The application of dirhodium tetraacetate to organic synthesis was pioneered by Teyssie and co-workers.[5] An extensive range of reactions including insertion into bonds and the cyclopropanation of alkenes[6] and aromatic systems.[7] It selectively binds ribonucleosides (vs. deoxynucleosides) by binding selectively to ribonucleosides at their 2′ and 3′ –OH groups.[8] Rhodium(II) acetate dimer, compared to copper(II) acetate, is more reactive and useful in differentiating ribonucleosides and deoxynucleosides because it is soluble in aqueous solution like water whereas copper(II) acetate only dissolves in non-aqueous solution.
Selected catalytic reactions
Dirhodium tetraacetate is also used as catalyst for insertion into C–H and X–H bonds (X = N, S, O).
Cyclopropanation
through the decomposition of diazocarbonyl compounds, the intra- and intermolecular cyclopropanation reactions occurs.
Aromatic cycloaddition
Rhodium acetate catalyzes both two-component cycloaddition as well as three-component 1,3-dipolar cycloadditions.
C–H insertion
Rh(II)-catalyzed regioselective intramolecular and regiospecific intermolecular C–H insertion into aliphatic and aromatic C–H bonds is a useful method for the synthesis of a diverse range of organic compounds.
Oxidation of alcohols
Allylic and benzylicalcohols were oxidized to the corresponding carbonyl compounds using tert-butyl hydroperoxide in stoichiometric amounts and Rh2(OAc)4 as catalyst in dichloromethane at ambient temperature.
X–H insertion (X = N, S, O)
Rh(II) carbenoid reacts with amines, alcohols or thiols to yield the product of a formal intra- or intermolecular X–H bond (X = N, S, O) insertion via the formation of an ylideintermediate.
References
^"Dirhodium tetraacetate". pubchem.ncbi.nlm.nih.gov. Retrieved 14 December 2021.
^Rempel, G. A.; Legzdins, P.; Smith, H.; Wilkinson, G. (1972). Tetrakis(acetato)dirhodium(II) and Similar Carboxylato Compounds. Inorg. Synth. Inorganic Syntheses. Vol. 13. pp. 90–91. doi:10.1002/9780470132449.ch16. ISBN9780470132449.
^Doyle, M. P. (2000). "Asymmetric Addition and Insertion Reactions of Catalytically-Generated Metal Carbenes". In Ojima, Iwao (ed.). Catalytic Asymmetric Synthesis (2nd ed.). New York: Wiley. ISBN978-0-471-29805-2.
^Cotton, F. A.; Deboer, B. G.; Laprade, M. D.; Pipal, J. R.; Ucko, D. A. (1971). "The crystal and molecular structures of dichromium tetraacetate dihydrate and dirhodium tetraacetate dihydrate". Acta Crystallogr B. 27 (8): 1664. doi:10.1107/S0567740871004527.
^Paulissen, R.; Reimlinger, H.; Hayez, E.; Hubert, A. J.; Teyssié, P. (1973). "Transition metal catalysed reactions of diazocompounds. II: Insertion in the hydroxylic bond". Tetrahedron Lett. 14 (24): 2233. doi:10.1016/S0040-4039(01)87603-6. hdl:2268/236113.
^Hubert, A. J.; Feron, A.; Warin, R.; Teyssie, P. (1976). "Synthesis of iminoaziridines from carbodiimides and diazoesters : A new example of transition metal salt catalysed reactions of carbenes". Tetrahedron Lett. 17 (16): 1317. doi:10.1016/S0040-4039(00)78050-6. hdl:2268/236097.
^Anciaux, A. J.; Demonceau, A.; Hubert, A. J.; Noels, A. F.; Petiniot, N.; Teyssié, P. (1980). "Catalytic control of reactions of dipoles and carbenes; an easy and efficient synthesis of cycloheptatrienes from aromatic compounds by an extension of Buchner's reaction". J. Chem. Soc., Chem. Commun. (16): 765–766. doi:10.1039/C39800000765. hdl:2268/237699.
^Berger, N. A.; Tarien, E.; Eichhorn, G. L. (1972). "Stereoselective Differentiation between Ribonucleosides and Deoxynucleosides by Reaction with the Copper(II) Acetate Dimer". Nature New Biology. 239 (95): 237–40. doi:10.1038/newbio239237a0. PMID 4538853.
January 21, 2023
rhodium, acetate, coordination, compound, with, formula, where, acetate, this, dark, green, powder, slightly, soluble, polar, solvents, including, water, used, catalyst, cyclopropanation, alkenes, widely, studied, example, transition, metal, carboxylate, compl. Rhodium II acetate is the coordination compound with the formula Rh2 AcO 4 where AcO is the acetate ion CH3 CO 2 This dark green powder is slightly soluble in polar solvents including water It is used as a catalyst for cyclopropanation of alkenes It is a widely studied example of a transition metal carboxylate complex Rhodium II acetate NamesIUPAC name Rhodium II acetateOther names Dirhodium tetraacetate Tetrakis acetato dirhodium II Rhodium diacetate dimer Tetrakis m acetato dirhodiumIdentifiersCAS Number 15956 28 2 Y3D model JSmol Interactive imageChemSpider 20370 YECHA InfoCard 100 036 425EC Number 240 084 8PubChem CID 152122RTECS number VI9361000UNII NK3058Z56X YInChI InChI 1S 2C2H4O2 Rh c2 1 2 3 4 h2 1H3 H 3 4 q 2 p 2 YKey ITDJKCJYYAQMRO UHFFFAOYSA L YInChI 1S 4C2H4O2 2Rh c4 1 2 3 4 h4 1H3 H 3 4 q 2 2 p 4Key SYBXSZMNKDOUCA UHFFFAOYSA JSMILES OH2 Rh 3 1234 Rh 3 OH2 o c C o1 o c C o2 oc C o 3 oc C o 4PropertiesChemical formula C8H12O8Rh2Molar mass 441 99 g molAppearance Emerald green powderDensity 1 126 g cm3Melting point gt 100 CBoiling point decomposesSolubility in water solubleSolubility in other solvents polar organic solventsStructureCrystal structure monoclinicCoordination geometry octahedralDipole moment 0 DHazardsGHS labelling 1 PictogramsSignal word WarningHazard statements H315 H319Precautionary statements P264 P280 P302 P352 P305 P351 P338 P321 P332 P313 P337 P313 P362NFPA 704 fire diamond 300Flash point low flammabilitySafety data sheet SDS Coleparmer MSDSRelated compoundsRelated compounds Copper II acetateChromium II acetateExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Contents 1 Preparation 2 Structure and properties 3 Chemical properties 3 1 Selected catalytic reactions 4 ReferencesPreparation EditRhodium II acetate is usually prepared by the heating of hydrated rhodium III chloride in acetic acid CH3COOH 2 Rhodium II acetate dimer undergoes ligand exchange the replacement of the acetate group by other carboxylates and related groups 3 Rh2 OAc 4 4 HO2CR Rh2 O2CR 4 4 HOAcStructure and properties EditThe structure of rhodium II acetate features a pair of rhodium atoms each with octahedral molecular geometry defined by four acetate oxygen atoms water and a Rh Rh bond of length 2 39 A The water adduct is exchangeable and a variety of other Lewis bases bind to the axial positions 4 Copper II acetate and chromium II acetate adopt similar structures Chemical properties EditThe application of dirhodium tetraacetate to organic synthesis was pioneered by Teyssie and co workers 5 An extensive range of reactions including insertion into bonds and the cyclopropanation of alkenes 6 and aromatic systems 7 It selectively binds ribonucleosides vs deoxynucleosides by binding selectively to ribonucleosides at their 2 and 3 OH groups 8 Rhodium II acetate dimer compared to copper II acetate is more reactive and useful in differentiating ribonucleosides and deoxynucleosides because it is soluble in aqueous solution like water whereas copper II acetate only dissolves in non aqueous solution Selected catalytic reactions Edit Dirhodium tetraacetate is also used as catalyst for insertion into C H and X H bonds X N S O Cyclopropanation through the decomposition of diazocarbonyl compounds the intra and intermolecular cyclopropanation reactions occurs Aromatic cycloaddition Rhodium acetate catalyzes both two component cycloaddition as well as three component 1 3 dipolar cycloadditions C H insertion Rh II catalyzed regioselective intramolecular and regiospecific intermolecular C H insertion into aliphatic and aromatic C H bonds is a useful method for the synthesis of a diverse range of organic compounds Oxidation of alcohols Allylic and benzylic alcohols were oxidized to the corresponding carbonyl compounds using tert butyl hydroperoxide in stoichiometric amounts and Rh2 OAc 4 as catalyst in dichloromethane at ambient temperature X H insertion X N S O Rh II carbenoid reacts with amines alcohols or thiols to yield the product of a formal intra or intermolecular X H bond X N S O insertion via the formation of an ylide intermediate References Edit Dirhodium tetraacetate pubchem ncbi nlm nih gov Retrieved 14 December 2021 Rempel G A Legzdins P Smith H Wilkinson G 1972 Tetrakis acetato dirhodium II and Similar Carboxylato Compounds Inorg Synth Inorganic Syntheses Vol 13 pp 90 91 doi 10 1002 9780470132449 ch16 ISBN 9780470132449 Doyle M P 2000 Asymmetric Addition and Insertion Reactions of Catalytically Generated Metal Carbenes In Ojima Iwao ed Catalytic Asymmetric Synthesis 2nd ed New York Wiley ISBN 978 0 471 29805 2 Cotton F A Deboer B G Laprade M D Pipal J R Ucko D A 1971 The crystal and molecular structures of dichromium tetraacetate dihydrate and dirhodium tetraacetate dihydrate Acta Crystallogr B 27 8 1664 doi 10 1107 S0567740871004527 Paulissen R Reimlinger H Hayez E Hubert A J Teyssie P 1973 Transition metal catalysed reactions of diazocompounds II Insertion in the hydroxylic bond Tetrahedron Lett 14 24 2233 doi 10 1016 S0040 4039 01 87603 6 hdl 2268 236113 Hubert A J Feron A Warin R Teyssie P 1976 Synthesis of iminoaziridines from carbodiimides and diazoesters A new example of transition metal salt catalysed reactions of carbenes Tetrahedron Lett 17 16 1317 doi 10 1016 S0040 4039 00 78050 6 hdl 2268 236097 Anciaux A J Demonceau A Hubert A J Noels A F Petiniot N Teyssie P 1980 Catalytic control of reactions of dipoles and carbenes an easy and efficient synthesis of cycloheptatrienes from aromatic compounds by an extension of Buchner s reaction J Chem Soc Chem Commun 16 765 766 doi 10 1039 C39800000765 hdl 2268 237699 Berger N A Tarien E Eichhorn G L 1972 Stereoselective Differentiation between Ribonucleosides and Deoxynucleosides by Reaction with the Copper II Acetate Dimer Nature New Biology 239 95 237 40 doi 10 1038 newbio239237a0 PMID 4538853 Retrieved from https en wikipedia org w index php title Rhodium II acetate amp oldid 1060344945, wikipedia, wiki, book, books, library,
