Dalton Transactions
Page 6 of 9
ARTICLE
Journal Name
2
3
(Eds.), Comprehensive CoordinationDCOhI:e1m0.1is0t3r9y/CI7ID, TV0o20l.415D,
Elsevier, 2003, pp. 127-270.
R. Alberto, U. Abram, in: A. Vértes, S. Nagy, Z. Klencsár, R. G.
Lovas, F. Rösch (Eds.), Handbook of Nuclear Chemistry, Vol.
4, Springer, 2011, pp. 2073–2120.
G. Bandoli, U. Mazzi, U. Abram, H. Spies, R. Münze,
Polyhedron, 1987, 6, 1547.
U. Abram, S. Abram, J. Stach, W. Dietzsch, W. Hiller, Z.
Naturforsch. 1991, 46b, 1183.
T. Yoshimura, T. Ikai, Y. Tooyama, T. Takayama,T. Sekine, Y.
Kino, A. Kirishima, N. Sato, T. Mitsugashira, N. Takahashi, A.
Shinohara, Eur. J. Inorg. Chem. 2010, 1214.
electronic charge gradient field establish the chemical bonds
between the Tc and chalcogen atoms.28
Table 4. Atomic orbital decomposition of the natural bonding orbitals between Tc and
chalcogen atoms at compounds 1, 2, 3, and 5
Tc
Se/Te
(sp)
4
5
6
(sp)
1.94
1.78
0.67
0.65
(d)
1
2
3
5
1.84
1.78
3.73
3.44
4.40
5.52
3.34
3.57
7
8
9
T. Yoshimura, T. Ikai, T. Takayama, T. Sekine, Y. Kino, A.
Shinohara, Inorg. Chem. 2010, 49, 5876.
A. Davison, H. S. Trop, B. V. DePamphilis, A. G. Jones, R. W.
Thomas, S. S. Jurisson, Inorg. Synth. 1982, 21, 160.
R. M. Pearlstein, W. M. Davis, A. G. Jones, A. Davison, Inorg.
Chem. 1989, 28, 3332.
The chemical bonds for Tc(V) and Tc(III) compounds show marked
differences. They are characterized by the charge gradient fields
around the Tc nucleus, atomic charges and bond orders. Figure 6
shows that the electronic charge around the Tc atoms in the Tc(V)
compounds is more homogeneously distributed than that for the
Tc(III) compounds, revealing a more directional character of the
chemical bonds in the Tc(III) compounds, with the charge being
concentrated along the lines connecting the Tc and Se/Te atoms.
Table 4 shows selected atomic charges and bond orders. It can be
derived that: (i) the bond orders between the Tc and chalcogen
atoms are greater for Tc(III) compounds, and (ii) there is a greater
ionicity in the Tc(III) compounds. This is consistent with the scenario
of more directional bonds revealed in Fig. 6. It can also be observed
that the bond orders and ionicity of the bonds is greater for the
tellurium compounds compared with the selenium ones.
Furthermore, the decomposition in atomic orbitals of the natural
bonding orbitals between Tc and the chalcogen atoms (see Table 4)
shows that there is a greater contribution of the Tc d- orbitals for
the Tc(III) compounds and a smaller one for the Tc(V) compounds.
10 W. S. Haller, K. J. Irgolic, J. Organomet. Chem. 1972, 38, 97.
11 G. A. Sheldrick, Acta Crystallogr. Sect. A, 2008, 64, 112.
12 G. A. Sheldrick, Crystal structure refinement with SHELXL.
Acta Crystallogr. Sect. C, 2015, 71, 3.
13 M. Miyashita, T. Suzuki, M. Hoshino, A. Yoshikoshi,
Tetrahedron, 1997, 53, 12469.
14 J. Arnold, Progress Inorg. Chem. 1995, 43, 353.
15 T. A Hamor, W.Hussain, C. J Jones, J. A. McCleverty, A. S
Rothin, Inorg. Chim. Acta, 1988, 146, 181.
16 H. Putz, K. Brandenburg, Diamond - Crystal and Molecular
Structure Visualization, Crystal Impact, Bonn, Germany.
17 B. Kuhn, U. Abram, Z. Anorg. Allg. Chem. 2011, 637, 242.
18 N. de Vries, J. C. Dewan, A. G. Jones, A. Davison, Inorg.
Chem. 1988, 27, 1574.
19 N. de Vries, A. G. Jones, A. Davison, Inorg. Chem. 1989, 28
,
3728.
20 N. de Vries, J. Cook, A. Davison, T. Nicholson, A. G. Jones,
Inorg. Chem. 1990, 29, 1062.
21 J. R. Dilworth, B. D. Neaves, J. P. Hutchinson, J. A. Zubieta,
Inorg. Chim. Acta, 1982, 65, L223.
22 J. R. Dilworth, C. Lu, Y. Zheng, J. Zubieta, Polyhedron, 1999,
18, 501.
Conclusions
23 J. R. Dilworth, J. Hu, J. R. Miller, D. L. Hughes, J. A. Zubieta,
Q. Chen, J. Chem. Soc. Dalton Trans. 1995, 3153.
In conclusion, the present study shows that arylselenolate and
aryltellurolate complexes of technetium can be prepared with the
transition metal in various oxidation states. The tellurolato
complexes represent the first examples of coordination compounds
with technetium-tellurium bonds. The Tc-Te bonds in the Tc(III)
complex 5 are more directional than in the Tc(V) compound 2.
24 Gaussian 09, Revision C, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.
Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M.
Caricato, A. Marenich, J. Bloino, B. G. Janesko, R. Gomperts,
B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L.
Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F.
Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D.
Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W.
Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H.
Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E.
Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N.
Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand,
K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J.
Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R.
Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O.
Farkas, J. B. Foresman, and D. J. Fox, Gaussian, Inc.,
Wallingford CT, 2016.
Acknowledgements
We gratefully acknowledge financial support by CNPq
(Conselho Nacional de Desenvolvimento Científico
Tecnológico, process: 200657/2015-1)
e
and
CAPES/DAAD/PROBRAL (Comissão de Aperfeiçoamento de
Pessoal do Nível Superior/Deutscher Akademischer
Austauschdienst, process: 10851/13-5). The calculations have
been performed using the computational facilities of
CPAD/UFSM
25 T. Yanai, D. P. Tew, N. C. Handy, Chem. Phys. Lett. 2004,
393, 51
26 M. J. G. Peach, T. Helgaker, P. Sałek, T. W. Keal, O. B.
Lutnæs, D. J. Tozer, N. C. Handy, Phys. Chem. Chem. Phys.
2006, 8, 558.
Notes and References
27 M. Yu, D. R. Trinkle, J. Chem. Phys. 2011, 134, 64111.
1
U. Abram, R. Alberto, J. Braz. Chem. Soc., 2006, 17, 1486.
6 | J. Name., 2012, 00, 1-3
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