The Formation of Heteroleptic Carbene Homologues by Ligand Exchange - Synthesis of the First Plumbanediyl Dimer

Angewandte Chemie - International Edition

Volumn 37, Issue 1-2, 1998, Pages 124-126

  Klinkhammer, Karl W ^a   Fässler, Thomas F ^b   Grützmacher, Hansjörg ^b  

^a UNIVERSITY OF STUTTGART   (Germany)

^b LABORATORY OF INORGANIC CHEMISTRY   (Switzerland)

Author keywords

Carbene homologues; Lead; Main group elements; Multiple bonds; Tin

Indexed keywords

EID: 0031906803     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19980202)37:1/2<124::aid-anie124>3.0.co;2-c     Document Type: Article

References (22)

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3. For recent reviews, see a) G. Rabe, J. Michl, Chem. Rev. 1985, 85,419; b) T. Tsumaraya, S. A. Batcheller, S. Masamune, Angew. Chem. 1991, 103, 916; Angew. Chem. Int. Ed. Engl. 1991, 30, 902; c) M. Driess, H. Grützmacher, ibid. 1996, 108, 900; and 1996, 35, 828; for the first structurally characterized Si=Si, Ge=Ge, and Sn=Sn double-bonded systems, see d) R. West, M. J. Fink, J. Michl, Science 1981, 214,1343; e) P. B. Hitchcock, M. F. Lappert, S. J. Miles, A. J. Thorne, J. Chem. Soc. Chem. Commun. 1984, 480; f) D. E. Goldberg, D. H. Harris, M. F. Lappert, K. M. Thomas, ibid. 1976, 261; g) M. Weidenbruch, H. Killian, K. Peters, H. G. von Schnering, H. Marsmann, Chem. Ber. 1995, 128, 973.
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5. For recent reviews, see a) G. Rabe, J. Michl, Chem. Rev. 1985, 85,419; b) T. Tsumaraya, S. A. Batcheller, S. Masamune, Angew. Chem. 1991, 103, 916; Angew. Chem. Int. Ed. Engl. 1991, 30, 902; c) M. Driess, H. Grützmacher, ibid. 1996, 108, 900; and 1996, 35, 828; for the first structurally characterized Si=Si, Ge=Ge, and Sn=Sn double-bonded systems, see d) R. West, M. J. Fink, J. Michl, Science 1981, 214,1343; e) P. B. Hitchcock, M. F. Lappert, S. J. Miles, A. J. Thorne, J. Chem. Soc. Chem. Commun. 1984, 480; f) D. E. Goldberg, D. H. Harris, M. F. Lappert, K. M. Thomas, ibid. 1976, 261; g) M. Weidenbruch, H. Killian, K. Peters, H. G. von Schnering, H. Marsmann, Chem. Ber. 1995, 128, 973.
6. For recent reviews, see a) G. Rabe, J. Michl, Chem. Rev. 1985, 85,419; b) T. Tsumaraya, S. A. Batcheller, S. Masamune, Angew. Chem. 1991, 103, 916; Angew. Chem. Int. Ed. Engl. 1991, 30, 902; c) M. Driess, H. Grützmacher, ibid. 1996, 108, 900; and 1996, 35, 828; for the first structurally characterized Si=Si, Ge=Ge, and Sn=Sn double-bonded systems, see d) R. West, M. J. Fink, J. Michl, Science 1981, 214,1343; e) P. B. Hitchcock, M. F. Lappert, S. J. Miles, A. J. Thorne, J. Chem. Soc. Chem. Commun. 1984, 480; f) D. E. Goldberg, D. H. Harris, M. F. Lappert, K. M. Thomas, ibid. 1976, 261; g) M. Weidenbruch, H. Killian, K. Peters, H. G. von Schnering, H. Marsmann, Chem. Ber. 1995, 128, 973.
7. For recent reviews, see a) G. Rabe, J. Michl, Chem. Rev. 1985, 85,419; b) T. Tsumaraya, S. A. Batcheller, S. Masamune, Angew. Chem. 1991, 103, 916; Angew. Chem. Int. Ed. Engl. 1991, 30, 902; c) M. Driess, H. Grützmacher, ibid. 1996, 108, 900; and 1996, 35, 828; for the first structurally characterized Si=Si, Ge=Ge, and Sn=Sn double-bonded systems, see d) R. West, M. J. Fink, J. Michl, Science 1981, 214,1343; e) P. B. Hitchcock, M. F. Lappert, S. J. Miles, A. J. Thorne, J. Chem. Soc. Chem. Commun. 1984, 480; f) D. E. Goldberg, D. H. Harris, M. F. Lappert, K. M. Thomas, ibid. 1976, 261; g) M. Weidenbruch, H. Killian, K. Peters, H. G. von Schnering, H. Marsmann, Chem. Ber. 1995, 128, 973.
8. For recent reviews, see a) G. Rabe, J. Michl, Chem. Rev. 1985, 85,419; b) T. Tsumaraya, S. A. Batcheller, S. Masamune, Angew. Chem. 1991, 103, 916; Angew. Chem. Int. Ed. Engl. 1991, 30, 902; c) M. Driess, H. Grützmacher, ibid. 1996, 108, 900; and 1996, 35, 828; for the first structurally characterized Si=Si, Ge=Ge, and Sn=Sn double-bonded systems, see d) R. West, M. J. Fink, J. Michl, Science 1981, 214,1343; e) P. B. Hitchcock, M. F. Lappert, S. J. Miles, A. J. Thorne, J. Chem. Soc. Chem. Commun. 1984, 480; f) D. E. Goldberg, D. H. Harris, M. F. Lappert, K. M. Thomas, ibid. 1976, 261; g) M. Weidenbruch, H. Killian, K. Peters, H. G. von Schnering, H. Marsmann, Chem. Ber. 1995, 128, 973.
9. For recent reviews, see a) G. Rabe, J. Michl, Chem. Rev. 1985, 85,419; b) T. Tsumaraya, S. A. Batcheller, S. Masamune, Angew. Chem. 1991, 103, 916; Angew. Chem. Int. Ed. Engl. 1991, 30, 902; c) M. Driess, H. Grützmacher, ibid. 1996, 108, 900; and 1996, 35, 828; for the first structurally characterized Si=Si, Ge=Ge, and Sn=Sn double-bonded systems, see d) R. West, M. J. Fink, J. Michl, Science 1981, 214,1343; e) P. B. Hitchcock, M. F. Lappert, S. J. Miles, A. J. Thorne, J. Chem. Soc. Chem. Commun. 1984, 480; f) D. E. Goldberg, D. H. Harris, M. F. Lappert, K. M. Thomas, ibid. 1976, 261; g) M. Weidenbruch, H. Killian, K. Peters, H. G. von Schnering, H. Marsmann, Chem. Ber. 1995, 128, 973.
10. a) H. Grützmacher, H. Pritzkow, F. T. Edelmann, Organometallics 1991, 10, 23;
11. b) U. Lay, H. Pritzkow, H. Grützmacher, J. Chem. Soc. Chem. Commun. 1992, 260.
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13. K. W. Klinkhammer, W. Schwarz, Angew. Chem. 1995, 107, 1448; Angew. Chem. Int. Ed. Engl. 1995, 34, 1334.
14. 13C) = 272.5 Hz]; UV/Vis (n-pentane): λ 586 nm; 1025 nm. Both compounds gave correct elemental analyses.
15. 2 at temperatures above room temperature, and the low solubility in inert solvents at low temperatures.
16. G. Trinquier, J. Am. Chem. Soc. 1991, 113, 144.
17. 2; all data] = 0.072. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication No. CCDC-100326. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: int. code + (44) 1223 336033; e-mail: deposit@ccdc.cam.ac.uk).
18. H. Jacobsen, T. Ziegler, J. Am. Chem. Soc. 1994, 116, 3667.
19. 4 were determined by CCD (Sn) and CCSD (Pb) calculations (Gaussian 94) with Stuttgart quasi-relativistic pseudopotentials [W. Kuechle, M. Dolg, H. Stoll, H. Preuss, J. Chem. Phys. 1991, 74, 1245] and extended basis sets for Sn and Pb: (4s4p2d)/[5s5p2d]; basis sets for H: (3s2p)/[4s2p] [T. H. Dunning, J. Chem. Phys. 1970, 19, 553]. The dimerization energies were calculated at the CCSD level and have been corrected with respect to basis set superposition errors (full Counterpoise method) and zero-point vibrations. The identification of local minima on the hypersurface was verified by frequency calculations [NIMAG = 0].
20. 4 were determined by CCD (Sn) and CCSD (Pb) calculations (Gaussian 94) with Stuttgart quasi-relativistic pseudopotentials [W. Kuechle, M. Dolg, H. Stoll, H. Preuss, J. Chem. Phys. 1991, 74, 1245] and extended basis sets for Sn and Pb: (4s4p2d)/[5s5p2d]; basis sets for H: (3s2p)/[4s2p] [T. H. Dunning, J. Chem. Phys. 1970, 19, 553]. The dimerization energies were calculated at the CCSD level and have been corrected with respect to basis set superposition errors (full Counterpoise method) and zero-point vibrations. The identification of local minima on the hypersurface was verified by frequency calculations [NIMAG = 0].
21. 2 using these methods elsewhere.
22. 2 using these methods elsewhere.