A triphosphete and a spirocyclic cation with a PP4 skeleton and a 10e spiro P atom

Angewandte Chemie (International Edition in English)

Volumn 35, Issue 19, 1996, Pages 2242-2244

  Karsch, Hans H ^a   Witt, Eva ^a   Ekkehardt Hahn, F ^b  

^a TECHNICAL UNIVERSITY OF MUNICH   (Germany)

^b FREIE UNIVERSITÄT BERLIN   (Germany)

Author keywords

Heterocycles; Low valent compounds; Phosphorus compounds; Redox processes

Indexed keywords

EID: 0030472518     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199622421     Document Type: Article

References (48)

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5. a) E = P: H. H. Karsch, E. Witt, A. Schneider, E. Herdtweck, M. Heckel, Angew. Chem. 1995, 107, 628-631; Angew. Chem. Int. Ed. Engl. 1995, 34, 557-560;
6. a) E = P: H. H. Karsch, E. Witt, A. Schneider, E. Herdtweck, M. Heckel, Angew. Chem. 1995, 107, 628-631; Angew. Chem. Int. Ed. Engl. 1995, 34, 557-560;
7. b) E = As: H. H. Karsch, A. Schier, J. Chem. Soc. Chem. Commun. 1994, 2703-2704.
8. G. Becker, W. Becker, G. Uhl, Z. Anorg. Allg. Chem. 1984, 518, 21-35.
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14. 2): H. H. Karsch, B. Deubelly, G. Müller, J. Chem. Soc. Chem. Commun. 1988, 517-518. In contrast to earlier reports (H. H. Karsch, B. Deubelly, G. Grauvogel, G. Müller, J. Organomet. Chem. 1993, 459, 95-105), this step can be ruled out for the analog with phenyl substituents. See also: P. Braunstein, R. Hasselbring, A. DeCian. J. Fischer, Bull. Soc. Chim. Fr. 1995, 132, 691-695. Accordingly, 3 does not react with excess 1 under the present conditions, as can be demonstrated independently.
15. 2): H. H. Karsch, B. Deubelly, G. Müller, J. Chem. Soc. Chem. Commun. 1988, 517-518. In contrast to earlier reports (H. H. Karsch, B. Deubelly, G. Grauvogel, G. Müller, J. Organomet. Chem. 1993, 459, 95-105), this step can be ruled out for the analog with phenyl substituents. See also: P. Braunstein, R. Hasselbring, A. DeCian. J. Fischer, Bull. Soc. Chim. Fr. 1995, 132, 691-695. Accordingly, 3 does not react with excess 1 under the present conditions, as can be demonstrated independently.
16. 2): H. H. Karsch, B. Deubelly, G. Müller, J. Chem. Soc. Chem. Commun. 1988, 517-518. In contrast to earlier reports (H. H. Karsch, B. Deubelly, G. Grauvogel, G. Müller, J. Organomet. Chem. 1993, 459, 95-105), this step can be ruled out for the analog with phenyl substituents. See also: P. Braunstein, R. Hasselbring, A. DeCian. J. Fischer, Bull. Soc. Chim. Fr. 1995, 132, 691-695. Accordingly, 3 does not react with excess 1 under the present conditions, as can be demonstrated independently.
17. 7 only reflects the chosen stochiometry and is also in agreement with the corresponding formulation in ref.[1].
18. 0)] and 577 [583] variables. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) on quoting the depository number CSD-59325.
19. 2[5b].
20. Here the extent of a possible delocalization of charges in the sense of heteroallyl cation/P anion is not considered, cf.: G. Alcaraz, A. Baceiredo, M. Niger, W. W. Schoeller, G. Bertrand, Inorg. Chem. 1996, 35, 2458-2462.
21. -.
22. This representation takes account of the (otherwise obsolete) assignment of the oxidation state of +1 between two identical elements for the bivalent P and As atoms.
23. o)] and 799 variables. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) on quoting the depository number CSD-59325.
24. o)] and 799 variables. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) on quoting the depository number CSD-59325.
25. o)] and 799 variables. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) on quoting the depository number CSD-59325.
26. o)] and 799 variables. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) on quoting the depository number CSD-59325.
27. o)] and 799 variables. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) on quoting the depository number CSD-59325.
28. H. H. Karsch, U. Keller, S. Gamper, G. Müller, Angew. Chem. 1990, 102, 297-298, Angew. Chem. Int. Ed. Engl. 1990, 29, 295-296.
29. H. H. Karsch, U. Keller, S. Gamper, G. Müller, Angew. Chem. 1990, 102, 297-298, Angew. Chem. Int. Ed. Engl. 1990, 29, 295-296.
30. H. H. Karsch, D. Deubelly, G. Hanika, J. Riede, G. Müller, J. Organomet. Chem. 1988, 344, 153-161.
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33. 2 see: A. L. Balch, D. E. Oram, Inorg. Chem. 1987, 26, 1906-1912.
34. 2 see: A. L. Balch, D. E. Oram, Inorg. Chem. 1987, 26, 1906-1912.
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39. b) R. Weiss, S. Engel, Angew. Chem. 1992, 104, 239-240, Angew. Chem. Int. Ed. Engl. 1992, 31, 216-217.
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43. + [1b] the phosphorus has a negative formal charge. The representation as a phosphane-base adduct of a triono-substituted phosphane[20a] with partial charge compensation by two carbanion functions is very artificial. However, it does illustrate that 4 can also be regarded as the first phosphane-phosphane adduct - if only for very specific phosphanes.
44. K. B. Dillon, Chem. Rev. 1994, 94, 1441-1456.
45. L. Lamandé, K. Dillon, R. Wolf, Phosphorus, Sulfur Silicon Relat. Elem. 1995, 103, 1-24.
46. H. H. Karsch, G. Grauvogl, P. Mikulcik, P. Bissinger, G. Müller, J. Organomet. Chem. 1994, 465, 65-71.
47. Note added in proof (August 15, 1996): Accordingly, in the first report on tetraphosphete derivatives published since submission of this manuscript the phosphonium centers each bear two amino groups: W. Frank, V. Petry, E. Gerwalin, G. J. Reiss, Angew. Chem. 1996, 108, 1616-1618; Angew. Chem. Int. Ed. Engl. 1996, 35, 1512-1514.
48. Note added in proof (August 15, 1996): Accordingly, in the first report on tetraphosphete derivatives published since submission of this manuscript the phosphonium centers each bear two amino groups: W. Frank, V. Petry, E. Gerwalin, G. J. Reiss, Angew. Chem. 1996, 108, 1616-1618; Angew. Chem. Int. Ed. Engl. 1996, 35, 1512-1514.