B. Machura et al. / Polyhedron 30 (2011) 354–363
363
comprise all the experimental absorption bands, thus the shortest
References
wavelength experimental bands of 1 and 2 are not assigned to the
calculated transitions. As the solution spectra of PPh3 and 4,7-di-
phenyl-1,10-phenanthroline exhibit intense absorption bands in
300–200 nm region, some additional intraligand and interligand
transitions are expected to be found at higher energies in the cal-
culations for 1 and 2.
In the visible region complex 1 displays multiple transitions
of moderate intensity in the form of peaks and shoulders. The
broad and asymmetric longest wavelength experimental band
with maximum at 624.3 nm is assigned to the transitions of
[1] U. Abram, in: J.A. McCleverty, T.J. Meyer (Eds.), Comprehensive Coordination
Chemistry, vol. 5, second ed., Elsevier, 2003, pp. 271–402 (Chapter 5.3).
[2] J.R. Dilworth, S.J. Parrott, Chem. Soc. Rev. 27 (1998) 43.
[3] P. Blower, Dalton Trans. (2006) 1705.
[4] R.L. Richards, Coord. Chem. Rev. 154 (1996) 83.
[5] M.D. Fryzuk, S.A. Johnson, Coord. Chem. Rev. 200–202 (2000) 379.
[6] A.J.L. Pombeiro, M.F.C. Guedes da Silva, R.A. Michelin, Coord. Chem. Rev. 218
(2001) 43.
[7] S. Das, I. Chakraborty, A. Chakravorty, Polyhedron 22 (2003) 901.
[8] I. Chakraborty, S. Bhattacharyya, S. Banerjee, B.K. Dirghang, A. Chakravorty, J.
Chem. Soc., Dalton Trans. (1999) 3747.
[9] S. Bhattacharyya, I. Chakraborty, B.K. Dirghangi, A. Chakravorty, Chem.
Commun. (2000) 1813.
[10] S. Sengupta, J. Gangopadhyay, A. Chakravorty, Dalton Trans. (2003) 4635.
[11] S. Bhattacharyya, I. Chakraborty, B.K. Dirghangi, A. Chakravorty, Inorg. Chem.
40 (2001) 286.
d/
p(Cl) ?
p
*(dpphen)/d type. They can be seen as mixed dRe
?
p*(dpphen) (MLCT), d ? d (LF) and
p
(Cl) ? *(dpphen) (LLCT) or
p
a delocalised MLLCT (metal–ligand-to-ligand CT) description can
be used. The transitions leading to the experimental bands at
492.0 and 451.5 nm have also delocalised MLLCT character. The
experimental absorption bands at 378.8 and 282.5 nm is mainly
attributed to Ligand–Ligand Charge Transfer and interligand (IL)
transitions. However, some contribution of the Ligand–Metal
Charge Transfer from the triphenylphosphine, chloride and dpphen
orbitals to the d rhenium orbitals in these bands is also confirmed
by the calculations.
The rhenium(IV) complex in which MLCT transitions are ex-
pected to shift to much higher energies, do not display any band
in the visible region except for two weak shoulders around 450
and 410 nm. The transitions leading to these absorptions can be as-
signed to Ligand–Metal Charge Transfer transitions occurring from
the Cl and dpphen ligands to the d rhenium orbitals and Ligand–
[12] J. Gangopadhyay, S. Sengupta, S. Bhattacharyya, I. Chakraborty, A. Chakravorty,
Inorg. Chem. 41 (2002) 2616.
´
[13] B. Machura, A. Switlicka, M. Wolff, J. Kusz, R. Kruszynski, Polyhedron 28 (2009)
3999.
[14] C.J. Cramer, D.G. Truhlar, Phys. Chem. Chem. Phys. 11 (2009) 10757.
[15] W. Koch, M.C. Holthausen, A Chemist’s Guide to Density Functional Theory,
Wiley-VCH, 2000.
[16] CRYSALIS RED, Oxford Diffraction Ltd., Version 1.171.33.46, 2009.
[17] G.M. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112.
[18] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann,
O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K.
Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, Gaussian 03, Revision B.03, Gaussian, Inc., Pittsburgh, PA, 2003.
[19] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82 (1985) 299.
Ligand Charge Transfer transitions (p(dpphen) ? p*(dpphen)). The
absorption band at 290.3 nm results from Ligand–Ligand Charge
Transfer and interligand (IL) transitions.
[20] K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 97 (1997)
119.
4. Conclusions
[21] P.M.W. Gill, B.G. Johnson, J.A. Pople, M.J. Frisch, Chem. Phys. Lett. 197 (1992)
499.
[22] M.E. Casida, in: J.M. Seminario (Ed.), Recent Developments and Applications in
Modern Density Functional Theory, Theoretical and Computational Chemistry,
vol. 4, Elsevier, Amsterdam, 1996.
[23] M. Cossi, G. Scalmani, N. Rega, V. Barone, J. Chem. Phys. 117 (2002) 43.
[24] E. König, Magnetic Properties of Coordination and Organometallic Transition
Metal Compounds, Springer-Verlag, Berlin, 1966.
[25] W.A. Herrmann, W.R. Thiel, E. Herdtweck, Chem. Ber. 123 (1990) 271.
[26] E.C.B. Alegria, L.M.D.R.S. Martins, M. Haukka, A.J.L. Pombeiro, Dalton Trans.
(2006) 4954.
[27] J. Martinez-Lillo, D. Armentano, G. De Munno, J. Faus, Polyhedron 27 (2008)
1447.
[28] R. Chiozzone, R. Gonzalez, C. Kremer, M.F. Cerda, D. Armentano, G. De Munno,
J. Martinez-Lillo, J. Faus, Dalton Trans. (2007) 653.
[29] M.N. Sokolov, N.E. Fedorova, E.V. Peresypkina, R. Patow, V.E. Federov, D.
Fenske, Inorg. Chim. Acta 358 (2005) 3914.
[30] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, fourth ed., Wiley-Interscience, New York, 1986.
[31] G.A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures, Springer-
Verlag, 1994.
The oxochelate [ReO(OMe)Cl2(dpphen)] has been shown to be
an excellent oxygen atom transfer reagent. In a mixture dichloro-
methane/acetone it undergoes facile transformation to [Re-
Cl3(dpphen)(PPh3)]ꢀMe2CO, whereas the same reaction carried
out in chloroform leads to [ReCl4(dpphen)]ꢀCHCl3. The Re(III) and
Re(IV) compounds have been characterised structurally and spec-
troscopically, as well as by magnetic measurements. The magnetic
behaviour of [ReIIICl3(dpphen)(PPh3)]ꢀMe2CO is characteristic of
mononuclear complexes with d4 low-spin octahedral Re(III) com-
plexes (3T1g ground state) and arise because of the large spin–orbit
coupling. For complex [ReCl4(dpphen)]ꢀCHCl3 the results of calcu-
lations revealed value of zero-field splitting parameter
D = 10.8 cmꢁ1, g|| = 2.49 and g\ = 1.51.
Acknowledgements
[32] G.R. Desiraju, T. Steiner, The Weak Hydrogen Bond in Structural Chemistry and
Biology, Oxford University Press, 1999.
[33] L.E. Helberg, S.D. Orth, M. Sabat, W.D. Harman, Inorg. Chem. 35 (1996) 5584.
[34] J. Rall, F. Weingart, D.M. Ho, M.J. Heeg, F. Tisato, E. Deutsch, Inorg. Chem. 33
(1994) 3442.
[35] S.D. Orth, J. Barrerra, M. Sabat, W.D. Harman, Inorg. Chem. 33 (1994) 3026.
[36] B. Coutinho, J.R. Dilworth, P. Jobanputra, R.M. Thompson, S. Schmidt, J. Strähle,
C.M. Archer, J. Chem. Soc., Dalton Trans. (1995) 1663.
The GAUSSIAN-03 calculations were carried out in the Wrocław
Centre for Networking and Supercomputing, WCSS, Wrocław,
51/96.
[37] C. Pearson, A.L. Beauchamp, Can. J. Chem. 75 (1997) 220.
[38] A. Earnshaw, B.N. Figgis, J. Lewis, R.D. Peacock, J. Chem. 75 (1997) 220.
[39] B. Machura, J. Mrozin´ ski, R. Kruszyn´ ski, J. Kusz, Polyhedron 28 (2009) 2821.
Appendix A. Supplementary data
´
´
[40] B. Machura, M. Wolf, R. Kruszynski, J. Mrozinski, J. Kusz, Polyhedron 28 (2009)
2377.
CCDC 793303 and 793304 contains the supplementary crystal-
lographic data for 1 and 2. These data can be obtained free of
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
´
[41] B. Machura, J. Mrozinski, J. Kusz, Inorg. Chem. Commun. 13 (2010) 231.
[42] B.N. Figgis, Trans. Faraday Soc. 56 (1960) 1553.
[43] O. Kahn, Molecular Magnetism, VCH, New York, 1993.
[44] R. Chiozzone, R. Gonzalez, C. Kremer, G. De Munno, J. Cano, F. Lloret, M. Julve, J.
Faus, Inorg. Chem. 38 (1999) 4745.
[45] C.J. O’Connor, E. Sinn, E.J. Cukauskas, B.S. Deaver, Inorg. Chim. Acta 32 (1979)
29.