Dutta, Saikat ; Jagirdar, Balaji R. ; Nethaji, Munirathinam (2008) Influence of the electronics of the phosphine ligands on the H−H bond elongation in dihydrogen complexes Inorganic Chemistry, 47 (2). pp. 548-557. ISSN 0020-1669
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Official URL: http://doi.org/10.1021/ic7016769
Related URL: http://dx.doi.org/10.1021/ic7016769
Abstract
Five new monocationic dihydrogen complexes of ruthenium of the type trans-[RuCl(η2-H2)(PP)2][BF4] (PP = bis-1,2(diarylphosphino)ethane, aryl = p-fluorobenzyl, 1a, benzyl, 2a, m-methylbenzyl, 3a, p-methylbenzyl, 4a, p-isopropylbenzyl, 5a) have been prepared by protonating the precursor hydride complexes trans-[RuCl(H)(PP)2] using HBF4·OEt2. The dihydrogen complexes are quite stable and have been isolated in the solid state. The intact nature of the H−H bond in these derivatives has been established from the short spin−lattice relaxation times (T1, ms) and observation of substantial H, D couplings in the HD isotopomers. The H−H bond distances (dHH, Å) increase systematically from 0.97 to 1.03 Å as the electron-donor ability of the substituent on the diphosphine ligand increases from the p-fluorobenzyl to the p-isopropylbenzyl moiety. The dHH in trans-[Ru(η2-H2)(Cl)((C6H5CH2)2PCH2CH2P(CH2C6H5)2)2][BF4], 2a, was found to be 1.08(5) Å by X-ray crystallography. In addition, two new 16-electron dicationic dihydrogen complexes of the type [Ru(η2-H2)(PP)2][OTf]2 (PP = (ArCH2)2PCH2CH2P(CH2Ar)2, Ar = m-CH3C6H4−, 6a, p-CH3C6H4−, 7a) have also been prepared and characterized. These derivatives were found to possess elongated dihydrogen ligands.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 102259 |
| Deposited On: | 12 Feb 2018 12:19 |
| Last Modified: | 12 Feb 2018 12:19 |
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