Abstract
The straightforward synthesis of two cationic iridium norbornadiene species bearing simple bidentate phosphines is reported [Ir(R2PCH2CH2PR2)(NBD)][BAr4F] [NBD = norbornadiene; R = tBu, Cy; ArF = 3,5–C6H3(CF3)2]. The hydrogenation of [Ir(tBu2PCH2CH2PtBu2)(NBD)][BAr4F] in the solution phase and in the solid state is described in which saturated (solution) or unsaturated (solid–state) dimeric species with bridging hydrides are formed. The solid–state structures, as determined by single crystal X-ray diffraction, of these dimeric species are also discussed.
Highlights
IntroductionWe have recently reported that addition of H2 to the norbornadiene precursors [Rh(R2PCH2CH2PR2)(NBD)][BArF4]
We have recently reported that addition of H2 to the norbornadiene precursors [Rh(R2PCH2CH2PR2)(NBD)][BArF4][NBD 1⁄4 norbornadiene; R 1⁄4 e.g. iBu, Cy; ArF 1⁄4 3,5eC6H3(CF3)2] [1,2]in a solidegas, singleecrystal to singleecrystal transformation [3,4]forms the corresponding norbornane (NBA) sigmaealkane complexes [Rh(R2PCH2CH2PR2)(h2:h2eC7H12)][BArF4] (Scheme 1)
Cation is coordinated with a bidentate phosphine and two CeH
Summary
We have recently reported that addition of H2 to the norbornadiene precursors [Rh(R2PCH2CH2PR2)(NBD)][BArF4]. NBDelike tetrafluorobenzobarrelene ligands complexed with iridium [9] This is in contrast with RheNBD complexes that are widely used as precursors for many catalytic processes [10], such as hydrogenation [11] and hydroacylation [12], when activated by simple addition of H2 in solution and loss of NBA. In this communication we report the straightforward synthesis of [Ir(R2PCH2CH2PR2)(NBD)][BArF4] [R 1⁄4 tBu, Cy] and subsequent reactivity with H2 in both solution and the solidestate [R 1⁄4 tBu] [13]. Hydrogenation in the solidestate of [Ir(L)(COD)]þ and [Ir(L)(C2H4)]þ cations (L 1⁄4 mono or multidentate phosphine ligand) have previously been reported by Siedle [14,15] and Bianchini [16]
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