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Issue 39, 2014
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Contrasting reactivity behaviour of the [RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH3, Me3Si)

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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(η2-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(η2-H2)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 SN2 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 electrophiles CH3+ and Me3Si+ onto the hydride moiety of the ruthenium fragment, which is sterically hindered.

Graphical abstract: Contrasting reactivity behaviour of the [RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH3, Me3Si)

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Publication details

The article was received on 28 May 2014, accepted on 28 Jul 2014 and first published on 29 Jul 2014


Article type: Paper
DOI: 10.1039/C4DT01570C
Citation: Dalton Trans., 2014,43, 14625-14635
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    Contrasting reactivity behaviour of the [RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH3, Me3Si)

    A. Ramaraj, M. Nethaji and B. R. Jagirdar, Dalton Trans., 2014, 43, 14625
    DOI: 10.1039/C4DT01570C

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