Elumalai, Palani and Thirupathi, Natesan and Nethaji, Munirathinam (2013) Six-membered C,N] cyclopalladated sym N,N `,N `'-tri(4-tolyl) guanidines: Synthesis, reactivity studies and structural aspects. In: JOURNAL OF ORGANOMETALLIC CHEMISTRY, 741 . pp. 141-147.
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Abstract
Six-membered C,N] cyclopalladated sym N,N',N `'-tri(4-tolyl)guanidines, (ArNH)(2)C=NAr] (sym = symmetrical; Ar = 4-MeC6H4; LH24-tolyl) of the types (C,N)Pd(mu-OC(O)R)](2) (1 and 2), (C,N)Pd(mu-Br)](2) (3), cis-(C,N)PdLBr] (4-7), and (C,N)Pd(acac)] (8) were prepared in high yield by established methods with a view aimed at understanding the influence of the 4-tolyl substituent of the guanidine moiety upon the solution behaviour of 1-8. The composition of 1-8 was confirmed by elemental analysis, IR, and NMR spectroscopy, and mass spectrometry. The molecular structures of 1-6 were determined by single-crystal X-ray diffraction. Palladacycles 1-3 exist as a dimer in transoid conformation in the solid state while 4-6 exist as a monomer with cis configuration around the palladium atom as the Lewis base is placed cis to the Pd-C bond due to antisymbiosis. The NMR spectra of 1-8 revealed the presence of a single isomer in solution and this spectral feature is ascribed to the rapid inversion of the six-membered ``C,N]Pd'' ring due to the presence of sterically less hindered and more symmetrical 4-tolyl substituent in the =NAr unit of the guanidine moiety. (C) 2013 Elsevier B.V. All rights reserved.
Item Type: | Journal Article |
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Publication: | JOURNAL OF ORGANOMETALLIC CHEMISTRY |
Publisher: | ELSEVIER SCIENCE SA |
Additional Information: | Copyright of this article is belongs to ELSEVIER SCIENCE SA |
Keywords: | Palladacycle; Guanidine; Bridge-splitting reaction; n-pi Conjugation |
Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry |
Date Deposited: | 30 Sep 2013 04:51 |
Last Modified: | 30 Sep 2013 04:51 |
URI: | http://eprints.iisc.ac.in/id/eprint/47338 |
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