1H, 13C, 15N NMR and 13C, 15N CPMAS studies of cobalt(III)-chloride-pyridine complexes, spontaneous py → Cl substitution in trans-[Co(py)4Cl2]Cl, and a new synthesis of mer-[Co(py)3Cl3]

• Authors: Leszek Pazderski , Andrzej Surdykowski , Małgorzata Pazderska-Szabłowicz , Jerzy Sitkowski , Lech Kozerski , Bohdan Kamieński , Edward Szłyk
• Languages of publication: EN

Abstracts

EN

trans-[Co(py)4Cl2]Cl·6H2O, mer-[Co(py)3Cl3] and mer-[Co(py)3(CO3)Cl] were studied by UV-Vis, far-IR and 1H, 13C, 15N NMR. The formation of Co-N bonds lead to variable in sign and magnitude changes of 1H NMR chemical shifts, heavily dependent on proton position, coordination sphere geometry and character of auxiliary ligands. 13C nuclei were deshielded upon Co(III) coordination, while 15N NMR studies exhibited ca. 85–110 ppm shielding effects (ca. 15–25 ppm more expressed for nitrogens trans to N than trans to Cl or O). 13C and 15N CPMAS spectra revealed a slight inequivalency of formally identical Co-py bonds in trans-[Co(py)4Cl2]Cl·6H2O and mer-[Co(py)3Cl3], suggesting for the latter complex an existence of distortion isomers. In chloroform, a spontaneous trans-[Co(py)4Cl2]Cl → mer-[Co(py)3Cl3] + py reaction was monitored by 1H NMR and UV-Vis. This process of py → Cl substitution allowed the design of a more convenient and efficient method of mer-[Co(py)3Cl3] preparation. [...]

Keywords

EN

Co(III) complexes; Pyridine complexes; 15N NMR; 15N CPMAS; NMR coordination shifts

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2008
• Volume: 6
• Issue: 1
• Pages: 55-64

Dates

published

1 - 3 - 2008

online

1 - 3 - 2008

Contributors

author

Leszek Pazderski

• Faculty of Chemistry, Nicholas Copernicus University, Gagarina 7, PL-87100, Toruń, Poland

author

Andrzej Surdykowski

• Faculty of Chemistry, Nicholas Copernicus University, Gagarina 7, PL-87100, Toruń, Poland

author

Małgorzata Pazderska-Szabłowicz

• Faculty of Chemistry, Nicholas Copernicus University, Gagarina 7, PL-87100, Toruń, Poland

author

Jerzy Sitkowski

author

Lech Kozerski

author

Bohdan Kamieński

• Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, PL-01224, Warsaw, Poland

author

Edward Szłyk

• Faculty of Chemistry, Nicholas Copernicus University, Gagarina 7, PL-87100, Toruń, Poland

References

• [1] A. Werner, R. Feenstra, Ber. 39, 1538 (1906) (in German)
• [2] T. Laier, C.E. Schäffer, J. Springborg, Acta Chem. Scand. A 34, 343 (1980) [Crossref]
• [3] L.I. Katzin, J.R. Ferraro, E. Gebert, J. Am. Chem. Soc. 72, 5471 (1950) http://dx.doi.org/10.1021/ja01168a026[Crossref]
• [4] M. Gerloch, R.F. McMeeking, A.M. White, J. Chem. Soc. Dalton Trans. 655 (1976) [Crossref]
• [5] A.V. Babayeva, I.B. Baranovskii, Zh. Neorg. Khim. 4, 755 (1959) (in Russian)
• [6] C.N. Elgy, C.F. Wells, J. Chem. Soc. Dalton Trans. 2405 (1980) [Crossref]
• [7] W.L. Purcell, Inorg. Chem. 25, 4068 (1986) http://dx.doi.org/10.1021/ic00243a002[Crossref]
• [8] M. Mori, M. Shibata, E. Kyuono, T. Adachi, Bull. Chem. Soc. Jpn. 29, 883 (1956) http://dx.doi.org/10.1246/bcsj.29.883[Crossref]
• [9] J. Springborg, C.E. Schäffer, Acta Chem. Scand. 27, 3312 (1973) [Crossref]
• [10] N.N. Greenwood, A. Earnshaw, In: Chemistry of the Elements (Pergamon Press, Oxford, 1984) 1301
• [11] A.V. Ablov, Zh. Neorg. Khim., 6, 309 (1961) (in Russian)
• [12] A.A. Vlček, Inorg. Chem. 6, 1425 (1967) http://dx.doi.org/10.1021/ic50053a028[Crossref]
• [13] H. Xu, J. Ji, Z. Wu, J. Zou, Z. Xu, X. You, Polyhedron 12, 2261 (1993) http://dx.doi.org/10.1016/S0277-5387(00)88265-0[Crossref]
• [14] Yu.N. Shevchenko, N.B. Golub, Ukr. Khim. Zh. 48, 345 (1982) (in Russian)
• [15] T. Mallen, K.E. Hyde, Inorg. Chim. Acta 130, 177 (1987) http://dx.doi.org/10.1016/S0020-1693(00)90432-8[Crossref]
• [16] K.E. Hyde, G.M. Harris, J. Phys. Chem. 82, 2204 (1978) http://dx.doi.org/10.1021/j100509a011[Crossref]
• [17] D.A. Gooden, H.A. Ewart, K.E. Hyde, Inorg. Chim. Acta 166, 263 (1989) http://dx.doi.org/10.1016/S0020-1693(00)80819-1[Crossref]
• [18] J. Glerup, C.E. Schäffer, J. Springborg, Acta Chem. Scand. A 32, 673 (1978) http://dx.doi.org/10.3891/acta.chem.scand.32a-0673[Crossref]
• [19] A.V. Babayeva, I.B. Baranovskii, Zh. Neorg. Khim. 6, 225 (1961) (in Russian)
• [20] M.A.S. Goher, R.J. Wang, T.C.W. Mak, Polyhedron 11, 829 (1992) http://dx.doi.org/10.1016/S0277-5387(00)86018-0[Crossref]
• [21] Cambridge Structural Database (Cambridge Crystallographic Data Centre, Cambridge, 2007)
• [22] J.V. Brencic, Z. Anorg. Allg. Chem. 403, 218 (1974) (in German) http://dx.doi.org/10.1002/zaac.19744030218[Crossref]
• [23] S.A. Howard, K.I. Hardcastle, J. Crystallogr. Spectrosc. Res. 15, 643 (1985) http://dx.doi.org/10.1007/BF01164777[Crossref]
• [24] L. Pazderski, E. Szłyk, J. Sitkowski, B. Kamieński, L. Kozerski, J. Toušek, R. Marek, Magn. Reson. Chem. 44, 163 (2006) http://dx.doi.org/10.1002/mrc.1740[Crossref]
• [25] L. Pazderski, Polish J. Chem. 80, 1083 (2006)
• [26] L. Pazderski, J. Toušek, J. Sitkowski, L. Kozerski, R. Marek, E. Szłyk, Magn. Reson. Chem. 45, 24 (2007) http://dx.doi.org/10.1002/mrc.1910[Crossref]
• [27] L. Pazderski, J. Toušek, J. Sitkowski, L. Kozerski, E. Szłyk, Magn. Reson. Chem. 45, 1045 (2007) http://dx.doi.org/10.1002/mrc.2104[Crossref]
• [28] L. Pazderski, J. Toušek, J. Sitkowski, L. Kozerski, E. Szłyk, Magn. Reson. Chem. 45, 1059 (2007) http://dx.doi.org/10.1002/mrc.2105[Crossref]
• [29] K. Nakamoto, In Infrared and Raman Spectra of Inorganic and Coordination Compounds Part A Ed. 5th, (Wiley, New York 1997), 346.
• [30] R.J.H. Clark, C.S. Williams, Inorg. Chem. 4, 350 (1965) http://dx.doi.org/10.1021/ic50025a020[Crossref]
• [31] F. Herbelin, J.D. Herbelin, J.P. Mathieu, H. Poulet, Spectrochim. Acta 22, 1515 (1966) http://dx.doi.org/10.1016/0371-1951(66)80146-7[Crossref]
• [32] R.D. Gillard, T. Heaton, J. Chem. Soc. A 451 (1969) [Crossref]
• [33] G. Daffner, D.A. Palmer, H. Kelm, Inorg. Chim. Acta 61, 57 (1982) http://dx.doi.org/10.1016/S0020-1693(00)89119-7[Crossref]
• [34] M. Goldstein, W.D. Unsworth, Spectrochim. Acta A 28, 1297 (1972) http://dx.doi.org/10.1016/0584-8539(72)80099-0[Crossref]
• [35] D.A. Thornton, Coord. Chem. Rev. 104, 251 (1990) http://dx.doi.org/10.1016/0010-8545(90)80044-T[Crossref]
• [36] I.I. Bhayat, W.R. McWhinnie, Spectrochim. Acta 28, 743 (1972) http://dx.doi.org/10.1016/0584-8539(72)80043-6[Crossref]
• [37] F. Bottomley, M. Mukaida, J. Chem. Soc. Dalton Trans. 1933 (1982) [Crossref]
• [38] A.M. El-Hendawy, W.P. Griffith, F.I. Taha, M.N. Moussa, J. Chem. Soc. Dalton Trans. 901 (1989) [Crossref]
• [39] B.J. Coe, T.J. Meyer, P.S. White, Inorg. Chem. 34, 593 (1995) http://dx.doi.org/10.1021/ic00107a011[Crossref]
• [40] K.R. Seddon, J.E. Turp, E.C. Constable, O. Wernberg, J. Chem. Soc. Dalton Trans. 293 (1987) [Crossref]
• [41] In Handbook of Chemistry and Physics, Ed. 85th (CRC Press, Boca-Raton, 2004-05) 12, 14.
• [42] N.C. Payne, M.E. Tkachuk, Chirality 1, 284 (1989) http://dx.doi.org/10.1002/chir.530010407[Crossref]
• [43] W.T. Wong, T.C. Lau, Acta Crystallogr. C 50, 1406 (1994) http://dx.doi.org/10.1107/S0108270194002088[Crossref]
• [44] M.R.J. Elsegood, D.A. Tocher, Acta Crystallogr. C 51, 40 (1995) http://dx.doi.org/10.1107/S0108270194006451[Crossref]
• [45] H.H. Drews, W. Preetz, Z. Anorg. Allg. Chem. 623, 509 (1997) (in German) http://dx.doi.org/10.1002/zaac.19976230180[Crossref]
• [46] F.A. Mautner, Cryst. Res. Technol. 26, 883 (1991) http://dx.doi.org/10.1002/crat.2170260713[Crossref]
• [47] M.A.S. Goher, N.A. Al-Salem, F.A. Mautner, Polyhedron 16, 3747 (1997) http://dx.doi.org/10.1016/S0277-5387(97)00160-5[Crossref]
• [48] G.F. Wang, F. Ji, X.L. Zhu, G.X. Wang, K.B. Yu, Wuji Huaxue Xuebao 15, 435 (1999) (in Chinese) - Chem. Abstr. 131, 193324 (1999)
• [49] D.V. Soldatov, Y. Lipkovski, Zh. Strukt. Khim. 36, 905 (1995) (in Russian)
• [50] G.J. Long, P.J. Clarke, Inorg. Chem. 17, 1394 (1978) http://dx.doi.org/10.1021/ic50184a002[Crossref]
• [51] D.V. Soldatov, Y. Lipkovski, Zh. Strukt. Khim. 36, 1070 (1995) (in Russian)
• [52] D.V. Soldatov, V.A. Logvinenko, Y.A. Dyadin, Y. Lipkowski, K. Suvinska, Zh. Strukt. Khim. 40, 935 (1999) (in Russian)
• [53] G.C. Dobinson, R. Mason, D.R. Russell, Chem. Commun. 62 (1967)
• [54] J. Roziere, M.S. Lehman, J. Potier, Acta Crystallogr. B 35, 1099 (1979) http://dx.doi.org/10.1107/S0567740879005653[Crossref]
• [55] R.D. Gillard, L.R. Hanton, S.H. Mitchell, Polyhedron 9, 2127 (1990) http://dx.doi.org/10.1016/S0277-5387(00)84042-5[Crossref]
• [56] R.D. Gillard, S.H. Mitchell, P.A. Williams, R.S. Vagg, J. Coord. Chem. 13, 325 (1984) http://dx.doi.org/10.1080/00958978408073886[Crossref]
• [57] H.L. Laity, M.R. Taylor, Acta Crystallogr. C. 51, 1791 (1995) http://dx.doi.org/10.1107/S0108270195004227[Crossref]
• [58] E. Szłyk, L. Pazderski, I. łakomska, A. Wojtczak, L. Kozerski, J. Sitkowski, B. Kamieński, H. Günther, Polyhedron 22, 391 (2003) http://dx.doi.org/10.1016/S0277-5387(02)01340-2[Crossref]
• [59] P. Pullmann, K. Hensen, Z. Naturforsch. B 37, 1312 (1982) (in German)
• [60] K.L. Sorensen, J.W. Ziller, N.M. Doherty, Acta Crystallogr. C 50, 407 (1994) http://dx.doi.org/10.1107/S0108270193005268[Crossref]
• [61] K.R. Acharya, S.S. Tavale, T.N. Guru Row, Acta Crystallogr. C 40, 1327 (1984) http://dx.doi.org/10.1107/S0108270184007848[Crossref]
• [62] M. Melnik, Coord. Chem. Rev. 47, 239 (1982) http://dx.doi.org/10.1016/0010-8545(82)85033-9[Crossref]
• [63] W.L Steffen, G.J. Palenik, Acta Crystallogr. B 32, 298 (1976) http://dx.doi.org/10.1107/S0567740876002859[Crossref]
• [64] J. Anbei, C. Krüger, B. Pfeil, Acta Crystallogr. C 43, 2334 (1987) http://dx.doi.org/10.1107/S0108270187087857[Crossref]
• [65] C.N. Elgy, C.F. Wells, J. Chem. Soc. Dalton Trans. 1617 (1982) [Crossref]
• [66] C.N. Elgy, C.F. Wells, J. Chem. Soc. Faraday Trans I 79, 2367 (1983) http://dx.doi.org/10.1039/f19837902367[Crossref]

Identifiers

DOI

10.2478/s11532-007-0063-3