1. Electron-Precise 1,3-Bishomocubanes - A Combined Experimental and Theoretical Study.
- Author
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Barik, Subrat Kumar, Rao, Chokkapu Eswara, Yuvaraj, K., Jagan, R., Kahlal, Samia, Halet, Jean-François, and Ghosh, Sundargopal
- Subjects
CUBANES ,CHALCOGENS ,BORON compounds ,RHODIUM ,RUTHENIUM ,MASS spectrometry ,NUCLEAR magnetic resonance spectroscopy - Abstract
A combined experimental and quantum-chemical study of a series of homometallic metallaheteroboranes [(Cp*M)
2 E6 B2 H2 ] (M = Rh or RuH; E = S or Se; Cp* = η5 -C5 Me5 ), which are analogues of 1,3-bishomocubane, is reported. The thermolysis of nido-[(Cp*Rh)2 B3 H7 ] ( 1) in the presence of S or Se powder in toluene yielded bishomocubane clusters [(Cp*Rh)2 (μ-E)2 (μ3 -E)4 B2 H2 ], ( 3: E = S; 4: E = Se). In a similar fashion, the treatment of nido-[(Cp*RuH)2 B3 H7 ] ( 2) with S or Se powder in p-xylene yielded [(Cp*Ru)2 (μ-E)2 (μ3 -E)4 B2 H2 ] ( 5: E = S; 6: E = Se) and [(Cp*Ru)2 (μ3 -Se)(μ4 -Se)B3 H5 ] ( 7). One of the noteworthy features of 3- 6 is the presence of an electron-precise trichalcogenoborato ligand. All of the compounds have been characterized by mass spectrometry; IR spectroscopy; and1 H,11 B, and13 C NMR spectroscopy. The structures of 3, 4, 6, and 7 were established unequivocally by X-ray crystallographic analysis. Quantum-chemical calculations by DFT methods for 3, 4, and 6 showed reasonable agreement with the experimentally observed structural parameters. The large HOMO-LUMO gaps are consistent with the high stabilities of these complexes. [ABSTRACT FROM AUTHOR]- Published
- 2015
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