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

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• 作者：Michael A. Shestopalov ; Yuri V. Mironov ; Konstantin A. Brylev ; Svetlana G. Kozlova ; Vladimir E. Fedorov ; Hartmut Spies ; Hans-J&uuml ; rgen Pietzsch ; Holger Stephan ; Gerhard Geipel ; Gerd Bernhard
• 刊名：Journal of the American Chemical Society
• 出版年：2007
• 出版时间：March 28, 2007
• 年：2007
• 卷：129
• 期：12
• 页码：3714 - 3721
• 全文大小：476K
• 年卷期：v.129,no.12(March 28, 2007)
• ISSN：1520-5126

文摘

Reactions of rhenium chalcobromides Cs₄[{Re₆(s/entities/mgr.gif">₃-S)₈}Br₆]·2H₂O, Cs₃[{Re₆(s/entities/mgr.gif">₃-Se)₈}Br₆]·2H₂O,Cs₃[{Re₆(s/entities/mgr.gif">₃-Q)₇(s/entities/mgr.gif">₃-Br)}Br₆]·H₂O (Q = S, Se), and K₂[{Re₆(s/entities/mgr.gif">₃-S)₆(s/entities/mgr.gif">₃-Br)₂}Br₆] with molten triphenylphosphine(PPh₃) have resulted in a family of novel molecular hybrid inorganic-organic cluster compounds. Sixoctahedral rhenium cluster complexes containing PPh₃ ligands with general formula [{Re₆(s/entities/mgr.gif">₃-Q)_8-n(s/entities/mgr.gif">₃-Br)_n}(PPh₃)_4-nBr_n+2] (Q = S, n = 0, 1, 2; Q = Se, n = 0, 1) have been synthesized and characterized byX-ray single-crystal diffraction and elemental analyses, ³¹P{¹H} NMR, luminescent measurements, andquantum-chemical calculations. It was found that the number of terminal PPh₃ ligands in the complexes iscontrolled by the composition and consequently by the charge of the cluster core {Re₆Q_8-nBr_n}ⁿ⁺². In crystalstructures of the complexes with mixed chalcogen/bromine ligands in the cluster core all positions of acube [Q_8-nBr_n] are ordered and occupied exclusively by Q or Br atoms. Luminescence characteristics ofthe compounds trans-[{Re₆Q₈}(PPh₃)₄Br₂] and fac-[{Re₆Se₇Br}(PPh₃)₃Br₃] (Q = S, Se) have beeninvestigated in CH₂Cl₂ solution and the broad emission spectra in the range of 600-850 nm were observed.