Chakraborty, Tapash ; Srivastava, Kriti ; Singh, Harkesh B. ; Butcher, Ray J. (2011) Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: synthesis, structure and spectroscopic investigation Journal of Organometallic Chemistry, 696 (15-16). pp. 2782-2788. ISSN 0022-328X
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Official URL: http://www.sciencedirect.com/science/article/pii/S...
Related URL: http://dx.doi.org/10.1016/j.jorganchem.2011.04.018
Abstract
Oxidative addition of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide to Pd(PPh3)4 provided two different mononuclear palladium selenolato complexes, Pd(Se∩N)(PPh3)Cl (4) [Se∩N=chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolate] and Pd(Se∩N)(Se∩N∗)(PPh3) (5) [Se∩N=chelating, Se∩N∗=non-chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolato ligand] in dicholoromethane and toluene respectively. Complex 4 has also been synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl)phenylselenenyl chloride to Pd(PPh3)4. The bromo and iodo analogs of 4 (9 and 10) were similarly synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl)phenylselenenyl bromide and iodide, respectively to Pd(PPh3)4. The oxidative addition of 2-(N,N-dimethylaminomethyl)phenylselenenyl bromide and iodide to Pd(PPh3)4 afforded mononuclear palladium selenolate complexes, Pd(Se∩N)(PPh3)X (13 and 14) [Se∩N=chelating 2-(N,N-dimethylaminomethyl)phenylselenolate, X=Br: 13, X=I: 14]. The reactions of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide and bis[2-(N,N-dimethylaminomethyl)phenyl] diselenide with Pd(COD)Cl2 provided dinuclear selenolato-bridged complexes [PdCl(Se∩N)]2 (15) [Se∩N=chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolate] and [PdCl(Se∩N)]2 (19) [Se∩N=chelating 2-(N,N-dimethylaminomethyl)phenylselenolate] respectively. The complexes were characterized by elemental analysis and NMR (1H and 77Se) spectroscopy. Complexes 4 and 5 were also characterized by mass spectrometry. Molecular structures of 4, 5, 9, 14 and 15 have been established by single crystal X-ray diffraction analysis. Complexes 4 and 9 are isomorphous and crystallize in the space group P21/c of the monoclinic system where the selenolato and halo ligands are trans to each other. Complex 5 crystallizes in the space group P21/n of the monoclinic system where one chelating and one non-chelating selenolato ligands are trans to each other. Mononuclear complex 14 and binuclear centrosymmetric complex 15 crystallize in the P1̅ space group of the triclinic system.
Item Type: | Article |
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Source: | Copyright of this article belongs to Elsevier Science. |
Keywords: | Selenolate; Palladium; Oxidative Addition; Selenenyl Halide; Diselenide |
ID Code: | 47591 |
Deposited On: | 11 Jul 2011 13:48 |
Last Modified: | 11 Jul 2011 13:48 |
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