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Photochemical studies of (η-CH )Ru(PPh)Cl and (η-C H)Ru(PPh)Me: Formation of Si-H and C-H bond activation products

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JournalDalton Transactions
DateE-pub ahead of print - 22 Oct 2013
DatePublished (current) - 21 Jan 2014
Issue number3
Volume43
Number of pages10
Pages (from-to)1162-1171
Early online date22/10/13
Original languageEnglish

Abstract

Studies examining the photochemical reactivity of CpRu(PPh )Cl and CpRu(PPh)Me towards the two electron donor ligands PEt, CH, DMSO, the CH bond activatable reagents tetrahydrofuran, toluene, and pyridine, and the SiH bond activatable reagents HSiEt and HSi(Me) CHCH) are presented. Broadband UV irradiation of CpRu(PPh)Cl leads to the formation of mono-substitution products such as CpRu(PPh)(PEt)Cl which are inert to further photochemical reaction, although thermally bis-substituted products such as CpRu(PEt)Cl can be formed. Room temperature irradiation of the related complex CpRu(PPh)Me with L = PEt, CH, and DMSO also produces CpRu(PPh)(L)Me. However, when these reactions are followed by in situ laser irradiation (325 nm source) at low temperature, three solvent activated isomers (ortho, meta and para) of CpRu(PPh) (CHMe) are detected in toluene in addition to η- and η-coordinated benzyl species. Furthermore, photolysis in THF leads to both the C-D bond activation product CpRu(PPh)(OCD) and the labile coordination complex CpRu(PPh)(THF)Me. Now CH rather than CHD is liberated which suggests the involvement of an orthometallated species. The photochemically driven reaction of CpRu(PPh )Me with HSiEt at 198 K generates CpRu(κ-2-CHPPh)(SiEt )H and thereby confirms a role for an orthometallated complex is this process. Irradiation in cyclohexane produces the known orthometallated complex, CpRu(κ-2-CHPPh )(PPh), and CH in accordance with this reactivity.

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