Ramaraj, A and Nethaji, Munirathinam and Jagirdar, Bataji R (2014) Contrasting reactivity behaviour of the RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH3, Me3Si). In: DALTON TRANSACTIONS, 43 (39). pp. 14625-14635.
Full text not available from this repository. (Request a copy)Abstract
A new ruthenium pincer complex RuHCl(CO)(PNP)] (PNP = PhCH2N(CH2CH2PPh2)(2)) (1) was synthesized and characterized. The reactivity of complex 1 with electrophilic reagents XOTf (X = H, CH3, and Me3Si; OTf = CF3SO3) was studied by variable temperature NMR spectroscopy with an aim to observe and characterize sigma complexes of type Ru(eta(2)-HX)Cl(CO)(PNP)]OTf] (X = H (2), CH3 (3), Me3Si (4)). Reaction of complex 1 with HOTf resulted in the formation of the dihydrogen complex, Ru(eta(2)-H-2)Cl(CO)(PNP)OTf] (2). On the other hand, the reaction between complex 1 and MeOTf and Me3SiOTf resulted in the direct elimination of MeCl and Me3SiCl via a S(N)2 type of reaction without the intermediacy of the respective sigma complexes 3 and 4. This contrasting reactivity behaviour has been rationalized taking into consideration the approach of the relatively bulky electrophites CH3+ and Me3Si+ onto the hydride moiety of the ruthenium fragment, which is sterically hindered.
| Item Type: | Journal Article |
|---|---|
| Publication: | DALTON TRANSACTIONS |
| Publisher: | ROYAL SOC CHEMISTRY |
| Additional Information: | Copy right for this article belongs to the ROYAL SOC CHEMISTRY, THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND |
| Department/Centre: | Division of Chemical Sciences > Inorganic & Physical Chemistry |
| Date Deposited: | 14 Nov 2014 07:25 |
| Last Modified: | 14 Nov 2014 07:25 |
| URI: | http://eprints.iisc.ac.in/id/eprint/50249 |
Actions (login required)
 |
View Item |
