Abstract
Electron-rich allenes and heterocumulenes are commonly described by the regular notations of organic chemistry. Following on from published results and recent computational studies, we present here a host of crystallographic and reactivity data, as well as theoretical results, that indicate a highly non-canonical bonding situation in many members of this series. These must actually be interpreted as coordination compounds, in which carbon serves as a ‘central atom’ that interacts with its ‘ligand sphere’ via donor–acceptor bonds, even if these internal ligands themselves are carbon based. This captodative description is not limited to compounds that supposedly comprise a carbon(0) centre, a peculiar oxidation state that can be probed experimentally by geminal diauration. As the available data suggest that this unconventional interpretation of C–C and C–X bonds is more generally applicable than previously anticipated, it may well affect our understanding of organic chemistry in general.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Igau, A., Grützmacher, H., Baceiredo, A. & Bertrand, G. Analogous α,α′-bis-carbenoid triply bonded species: synthesis of a stable λ3-phosphinocarbene-λ5-phosphaacetylene. J. Am. Chem. Soc. 110, 6463–6466 (1988).
Arduengo, A. J., Harlow, R. L. & Kline, M. A stable crystalline carbene. J. Am. Chem. Soc. 113, 361–363 (1991).
Bertrand, G. Carbene Chemistry. From Fleeting Intermediates to Powerful Reagents (Dekker, 2002).
Herrmann, W. A. N-Heterocyclic carbenes: a new concept in organometallic catalysis. Angew. Chem. Int. Ed. 41, 1290–1309 (2002).
Hahn, F. E. & Jahnke, M. C. Heterocyclic carbenes: synthesis and coordination chemistry. Angew. Chem. Int. Ed. 47, 3122–3172 (2008).
Tonner, R. & Frenking, G. Divalent carbon(0) chemistry, part 1: parent compounds. Chem. Eur. J. 14, 3260–3272 (2008).
Tonner, R. & Frenking, G. Divalent carbon(0) chemistry, part 2: protonation and complexes with main group and transition metal Lewis acids. Chem. Eur. J. 14, 3273–3289 (2008).
Kaska, W. C., Mitschell, D. K. & Reichelderfer, R. F. Transition metal complexes of hexaphenyl-carbodiphosphorane. J. Organomet. Chem. 47, 391–402 (1973).
Schmidbaur, H. Phosphorus ylides in the coordination sphere of transition metals: an inventory. Angew. Chem. Int. Ed. Engl. 22, 907–927 (1983).
Tonner, R., Öxler, F., Neumüller, B., Petz, W. & Frenking, G. Carbodiphosphoranes: the chemistry of divalent carbon(0). Angew. Chem. Int. Ed. 45, 8038–8042 (2006).
Schmidbaur, H. & Gasser, O. The ambident ligand properties of bis(trimethylphosphoranylidene)-methane. Angew. Chem. Int. Ed. Engl. 15, 502–503 (1976).
Vicente, J., Singhal, A. R. & Jones, P. G. New ylide-, alkynyl-, and mixed alkynyl/ylide-gold(I) complexes. Organometallics 21, 5887–5900 (2002).
Marrot, S., Kato, T., Gornitzka, H. & Baceiredo, A. Cyclic carbodiphosphoranes: strongly nucleophilic σ-donor ligands. Angew. Chem. Int. Ed. 45, 2598–2601 (2006).
Tonner, R. & Frenking, G. C(NHC)2: divalent carbon(0) compounds with N-heterocyclic carbene ligands—theoretical evidence for a class of molecules with promising chemical properties. Angew. Chem. Int. Ed. 46, 8695–8698 (2007).
Viehe, H. G., Janousek, Z., Gompper, R. & Lach, D. Allenetetramine and dialkoxydiaminoallene. Angew. Chem. Int. Ed. Engl. 12, 566–567 (1973).
Taylor, M. J., Surman, P. W. J. & Clark, G. R. Allyl, amidinium and cyclopropenyl cations from the reaction of primary and secondary amines with pentachlorocyclopropane. J. Chem. Soc. Chem. Commun. 2517–2518 (1994).
Fürstner, A., Alcarazo, M., Goddard, R. & Lehmann, C. W. Coordination chemistry of ene-1,1-diamines and a prototype ‘carbodicarbene’. Angew. Chem. Int. Ed. 47, 3210–3214 (2008).
Dyker, C. A., Lavallo, V., Donnadieu, B. & Bertrand G. Synthesis of an extremely bent acyclic allene (a ‘carbodicarbene’): a strong donor ligand. Angew. Chem. Int. Ed. 47, 3206–3209 (2008).
Pascual, S. et al. Synthesis of a mixed phosphonium-sulfonium bisylide R3P = C = SR2 . Angew. Chem. Int. Ed. 46, 9078–9080 (2007).
Lavallo, V., Dyker, C. A., Donnadieu, B. & Bertrand, G. Synthesis and ligand properties of stable five-membered-ring allenes containing only second-row elements. Angew. Chem. Int. Ed. 47, 5411–5414 (2008).
Lavallo, V., Dyker, C. A., Donnadieu, B. & Bertrand, G. Are allenes with zwitterionic character still allenes? Of course! Angew. Chem. Int. Ed. 48, 1540–1542 (2009).
Christl, M. & Engels, B. Stable five-membered-ring allenes with second-row elements only: not allenes, but zwitterions. Angew. Chem. Int. Ed. 48, 1538–1539 (2009).
Kaufhold, O. & Hahn, F. E. Carbodicarbenes: divalent carbon(0) compounds. Angew. Chem. Int. Ed. 47, 4057–4061 (2008).
Collmann, J. P., Hegedus, L. S., Norton, J. R. & Finke, R. G. Principles and Applications of Organotransition Metal Chemistry (University Science Books, 1987).
Asay, M. et al. Synthesis and ligand properties of a stable five-membered-ring vinylidenephosphorane. Angew. Chem. Int. Ed. 47, 7530–7533 (2008).
Fürstner, A., Alcarazo, M., Krause, H. & Lehmann, C. W. Effective modulation of the donor properties of N-heterocyclic carbene ligands by ‘through-space’ communication within a planar chiral scaffold. J. Am. Chem. Soc. 129, 12676–12677 (2007).
Tonner, R., Heydenrych, G. & Frenking, G. First and second proton affinities of carbon bases. ChemPhysChem 9, 1474–1481 (2008).
Saalfrank, R. W. & Lurz, C.-J. in Methoden der Organischen Chemie (Houben-Weyl) 4th edn, Vol. E15/3 (eds Kropf, H. & Schaumann, E.) 3056–3051 (Thieme, 1993).
Braverman, S., Cherkinsky, M. & Birsa, M. L. in Science of Synthesis, Vol. 18 (ed. Knight, J. G.) 282–286 (Thieme, 2005).
Fürstner, A., Alcarazo, M., Radkowski, K. & Lehmann, C. W. Carbenes stabilized by ylides: pushing the limits. Angew. Chem. Int. Ed. 47, 8302–8306 (2008).
Wang, Y. et al. A stable silicon(0) compound with a Si=Si double bond. Science 321, 1069–1071 (2008).
Dyker, C. A. & Bertrand, G. Soluble allotropes of main-group elements. Science 321, 1050–1051 (2008).
Hoffmann, R. Building bridges between inorganic and organic chemistry. Angew. Chem. Int. Ed. Engl. 21, 711–724 (1982).
Johnson, B. F. G., Lewis, J., Raithby, P. R. & Sanders, A. Structure and bonding in Au2Os mixed-metal carbonyl clusters: the crystal and molecular structure of [Os(CO)4{AuPPh3}2]. J. Organomet. Chem. 260, C29–C32 (1984).
Gladysz, J. A. & Tam, W. A one-flask preparation of analytically pure K2Fe(CO)4 . J. Org. Chem. 43, 2279–2280 (1978).
Hill, N. J. & West, R. Recent developments in the chemistry of stable silylenes. J. Organomet. Chem. 689, 4165–4183 (2004).
Fürstner, A., Krause, H. & Lehmann, C. W. Preparation, structure and catalytic properties of a binuclear Pd(0) complex with bridging silylene ligands. Chem. Commun. 2372–2372 (2001).
Arduengo, A. J. et al. Photoelectron spectroscopy of a carbene/silylene/germylene series. J. Am. Chem. Soc. 116, 6641–6649 (1994).
Tuononen, H. M., Roesler, R., Dutton, J. L. & Ragogna, P. J. Electronic structures of main-group carbene analogues. Inorg. Chem. 46, 10693–10706 (2007).
Böhm, V. P. W., Gstöttmayr, C. W. K., Weskamp, T. & Herrmann, W. A. N-Heterocyclic carbene complexes of palladium(0): synthesis and application in the Suzuki cross-coupling reaction. J. Organomet. Chem. 595, 186–190 (2000).
Acknowledgements
Generous financial support by the Max Planck Gesellschaft, the Spanish Ministerio de Educación y Ciencia (fellowship for M.A.) and the Fonds der Chemischen Industrie is gratefully acknowledged. We thank R. Goddard and J. Rust for solving the X-ray structures and H. Bruns for experimental support.
Author information
Authors and Affiliations
Contributions
A.F. and M.A. designed the research, M.A. performed the experimental work, C.W.L. was responsible for the crystal structures, A.A. and W.T. performed the computational studies; A.F. supervised the project and wrote the paper. All authors discussed the results and commented on the manuscript.
Corresponding author
Supplementary information
Supplementary information
Supplementary information (PDF 575 kb)
Supplementary information
Crystallographic data for compound 10 (CIF 19 kb)
Supplementary information
Crystallographic data for compound 13 (CIF 22 kb)
Supplementary information
Crystallographic data for compound 16 (CIF 18 kb)
Supplementary information
Crystallographic data for compound 17 (CIF 19 kb)
Supplementary information
Crystallographic data for compound 20 (CIF 21 kb)
Supplementary information
Crystallographic data for compound 21 (CIF 31 kb)
Supplementary information
Crystallographic data for compound 23 (CIF 19 kb)
Rights and permissions
About this article
Cite this article
Alcarazo, M., Lehmann, C., Anoop, A. et al. Coordination chemistry at carbon. Nature Chem 1, 295–301 (2009). https://doi.org/10.1038/nchem.248
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nchem.248
This article is cited by
-
Isolation and reactivity of an elusive diazoalkene
Nature Chemistry (2021)
-
Charge frustration in ligand design and functional group transfer
Nature Reviews Chemistry (2021)
-
Double dative bond between divalent carbon(0) and uranium
Nature Communications (2018)
-
C → N coordination bonds in (CCC) → N + ← (L) complexes
Theoretical Chemistry Accounts (2018)
-
Carbene →N+ Coordination Bonds in Drugs: A Quantum Chemical Study
Journal of Chemical Sciences (2016)