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It should be noted that for third period elements such as silicon, phosphorus, and sulfur, the low-lying 3d orbitals can be utilized not only for pπ-dπ multiple bonding but also for additional bond formation. See for example: Cotton, F. A, Wilkinson, G, Gaus, P. L. Basic Inorganic Chemistry, 3rd ed, John Wiley & Sons, Inc, New York, 1995; pp 258-259
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2 at -78°C followed by warming to room temperature, the color of 1 changed from yellowish to brown, but no identifiable product was obtained. No significant color change was observed for 2. This is common for most compounds of this type as only a few dimers of dimers having mixed-valence species have been isolated and characterized.
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2 at -78°C followed by warming to room temperature, the color of 1 changed from yellowish to brown, but no identifiable product was obtained. No significant color change was observed for 2. This is common for most compounds of this type as only a few dimers of dimers having mixed-valence species have been isolated and characterized.
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34948867234
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4(NSC-CNS))} ·2THF, 3·2THF was isolated. See the supporting information.
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4(NSC-CNS))} ·2THF, 3·2THF was isolated. See the supporting information.
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For the functionalized terephthalate-linked compounds, the electronic spectra changed according to the dihedral angles between the two [Mo 2] axes, but the electrochemistry was not studied. See ref 8
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2] axes, but the electrochemistry was not studied. See ref 8.
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44
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34948836232
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It should be noted that the electronic coupling between the dimetal centers is not necessarily enhanced if the core structure has a π system or if the conformation is changed by the substitution of oxygen to sulfur atoms
-
It should be noted that the electronic coupling between the dimetal centers is not necessarily enhanced if the core structure has a π system or if the conformation is changed by the substitution of oxygen to sulfur atoms.
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45
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34948877557
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As it is often recognized (ref 13), an important difference between sulfur and oxygen compounds is that the sulfur d orbitals are available for additional bonding interactions, and sulfur atoms frequently use dπ interactions to form multiple bonds. For example, in the sulfate ion, the S-O bonds have considerable multiple-bond character, as evidenced by the shortness of the bond distance. See: Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th Ed.; John Wiley & Sons, Inc: New York, 1999.
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As it is often recognized (ref 13), an important difference between sulfur and oxygen compounds is that the sulfur d orbitals are available for additional bonding interactions, and sulfur atoms frequently use dπ interactions to form multiple bonds. For example, in the sulfate ion, the S-O bonds have considerable multiple-bond character, as evidenced by the shortness of the bond distance. See: Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th Ed.; John Wiley & Sons, Inc: New York, 1999.
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It should be noted that the donation of electrons in the ä orbitale is unique to compounds with quadruply bonded units
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It should be noted that the donation of electrons in the ä orbitale is unique to compounds with quadruply bonded units.
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Casida, M. E.; Jamorski, C.; Casida, K. C.; Salahub, D. R. J. Chem. Phys. 1998, 108, 4439.
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(1998)
J. Chem. Phys
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Casida, M.E.1
Jamorski, C.2
Casida, K.C.3
Salahub, D.R.4
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