Cluster Core Controlled Reactions of Substitution of Terminal Bromide Ligands by Triphenylphosphine in Octahedral Rhenium Chalcobromide Complexes

Cluster Core Controlled Reactions of Substitution of Terminal Bromide Ligands by Triphenylphosphine in Octahedral Rhenium Chalcobromide Complexes Научная публикация

Журнал

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Вых. Данные

Год: 2007, Том: 129, Номер: 12, Страницы: 3714-3721 Страниц : 8 DOI: 10.1021/ja0668062

Авторы

Shestopalov Michael A. ¹ , Mironov Yuri V. ¹ , Brylev Konstantin A. ¹ , Kozlova Svetlana G. ¹ , Fedorov Vladimir E. ¹ , Spies Hartmut ² , Pietzsch Hans-Jürgen ² , Stephan Holger ² , Geipel Gerhard ² , Bernhard Gerd ²

Организации

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences
2	Institut für Radiopharmazie and Institut für Radiochemie, Forschungszentrum Dresden-Rossendorf

Reactions of rhenium chalcobromides Cs-4[{Re-6(mu(3)-S)(8)}Br-6]center dot 2H(2)O, Cs-3[{Re-6(mu(3)-Se)(8)}Br-6]center dot 2H(2)O, Cs-3[{Re-6(mu(3)-Q)(7)(mu(3)-Br)}Br-6]center dot H2O (Q = S, Se), and K-2[{Re-6(mu(3)-S)(6)(mu(3)-Br)(2)}Br-6] with molten triphenylphosphine (PPh3) have resulted in a family of novel molecular hybrid inorganic-organic cluster compounds. Six octahedral rhenium cluster complexes containing PPh3 ligands with general formula [{Re-6(mu(3)-Q)(8-n)(mu(3)-Br)(n)}(PPh3)(4-n)Brn+2] (Q = S, n = 0, 1, 2; Q = Se, n = 0, 1) have been synthesized and characterized by X-ray single-crystal diffraction and elemental analyses, P-31{H-1} NMR, luminescent measurements, and quantum-chemical calculations. It was found that the number of terminal PPh3 ligands in the complexes is controlled by the composition and consequently by the charge of the cluster core {Re(6)Q(8-n)Br(n)}(n+2). In crystal structures of the complexes with mixed chalcogen/bromine ligands in the cluster core all positions of a cube [Q(8-n)Br(n)] are ordered and occupied exclusively by Q or Br atoms. Luminescence characteristics of the compounds trans-[{Re(6)Q(8)}(PPh3)(4)Br-2] and fac-[{Re6Se7Br}(PPh3)(3)Br-3] (Q = S, Se) have been investigated in CH2Cl2 solution and the broad emission spectra in the range of 600-850 nm were observed.

Shestopalov M.A. , Mironov Y.V. , Brylev K.A. , Kozlova S.G. , Fedorov V.E. , Spies H. , Pietzsch H-J. , Stephan H. , Geipel G. , Bernhard G.
Cluster Core Controlled Reactions of Substitution of Terminal Bromide Ligands by Triphenylphosphine in Octahedral Rhenium Chalcobromide Complexes
Journal of the American Chemical Society. 2007. V.129. N12. P.3714-3721. DOI: 10.1021/ja0668062 WOS OpenAlex

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