultaneously reported. A. Fürstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. 2008, 120, 3254–3258;
10.1002/ange.200705798 Google ScholarAngew. Chem. Int. Ed. 2008, 47, 3210–3214.
- 10
- 10aR. Tonner, G. Frenking, Angew. Chem. 2007, 119, 8850–8853;
10.1002/ange.200701632 Google ScholarAngew. Chem. Int. Ed. 2007, 46, 8695–8698;
- 10bN. Takagi, T. Shimizu, G. Frenking, Chem. Eur. J. 2009, 15, 8593–8604.
- 11
- 11aY. Wang, B. Quillian, P. Wei, Y. Xie, C. S. Wannere, R. B. King, H. F. Schaefer III, P. von R. Schleyer, G. H. Robinson, J. Am. Chem. Soc. 2008, 130, 3298–3299;
- 11bY. Wang, B. Quillian, P. Wei, C. S. Wannere, Y. Xie, R. B. King, H. F. Schaefer III, P. von R. Schleyer, G. H. Robinson, J. Am. Chem. Soc. 2007, 129, 12412–12413.
- 12M. Zhou, L. Jiang, Q. Xu, J. Phys. Chem. A 2005, 109, 3325–3330.
- 13P. P. Power, ACS Symp. Ser. 2006, 917, 179–190, and references therein.
- 14P. P. Power, Organometallics 2007, 26, 4362–4372, and references therein.
- 15In one attempted preparation of 4 in THF, a small amount of [IPrH(THF)][GeCl3] was isolated. See the Supporting Information for crystallographic details of this compound.
- 16R. S. Ghadwal, H. W. Roesky, S. Merkel, J. Henn, D. Stalke, Angew. Chem. 2009, 121, 5793–5796; Angew. Chem. Int. Ed. 2009, 48, 5683–5686.
- 17A. C. Filippou, O. Chernov, G. Schnakenburg, Angew. Chem. 2009, 121, 5797–5800;
10.1002/ange.200902431 Google ScholarAngew. Chem. Int. Ed. 2009, 48, 5687–5690.
- 18P. A. Rupar, V. N. Staroverov, P. J. Ragogna, K. M. Baines, J. Am. Chem. Soc. 2007, 129, 15138–15139. NHC adducts of GeBr2 and GeI2 have also been reported. See A. J. Arduengo III, H. V. Rasika Dias, J. C. Calabrese, F. Davidson, Inorg. Chem. 1993, 32, 1541–1542; P. A. Rupar, M. C. Jennings, K. M. Baines, Organometallics 2008, 27, 5043–5051.
- 19S. P. Green, C. Jones, A. Stasch, Science 2007, 318, 1754–1757.
- 20S. J. Bonyhady, S. P. Green, C. Jones, S. Nembenna, A. Stasch, Angew. Chem. 2009, 121, 3017–3021;
10.1002/ange.200900331 Google ScholarAngew. Chem. Int. Ed. 2009, 48, 2973–2977.
- 21S. J. Bonyhady, C. Jones, S. Nembenna, A. Stasch, A. J. Edwards, G. J. McIntyre, Chem. Eur. J., in press.
- 22A. J. Arduengo III, R. Krafczyk, R. Schmutzler, H. A. Craig, J. R. Goerlich, W. J. Marshall, M. Unverzagt, Tetrahedron 1999, 55, 14523–14534.
- 23As determined from a survey of the Cambridge Crystallographic Database, September, 2009.
- 24I. Shim, M. S. Baba, K. A. Gingerich, Chem. Phys. 2002, 277, 9–20.
- 25V. Jonas, G. Frenking, M. T. Reetz, J. Am. Chem. Soc. 1994, 116, 8741–8753.
- 26C. C. Arnold, C. Xu, G. R. Burton, D. M. Neumark, J. Chem. Phys. 1995, 102, 6982–6989.
- 27
- 27aF. M. Bickelhaupt, E. J. Baerends, Rev. Comput. Chem. 2000, 15, 1–86;
- 27bG. Frenking, K. Wichmann, N. Fröhlich, C. Loschen, M. Lein, J. Frunzke, J. V. M. Rayón, Coord. Chem. Rev. 2003, 238–239, 55–82;
- 27cM. Lein, G. Frenking in Theory and Applications of Computational Chemistry: The First 40 Years (Eds.: ), Elsevier, Amsterdam, 2005, p. 367.
- 28K. Morokuma, J. Chem. Phys. 1971, 55, 1236–1244.
- 29
- 29aT. Ziegler, A. Rauk, Inorg. Chem. 1979, 18, 1755–1759;
- 29bT. Ziegler, A. Rauk, Inorg. Chem. 1979, 18, 1558–1565.
- 30The calculated excitation energy X3Σg−→1Δg for Ge2 at BP86/TZ2P is 18.0 kcal mol−1, which is somewhat higher than the experimental value of 9.5 kcal mol−1.[26] The difference between the calculated and experimental values is not relevant for the bonding analysis.
- 31Note added in proof (10.11.2009): The preparation and structural characterization of compound 4 was reported independently after the submission of this manuscript, see: K. C. Thimer, S. M. I. Al-Rafia, M. J. Ferguson, R. McDonald, E. Rivard, Chem. Commun. 2009, DOI:.
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