Activation of hydrogen by bridged transition metal carboxylates. Rhodium(II) acetate catalyzed hydrogenation of olefins

Hui, B. C. Y.; Teo, W. K.; Rempel, Garry L.

doi:10.1021/ic50122a010

Cited by 51 publications

(14 citation statements)

References 3 publications

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“…Theapparent activation energy for the Rh 2 (OAc) 4 catalyst determined from activity measurements at 0-40 8 8Cis5.4 kcal mol À1 (Figure S4 b), which is avalue similar to that of CuRhBTC and suggests acommon mechanism. Hydrogenation activity for Rh 2+ is consistent with reports in the literature for Rh 2 (OAc) 4 , [11] as well as for Rh 2+ ions in amorphous coordination polymers containing dinuclear rhodium paddle-wheel units. [6,12] However,the Rh 2+ active site in Rh 2 (OAc) 4 is unstable under reaction conditions, in contrast to the high stability of Rh 2+ in CuRhBTC.…”

Section: Angewandte Chemiesupporting

confidence: 90%

Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks

et al. 2019

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We report the first study of ag as-phase reaction catalyzedb yh ighly dispersed sites at the metal nodes of ac rystalline metal-organic framework (MOF). Specifically, CuRhBTC (BTC 3À = benzenetricarboxylate) exhibited hydrogenation activity,w hile other isostructural monometallic and bimetallic MOFs did not. Our multi-technique characterization identifies the oxidation state of Rh in CuRhBTC as + 2, which is aR ho xidation state that has not previously been observed for crystalline MOF metal nodes.These Rh 2+ sites are active for the catalytic hydrogenation of propylene to propane at room temperature,and the MOF structure stabilizes the Rh 2+ oxidation state under reaction conditions.D ensity functional theory calculations suggest am echanism in which hydrogen dissociation and propylene adsorption occur at the Rh 2+ sites. The ability to tailor the geometry and ensemble size of the metal nodes in MOFs allows for unprecedented control of the active sites and could lead to significant advances in rational catalyst design.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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Section: Angewandte Chemiesupporting

confidence: 90%

Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks

et al. 2019

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“…Dinuclear complexes with a paddlewheel structure show a rich chemistry and different electronic configurations as a consequence of the distribution of the energy levels and the number of electrons in the dimetallic unit [1,2]. Dirhodium complexes and, in particular, the tetracarboxylato derivatives, are among the most important and versatile paddlewheel compounds [1,2], and their reactivity has been explored in several fields such as catalysis [3][4][5][6][7][8][9] or bioinorganic chemistry [10][11][12][13]. The ground state electron configuration for most of these complexes is σ 2 π 4 δ 2 δ* 2 π* 4 for a diamagnetic Rh 2 4+ unit, which, therefore, displays a single metal-metal bond order [1,2].…”

Section: Introductionmentioning

confidence: 99%

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

et al. 2019

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In this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.

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“…Dirhodium( ii ) complexes act as sensors,1 show antitumor activity,2 are capable of cross-linking DNA,3 and can be used to control peptide structures by binding carboxylate side chains to the Rh core,4 thus enabling site-specific modifications of polypeptides and proteins 5. They act as Lewis acids to activate alkynes,6 as well as enynes7 or serve as hydrogenation catalysts 8. The well-known Rh( ii ) carbenoid9 and nitrenoid10 transfer catalysts are capable of catalyzing X–H insertions,11 cyclopropanations,11a,12 aziridinations,13 ylide formation,11a,14 and allylic oxidations 15.…”

Section: Introductionmentioning

confidence: 99%

Site-selective nitrenoid insertions utilizing postfunctionalized bifunctional rhodium(ii) catalysts

Berndt

Radchenko

Becker³

et al. 2019

Chem. Sci.

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Activation of hydrogen by bridged transition metal carboxylates. Rhodium(II) acetate catalyzed hydrogenation of olefins

Cited by 51 publications

References 3 publications

Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks

Selective Catalytic Chemistry at Rhodium(II) Nodes in Bimetallic Metal–Organic Frameworks

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

Site-selective nitrenoid insertions utilizing postfunctionalized bifunctional rhodium(ii) catalysts

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