J.G. Małecki et al. / Polyhedron 24 (2005) 359–368
367
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0
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tion may be obtained free of charge from The Director,
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Acknowledgements
Crystallographic part was financed by funds allocated
by the State Committee for Scientific Research to the
Institute of General and Ecological Chemistry, Techni-
cal University of Ł o´ d z´ . The GAUSSIAN03 calculations
were carried out in the Wrocław Centre for Networking
and Supercomputing, WCSS, Wrocław, Poland under
calculational Grant No. 51/96.
2
00.0
300.0
400.0
500.0
600.0
λ
Fig. 5. Calculated electronic spectrum of [RuCl
solid line – LANL2DZ, dashed line – SSD).
3
(NO)(PPh
3
)(HPz)]
(
calculation with LANL2DZ basis and with SSD basis set
the band we ascribe to the calculated transition at 498.3
References
nm. These transitions are of d!d and pCl ! pꢂ type
NO
[1] D.S. Bohle, C. Hung, A.K. Powell, B.D. Smith, S. Wocaldo,
Inorg. Chem. 36 (1997) 1992.
(
LLCT). In these range of energy transitions the predic-
[
[
[
2] S.S.S. Borges, C.U. Davanzo, E.E. Castellano, J. Z-Schpector,
S.C. Silva, D.W. Franco, Inorg. Chem. 37 (1998) 2670.
tion of experimental values with LANL2DZ basis set is
better than with using the ECP basis (SSD). The transi-
tions calculated between 418 and 400 nm (442–407 nm
SSD) are ascribed to the band at 438 nm. These transi-
tions are again of LCT type and occur from the chlorine,
3] M.G. Gomes, C.U. Davanzo, S.C. Silva, L.G. Lopes, P.S. Santos,
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ꢂ
[5] C.W.B. Bezerra, S.C. da Silva, M.T.P. Gambardella, R.H.A.
Santos, L.M.A. Plicas, E. Tfouni, D.W. Franco, Inorg. Chem. 38
phenyl and pyrazole orbitals to the p orbitals.
NO
The experimental band at 330 nm is ascribed to the
transitions calculated between 356 and 312 nm with med-
ium oscillator strengths and to transitions between 366.3
and 311.0 nm while the SSD basis set was using. These are
mainly transitions from the pyrazole, phenyl and chlorine
ligands orbitals to the metal d orbitals (LMCT). The tran-
sitions 289 and 263 nm (304.4 to 269.9 – SSD) are assigned
to the band at 300 nm and shoulder at about 270 nm.
These are again transitions of LMCT character.
(
1999) 5660.
[
[
6] D.H. Bohle, E.S. Sagan, Eur. J. Inorg. Chem. (2000) 1609.
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1
9] L.G.F. Lopes, A. Wieraszko, Y. El-Sherif, M.J. Clarke, Inorg.
[
Chim. Acta 312 (2001) 15.
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[
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[11] R.A. Sanchez-Delgado, A. Andriollo, O.L. DeOchoa, T. Suarez,
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The transitions between 240 and 231 nm and 259.8 to
22.2 nm in calculation with SSD, respectively, are as-
[
12] M.-Y. Park, Y.J. Kim, O.-J. Cho, I.-M. Lee, J. Kor. Chem. Soc.
0 (1996) 445.
2
signed to the band at 228 nm. They are of LLCT type
4
13] F. Jo o´ , J. Kov a´ cs, A. Kath o´ , A.C. B e´ nyei, T. Decuir, D.J.
´
[
ꢂ
(
(
interligand transitions) and intraligand ðpPh ! p Þ
Ph
Darensbourg, Inorg. Synth. 32 (1998) 1.
´
[14] F. Jo o´ , J. Kov a´ cs, A.C. B e´ nyei, A. Kath o´ , Angew. Chem. 110
transitions). The experimental band at 216 nm could
(
1998) 1024.
[15] F. Jo o´ , G. Laurenczy, L. N a´ dasdi, J. Elek, Chem. Commun.
1999) 971.
not be assigned on the basis of the calculated transitions.
This band probably corresponds also to pPh ! pꢂ tran-
Ph
(
sitions in the PPh ligand.
3
[
16] G. Laurenczy, F. Jo o´ , L. N a´ dasdi, Inorg. Chem. 39 (2000) 5083.
17] N. Ahmad, J.J. Levinson, S.D. Robinson, M.F. Uttley, Inorg.
Synth. 15 (1974) 51.
As it can be seen from Tables 7 and 8 the UV–Vis
spectrum calculated with the SSD basis set on the ruthe-
nium atom gave better results in the higher energy and
the LANL2DZ basis set in the lower energy range of
the spectrum.
[
[
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.
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Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck,
4
. Supplementary material
Crystallographic data for the structure of the com-
plex have been deposited at Cambridge Crystallographic
Data Center (CCDC 239378). Copies of this informa-