Abstract
Reactions of {(C6F5)Pt[S(CH2CH2-)2](μ-Cl)}2 and R3P yield the bis(phosphine) species trans-(C6F5)(R3P)2PtCl [R = Et (Pt'Cl), Ph, (p-CF3C6H4)3P; 88-81 %]. Additions of Pt'Cl and H(C≡C)nH (n = 1, 2; HNEt2, 20 mol % CuI) give Pt'C2H (37 %, plus Pt'I, 16 %) and Pt'C4H (88 %). Homocoupling of Pt'C4H under Hay conditions (O2, CuCl, TMEDA, acetone) gives Pt'C8Pt' (85 %), but Pt'C2H affords only traces of Pt'C4Pt'. However, condensation of Pt'C4H and Pt'Cl (HNEt2, 20 mol % CuI) yields Pt'C4Pt' (97 %). Hay heterocouplings of Pt'C4H or trans-(p-tol)(Ph3P)2Pt(C≡C)2H (Pt*C4H) and excess HC≡CSiEt3 give Pt'C6SiEt3 (76 %) or Pt*C6SiEt3 (89 %). The latter and wet n-Bu4N+ F- react to yield labile Pt*C6H (60 %). Hay homocouplings of Pt*C4H and Pt*C6H give Pt*C8Pt* (64 %) and Pt*C12Pt* (64 %). Reaction of trans-(C6F5)(p-tol3P)2PtCl (PtCl) and HC≡CH (HNEt2, 20 mol % CuI) yields only traces of PtC2H. However, an analogous reaction with HC≡CSiMe3 gives PtC2SiMe3 (75 %), which upon treatment with silica yields PtC2H (77 %). An analogous coupling of trans-(C6F5)(Ph3P)2PtCl with H(C≡C)2H gives trans-(C6F5)(Ph3P)2Pt(C≡C)2H (34 %). Advantages and disadvantages of the various trans-(Ar)(R3P)2Pt end-groups are analyzed.
Conference
International Symposium on Novel Aromatic Compounds (ISNA-12), International Symposium on Novel Aromatic Compounds, ISNA, Novel Aromatic Compounds, 12th, Awaji Island, Japan, 2007-07-22–2007-07-27
References
1. doi:10.1002/chem.200204741, W. Mohr, J. Stahl, F. Hampel, J. A. Gladysz. Chem.Eur. J. 9, 3324 (2003).Search in Google Scholar
2. doi:10.1002/chem.200600615, Q. Zheng, J. C. Bohling, T. B. Peters, A. C. Frisch, F. Hampel, J. A. Gladysz. Chem.Eur. J. 12, 6486 (2006).Search in Google Scholar
3. doi:10.1021/ja0716103, J. Stahl, W. Mohr, L. de Quadras, T. B. Peters, J. C. Bohling, J. M. Martin-Alvarez, G. R. Owen, F. Hampel, J. A. Gladysz. J. Am. Chem. Soc. 129, 8282 (2007).Search in Google Scholar
4. doi:10.1021/ja071612n, L. de Quadras, E. B. Bauer, W. Mohr, J. C. Bohling, T. B. Peters, J. M. Martin-Alvarez, F.Hampel, J. A. Gladysz. J. Am. Chem. Soc. 129, 8296 (2007).Search in Google Scholar
5. (a) doi:10.1039/b604465b, L. de Quadras, F. Hampel, J. A. Gladysz. Dalton Trans. 2929 (2006);Search in Google Scholar
5. (b) doi:10.1039/b708690n, L. de Quadras, E. B. Bauer, J. Stahl, F. Zhuravlev, F. Hampel, J. A. Gladysz. New. J. Chem. 31, 1594 (2007).Search in Google Scholar
6. (a) doi:10.1021/om0493558, G. R. Owen, J. Stahl, F. Hampel, J. A. Gladysz. Organometallics 23, 5889 (2004);Search in Google Scholar
6. (b) doi:10.1002/chem.200701268, G. R. Owen, J. Stahl, F. Hampel, J. A. Gladysz. Chem.Eur. J. 14, 73 (2008).Search in Google Scholar
7. doi:10.1021/om049354f, G. R. Owen, F. Hampel, J. A. Gladysz. Organometallics 23, 5893 (2004).Search in Google Scholar
8. doi:10.1021/om049353n, Q. Zheng, F. Hampel, J. A. Gladysz. Organometallics 23, 5896 (2004).Search in Google Scholar
9. Computational study: F. Zhuravlev, J. A. Gladysz. Chem.Eur. J. 10, 6510 (2004).Search in Google Scholar
10. (a) doi:10.1016/S0022-328X(99)00500-8, A. Klein, K.-W. Klinkhammer, T. Scheiring. J. Organomet. Chem. 592, 128 (1999);Search in Google Scholar
10. (b) doi:10.1021/om010984g, C. Muller, R. J. Lachicotte, W. D. Jones. Organometallics 21, 1190 (2002);Search in Google Scholar
10. (c) doi:10.1039/b207575j, W.-Y. Wong, C.-K. Wong, G.-L. Lu, K.-W. Cheah, J.-X. Shi, Z. Lin. J. Chem. Soc., Dalton Trans. 4587 (2002);Search in Google Scholar
10. (d) doi:10.1002/anie.200390360, V. W.-W. Yam, K. M.-C. Wong, N. Zhu. Angew. Chem., Int. Ed. 42, 1400 (2003);Search in Google Scholar
10. (e) doi:10.1002/ange.200390332, V. W.-W. Yam, K. M.-C. Wong, N. Zhu. Angew. Chem. 115, 1438 (2003).Search in Google Scholar
11. (a) doi:10.1021/ja992002t, M. I. Bruce, P. J. Low, K. Costuas, J.-F. Halet, S. P. Best, G. A. Heath. J. Am. Chem. Soc. 122, 1949 (2000);Search in Google Scholar
11. (b) doi:10.1016/S0022-328X(03)00709-5, F. Coat, F. Paul, C. Lapinte, L. Toupet, K.Costuas, J.-F. Halet. J. Organomet. Chem. 683, 368 (2003);Search in Google Scholar
11. (c) doi:10.1021/ja035434j, G.-L. Xu, G. Zou, Y.-H. Ni, M.C. DeRosa, R. J. Crutchley, T. Ren. J. Am. Chem. Soc. 125, 10057 (2003);Search in Google Scholar
11. (d) doi:10.1039/b615578b, K. Venkatesan, O. Blacque, H. Berke. Dalton Trans. 1091 (2007).Search in Google Scholar
12. (a) doi:10.1016/S0065-3055(03)50004-1, M. I. Bruce, P. J. Low. Adv. Organomet. Chem. 50, 179 (2004);Search in Google Scholar
12. (b) F. Paul, C. Lapinte. In Unusual Structures and Physical Properties in Organometallic Chemistry, M.Gielen, R. Willem, B. Wrackmeyer (Eds.), pp. 220-291, John Wiley, New York (2002);Search in Google Scholar
12. (c) doi:10.1021/cr030041o, S.Szafert, J. A. Gladysz. Chem. Rev. 103, 4175 (2003);Search in Google Scholar
12. (d) doi:10.1021/cr068016g, S. Szafert, J. A. Gladysz. Chem. Rev. 106, PR1 (2006).Search in Google Scholar
13. J. Stahl. Doctoral thesis, Universitat Erlangen-Nurnberg (2003).Search in Google Scholar
14. L. de Quadras. Doctoral thesis, Universitat Erlangen-Nurnberg (2006).Search in Google Scholar
15. doi:10.1021/om00017a027, K. Sunkel, U. Birk, C. Robl. Organometallics 13, 1679 (1994).Search in Google Scholar
16. R. Uson, J. Fornies, P. Espinet, G. Alfranca. Synth. React. Inorg. Met.-Org. Chem. 10, 579 (1980).Search in Google Scholar
17. (a) doi:10.1021/om030195u, E. B. Bauer, S. Szafert, F. Hampel, J. A. Gladysz. Organometallics 22, 2184 (2003);Search in Google Scholar
17. (b) doi:10.1039/b400156g, T.Shima, E. B. Bauer, F. Hampel, J. A. Gladysz. Dalton Trans. 1012 (2004);Search in Google Scholar
17. (c) doi:10.1002/adsc.200404026, E. B. Bauer, F.Hampel, J. A. Gladysz. Adv. Synth. Catal. 346, 812 (2004);Search in Google Scholar
17. (d) doi:10.1016/j.molcata.2005.12.047, N. Lewanzik, T. Oeser, J.Blumel, J. A. Gladysz. J. Mol. Catal. A 254, 20 (2006);Search in Google Scholar
17. (e) doi:10.1016/j.jorganchem.2006.12.023, L. de Quadras, J. Stahl, F. Zhuravlev, J. A. Gladysz. J. Organomet. Chem. 692, 1859 (2007).Search in Google Scholar
18. doi:10.1039/jr9650005275, D. T. Rosevear, F. G. A. Stone. J. Chem. Soc. 5275 (1965).Search in Google Scholar
19. doi:10.1039/j19660001326, F. J. Hopton, A. J. Rest, D. T. Rosevear, F. G. A. Stone. J. Chem. Soc. A 1326 (1966).Search in Google Scholar
20. doi:10.1016/S0022-328X(00)95093-9, R. Eastmond, T. R. Johnson, D. R. M. Walton. J. Organomet. Chem. 50, 87 (1973).Search in Google Scholar
21. doi:10.1021/ic50052a015, S. O. Grim, R. L. Keiter, W. McFarlane. Inorg. Chem. 6, 1133 (1967).Search in Google Scholar
22. (a) doi:10.1002/1521-3773(20000804)39:15<2632::AID-ANIE2632>3.0.CO;2-F, P. Siemsen, R. C. Livingston, F. Diederich. Angew. Chem., Int. Ed. 39, 2632 (2000);Search in Google Scholar
22. (b) doi:10.1002/1521-3757(20000804)112:15<2740::AID-ANGE2740>3.0.CO;2-F, P.Siemsen, R. C. Livingston, F. Diederich. Angew. Chem. 112, 2740 (2000).Search in Google Scholar
23. doi:10.1016/S0022-328X(01)01311-0, T. B. Peters, Q. Zheng, J. Stahl, J. C. Bohling, A. M. Arif, F. Hampel, J. A. Gladysz. J. Organomet. Chem. 641, 53 (2002).Search in Google Scholar
24. W. Mohr, T. B. Peters, J. C. Bohling, F. Hampel, A. M. Arif, J. A. Gladysz. C. R. Chemie 5, 111 (2002).10.1016/S1631-0748(02)01351-6Search in Google Scholar
25. doi:10.1039/b605509e, G. Vives, A. Carella, S. Sistach, J.-P. Launey, G. Rapenne. New J. Chem. 30, 1429 (2006).Search in Google Scholar
26. L. de Quadras, A. Hobbs, H. Kuhn, F. Hampel, K. S. Schanze. Submitted for publication.Search in Google Scholar
27. R. Uson, J. Fornies. Adv. Organomet. Chem. 28, 219 (1988).Search in Google Scholar
28. (a) doi:10.1039/b406892k, K. Reichenbacher, H. I. Suss, J. Hulliger. Chem. Soc. Rev. 34, 22 (2005);Search in Google Scholar
28. (b) doi:10.1021/jo061235h, B. W. Gung, J.C. Amicangelo. J. Org. Chem. 71, 9261 (2006).Search in Google Scholar
29. doi:10.1002/1099-0682(200104)2001:4<925::AID-EJIC925>3.0.CO;2-N, W. Mohr, G. A. Stark, H. Jiao, J. A. Gladysz. Eur. J. Inorg. Chem. 925 (2001).Search in Google Scholar
30. T. B. Patrick. In Chemistry of Organic Fluorine Compounds II, M. Hudlicky, A. E. Pavlath (Eds.), ACS Monograph 187, pp. 501-524, American Chemical Society, Washington, DC (1995).Search in Google Scholar
31. (a) doi:10.1002/anie.199511711, H. K. Cammenga, M. Epple. Angew. Chem., Int. Ed. Engl. 34, 1171 (1995);Search in Google Scholar
31. (b) doi:10.1002/ange.19951071105, H. K. Cammenga, M. Epple. Angew. Chem. 107, 1284 (1995). The Te values best represent the temperature of the phase transition or exotherm.Search in Google Scholar
32. (b) For virtual triplets [W. H. Hersh. J. Chem. Educ. 74, 1485 (1997)], the J values represent the apparent couplings between adjacent peaks. (c) The 19F{1H} NMR spectra were referenced to external C6F6 (d, -162.00 ppm), and the 195Pt{1H} spectra to external K2PtCl4 (saturated D2O solution; d, 0.00 ppm).Search in Google Scholar
33. This coupling represents a satellite (d, 195Pt = 33.8 %), and is not reflected in the peak multiplicity given.Search in Google Scholar
34. m/z (FAB, 3-NBA) for the most intense peak of the isotope envelope. For some complexes, a background peak from the matrix was the most intense; in these cases, no ion of 100% intensity is specified.Search in Google Scholar
35. H. D. Verkruijsse, L. Brandsma. Synth. Commun. 21, 657 (1991). The H(C∫C)2H concentration was calculated from the mass increase of the THF solution. CAUTION: this compound is explosive and literature precautions should be followed.Search in Google Scholar
36. Platinum coupling would be expected based upon spectra of related compounds; however, the signal/noise ratio was not sufficient.Search in Google Scholar
37. This complex was too insoluble for a 13C NMR spectrum to be recorded.Search in Google Scholar
38. doi:10.1021/jo00008a036, W.-N. Chou, M. Pomerantz. J. Org. Chem. 56, 2762 (1991).Search in Google Scholar
© 2013 Walter de Gruyter GmbH, Berlin/Boston