MetalMetal Bond Formation Between [n]Metallocenophanes: Synthesis and Characterisation of a Dicarba[2]ruthenocenophanium Dimer
Andrew D. Russell
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorDr. Joe B. Gilroy
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorDr. Kevin Lam
Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Search for more papers by this authorMairi F. Haddow
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. Jeremy N. Harvey
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Jeremy N. Harvey, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
William E. Geiger, Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Ian Manners, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. William E. Geiger
Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Jeremy N. Harvey, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
William E. Geiger, Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Ian Manners, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. Ian Manners
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Jeremy N. Harvey, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
William E. Geiger, Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Ian Manners, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorAndrew D. Russell
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorDr. Joe B. Gilroy
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorDr. Kevin Lam
Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Search for more papers by this authorMairi F. Haddow
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. Jeremy N. Harvey
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Jeremy N. Harvey, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
William E. Geiger, Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Ian Manners, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. William E. Geiger
Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Jeremy N. Harvey, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
William E. Geiger, Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Ian Manners, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorCorresponding Author
Prof. Dr. Ian Manners
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Jeremy N. Harvey, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
William E. Geiger, Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 (USA)
Ian Manners, School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS (UK)
Search for more papers by this authorGraphical Abstract
Feeling the strain: The first example of metal–metal bonding between strained [n]metallocenophanes is reported. A dicarba[2]ruthenocenophanium dimer has been synthesised through the oxidation of a dicarba[2]ruthenocenophane (see figure). The structural and electrochemical characterisation of the dimer is also discussed.
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References
- 1
- 1aJ. C. Green, Chem. Soc. Rev. 1998, 27, 263–272;
- 1bD. E. Herbert, U. F. J. Mayer, I. Manners, Angew. Chem. 2007, 119, 5152–5173;
10.1002/ange.200604409 Google ScholarAngew. Chem. Int. Ed. 2007, 46, 5060–5081.
- 2
- 2aT. Mizuta, Y. Imamura, K. Miyoshi, J. Am. Chem. Soc. 2003, 125, 2068–2069;
- 2bJ. A. Schachner, S. Tockner, C. L. Lund, J. W. Quail, M. Rehahn, J. Müller, Organometallics 2007, 26, 4658–4662;
- 2cP. Chadha, J. L. Dutton, M. J. Sgro, P. J. Ragogna, Organometallics 2007, 26, 6063–6065;
- 2dD. M. Khramov, E. L. Rosen, V. M. Lynch, C. W. Bielawski, Angew. Chem. 2008, 120, 2299–2302;
10.1002/ange.200704978 Google ScholarAngew. Chem. Int. Ed. 2008, 47, 2267–2270;
- 2eM. Tamm, Chem. Commun. 2008, 3089–3100;
- 2fB. Bagh, J. B. Gilroy, A. Staubitz, J. Müller, J. Am. Chem. Soc. 2010, 132, 1794–1795.
- 3J. M. Nelson, A. J. Lough, I. Manners, Angew. Chem. 1994, 106, 1019–1021; Angew. Chem. Int. Ed. Engl. 1994, 33, 989–991.
- 4
- 4aH. Braunschweig, F. Breher, M. Kaupp, M. Gross, T. Kupfer, D. Nied, K. Radacki, S. Schinzel, Organometallics 2008, 27, 6427–6433;
- 4bU. F. J. Mayer, J. B. Gilroy, D. O’Hare, I. Manners, J. Am. Chem. Soc. 2009, 131, 10382–10383.
- 5H. Braunschweig, M. Gross, K. Radacki, Organometallics 2007, 26, 6688–6690.
- 6H. Braunschweig, M. Gross, K. Radacki, C. Rothgaengel, Angew. Chem. 2008, 120, 10127–10129; Angew. Chem. Int. Ed. 2008, 47, 9979–9981.
- 7
- 7aA. Berenbaum, I. Manners, Dalton Trans. 2004, 2057–2058;
- 7bM. Tamm, A. Kunst, T. Bannenberg, E. Herdtweck, P. Sirsch, C. J. Elsevier, J. M. Ernsting, Angew. Chem. 2004, 116, 5646–5650;
10.1002/ange.200460538 Google ScholarAngew. Chem. Int. Ed. 2004, 43, 5530–5534;
- 7cC. L. Lund, J. A. Schachner, J. W. Quail, J. Müller, J. Am. Chem. Soc. 2007, 129, 9313–9320;
- 7dH. Braunschweig, M. Kaupp, C. J. Adams, T. Kupfer, K. Radacki, S. Schinzel, J. Am. Chem. Soc. 2008, 130, 11376–11393;
- 7eH. Braunschweig, T. Kupfer, Acc. Chem. Res. 2010, 43, 455–465.
- 8G. Masson, D. E. Herbert, G. R. Whittell, J. P. Holland, A. J. Lough, J. C. Green, I. Manners, Angew. Chem. 2009, 121, 5061–5064;
10.1002/ange.200901213 Google ScholarAngew. Chem. Int. Ed. 2009, 48, 4961–4964.
- 9
- 9aJ. K. Pudelski, I. Manners, J. Am. Chem. Soc. 1995, 117, 7265–7266;
- 9bR. Rulkens, A. J. Lough, I. Manners, S. R. Lovelace, C. Grant, W. E. Geiger, J. Am. Chem. Soc. 1996, 118, 12683–12695;
- 9cT. J. Peckham, J. A. Massey, C. H. Honeyman, I. Manners, Macromolecules 1999, 32, 2830–2837;
- 9dK. Temple, F. Jäkle, J. B. Sheridan, I. Manners, J. Am. Chem. Soc. 2001, 123, 1355–1364.
- 10
- 10aM. Tanabe, G. W. M. Vandermeulen, W. Y. Chan, P. W. Cyr, L. Vanderark, D. A. Rider, I. Manners, Nature Mater. 2006, 5, 467–470;
- 10bD. E. Herbert, U. F. J. Mayer, J. B. Gilroy, M. J. López-Gómez, A. J. Lough, J. P. H. Charmant, I. Manners, Chem. Eur. J. 2009, 15, 12234–12246;
- 10cJ. B. Gilroy, A. D. Russell, A. J. Stonor, L. Chabanne, S. Baljak, M. F. Haddow, I. Manners, Chem. Sci. 2012, 3, 830–841.
- 11G. R. Whittell, M. D. Hager, U. S. Schubert, I. Manners, Nature Mater. 2011, 10, 176–188.
- 12V. Bellas, M. Rehahn, Angew. Chem. 2007, 119, 5174–5197;
10.1002/ange.200604420 Google ScholarAngew. Chem. Int. Ed. 2007, 46, 5082–5104.
- 13
- 13aM. J. MacLachlan, M. Ginzburg, N. Coombs, T. W. Coyle, N. P. Raju, J. E. Greedan, G. A. Ozin, I. Manners, Science 2000, 287, 1460–1463;
- 13bH. Tang, Y. Liu, X. Chen, J. Qin, M. Inokuchi, M. Kinoshita, X. Jin, Z. Wang, B. Xu, Macromolecules 2004, 37, 9785–9792;
- 13cI. Korczagin, R. G. H. Lammertink, M. A. Hempenius, S. Golze, G. J. Vancso, Adv. Polym. Sci. 2006, 200, 91–117;
- 13dY. Ma, W.-F. Dong, M. A. Hempenius, H. Möhwald, G. J. Vancso, Nature Mater. 2006, 5, 724–729;
- 13eD. P. Puzzo, A. C. Arsenault, I. Manners, G. A. Ozin, Angew. Chem. 2009, 121, 961–965;
10.1002/ange.200804391 Google ScholarAngew. Chem. Int. Ed. 2009, 48, 943–947.
- 14D. E. Herbert, J. B. Gilroy, A. Staubitz, M. F. Haddow, J. N. Harvey, I. Manners, J. Am. Chem. Soc. 2010, 132, 1988–1998.
- 15
- 15aW. Finckh, B. Z. Tang, A. J. Lough, I. Manners, Organometallics 1992, 11, 2904–2911;
- 15bM. Herberhold, U. Steffl, W. Milius, B. Wrackmeyer, Angew. Chem. 1997, 109, 1545–1546;
10.1002/ange.19971091324 Google ScholarAngew. Chem. Int. Ed. Engl. 1997, 36, 1508–1510;
- 15cH. Bera, H. Braunschweig, A. Oechsner, F. Seeler, R. Sigritz, J. Organomet. Chem. 2010, 695, 2609–2613.
- 16N. G. Connelly, W. E. Geiger, Chem. Rev. 1996, 96, 877–910.
- 17
- 17aJ. K. Pudelski, D. A. Foucher, C. H. Honeyman, A. J. Lough, I. Manners, S. Barlow, D. O’Hare, Organometallics 1995, 14, 2470–2479;
- 17bR. Rulkens, D. P. Gates, D. Balaishis, J. K. Pudelski, D. F. McIntosh, A. J. Lough, I. Manners, J. Am. Chem. Soc. 1997, 119, 10976–10986.
- 18D. E. Herbert, J. B. Gilroy, W. Y. Chan, L. Chabanne, A. Staubitz, A. J. Lough, I. Manners, J. Am. Chem. Soc. 2009, 131, 14958–14968.
- 19
- 19aM. G. Hill, W. M. Lamanna, K. R. Mann, Inorg. Chem. 1991, 30, 4687–4690;
- 19bS. Trupia, A. Nafady, W. E. Geiger, Inorg. Chem. 2003, 42, 5480–5482;
- 19cJ. C. Swarts, A. Nafady, J. H. Roudebush, S. Trupia, W. E. Geiger, Inorg. Chem. 2009, 48, 2156–2165;
- 19dC. E. Banks, K. L. Robinson, H.-P. Laing, A. W. Meredith, N. S. Lawrence, Electroanalysis 2007, 19, 555–560;
- 19eE. I. Rogers, N. S. Lawrence, R. G. Compton, J. Electroanal. Chem. 2011, 657, 144–149.
- 20W. E. Geiger, F. Barrière, Acc. Chem. Res. 2010, 43, 1030–1039.
- 21The osmocenium dicationic dimer has been synthesised and structurally characterised through a reaction of osmocene with [NH4]2[Ce(NO3)6] followed by a salt metathesis of the ceric salt with NH4PF6 to yield the [(Cp2Os)2][PF6]2 product. For details see: M. W. Droege, W. D. Harman, H. Taube, Inorg. Chem. 1987, 26, 1309–1315.
- 22To establish the chemical reversibility of the synthesis of dimer 4, reduction with an excess of decamethylcolbaltocene in CD3NO2 was studied. 1H NMR spectroscopic analysis revealed complete conversion of dimer 4 to the precursor dicarba[2]ruthenocenophane 3.
- 23The UV/Vis solvent cut-off for Me3NO2 was taken to be 400 nm. For details, see: G. W. C. Kaye, T. H. Laby, Tables of Physical and Chemical Constants, 16th ed., The National Physics Laboratory, Middlesex, 1995.
- 24
- 24aK. M. Kadish, L.-L. Wang, A. Thuriere, E. Van Caemelbecke, J. L. Bear, Inorg. Chem. 2003, 42, 834–843;
- 24bK. M. Kadish, R. Garcia, T. Phan, J. Wellhoff, E. Van Caemelbecke, J. L. Bear, Inorg. Chem. 2008, 47, 11423–11428.
- 25The torsion angles between the four Cp centroid positions and the two Ru-metal centres are as follows: 87.2(1), 88.9(1), 89.1(1), 94.8(1)o. The variation in these values reflects slight distortions in each dicarba[2]ruthenocenophane.
- 26
- 26aF. A. Cotton, T. Ren, J. L. Eglin, J. Am. Chem. Soc. 1990, 112, 3439–3445;
- 26bJ.-L. Zuo, E. Herdtweck, F. E. Kühn, J. Chem. Soc. Dalton Trans. 2002, 1244–1246;
- 26cP. Angardis, in Multiple Bonds Between Metal Atoms, 3rd ed. ), Springer, New York, 2005, pp. 377–430;
10.1007/0-387-25829-9_9 Google Scholar
- 26dS. K. Patra, N. Sadhukhan, J. K. Bera, Inorg. Chem. 2006, 45, 4007–4015.
- 27
- 27aM. O. Albers, D. C. Liles, E. Singleton, J. E. Stead, M. M. de. V. Steyn, Organometallics 1986, 5, 1262–1264;
- 27bK.-B. Shiu, C.-H. Li, T.-J. Chan, S.-M. Peng, M.-C. Cheng, S.-L. Wang, F.-L. Liao, M. Y. Chiang, Organometallics 1995, 14, 524–529;
- 27cT. Funaioli, F. Marchetti, G. Fachinetti, Chem. Commun. 1999, 2043–2044.
- 28U. T. Mueller-Westerhoff, A. L. Rheingold, G. F. Swiegers, Angew. Chem. 1992, 104, 1398–1400; Angew. Chem. Int. Ed. Engl. 1992, 31, 1352–1354.
- 29The differences in the α angles between the two dicarba[2]ruthenocenophane units in dimer 4 appear to arise due to crystal packing effects.