Portal de Periódicos da CAPES

Dimetallic Dioxygen Activation Leading to a Doubly Oxygen‐Bridged Dirhodium Complex

2005; Wiley; Volume: 117; Issue: 21 Linguagem: Inglês

10.1002/ange.200463073

1521-3757

Cristina Tejel, Miguel A. Ciriano, Eduardo Sola, M. Pilar del Rı́o, G. Rios-Moreno, Fernando J. Lahoz, Luis A. Oro,

Catalytic C–H Functionalization Methods

Angewandte ChemieVolume 117, Issue 21 p. 3331-3335 Zuschrift Dimetallic Dioxygen Activation Leading to a Doubly Oxygen-Bridged Dirhodium Complex† Cristina Tejel Dr., Cristina Tejel Dr. [email protected] Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorMiguel A. Ciriano Prof., Miguel A. Ciriano Prof. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorEduardo Sola Dr., Eduardo Sola Dr. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorM. Pilar del Río, M. Pilar del Río Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorGustavo Ríos-Moreno Dr., Gustavo Ríos-Moreno Dr. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorFernando J. Lahoz Prof., Fernando J. Lahoz Prof. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorLuis A. Oro Prof., Luis A. Oro Prof. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187 Instituto Universitario de Catálisis Homogénea, Universidad de Zaragoza, 50009 Zaragoza, SpainSearch for more papers by this author Cristina Tejel Dr., Cristina Tejel Dr. [email protected] Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorMiguel A. Ciriano Prof., Miguel A. Ciriano Prof. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorEduardo Sola Dr., Eduardo Sola Dr. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorM. Pilar del Río, M. Pilar del Río Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorGustavo Ríos-Moreno Dr., Gustavo Ríos-Moreno Dr. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorFernando J. Lahoz Prof., Fernando J. Lahoz Prof. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187Search for more papers by this authorLuis A. Oro Prof., Luis A. Oro Prof. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, 50009 Zaragoza, Spain, Fax: (+34) 976-761-187 Instituto Universitario de Catálisis Homogénea, Universidad de Zaragoza, 50009 Zaragoza, SpainSearch for more papers by this author First published: 17 May 2005 https://doi.org/10.1002/ange.200463073Citations: 21 † The generous financial support from MCyT(DGI)/FEDER (Projects BQU2002-00074 and BQU2003-05412) is gratefully acknowledged. Read the full textAboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Die einfache Spaltung von Disauerstoff und seine selektive Insertion in Rh-Alken-Bindungen beobachtet man in Gegenwart von [{Rh(PhN3Ph)(C8H12)}n] (n=1 und 2). Die Struktur des gebildeten Dirhodadioxetankomplexes (siehe Bild) und kinetische Messungen stützen einen Dimetallmechanismus für diesen Prozess, der mit 100 % Atomökonomie abläuft. References 1D. H. R. Barton, The Activation of Dioxygen and Homogeneous Catalytic Oxidation, Plenum, New York, 1993. 10.1007/978-1-4615-3000-8 Google Scholar 2W. N. M. Van Leeuwen, Homogeneous Catalysis, Kluwer Academic Publisher, Dordrecht, 2004. 10.1007/1-4020-2000-7 Google Scholar 3 3aS. S. Stahl, Angew. Chem. 2004, 116, 3480; 10.1002/ange.200300630 Google ScholarAngew. Chem. Int. Ed. 2004, 43, 3400; 10.1002/anie.200300630 CASPubMedWeb of Science®Google Scholar 3b“Catalysis by Metal Complexes”: Advances in Catalytic Activation of Dioxygen by Metal Complexes, Vol. 26 (Ed.: ), Kluwer Academic Publisher, Dordrecht 2003; Google Scholar 3cA. L. Gavrilova, C. J. Qin, R. D. Sommer, A. L. Rheingold, B. Bosnich, J. Am. Chem. Soc. 2002, 124, 1714. 10.1021/ja012386z CASPubMedWeb of Science®Google Scholar 4B. De Bruin, P. H. M. Budzelaar, A. W. Gal, Angew. Chem. 2004, 116, 4236; 10.1002/ange.200300629 Google ScholarAngew. Chem. Int. Ed. 2004, 43, 4142. 10.1002/anie.200300629 CASPubMedWeb of Science®Google Scholar 5 5aB. De Bruin, J. A. E. Verhagen, C. H. J. Shouten, A. W. Gal, D. Feichtinger, D. A. Plattner, Chem. Eur. J. 2001, 7, 416; 10.1002/1521-3765(20010119)7:2 3.0.CO;2-Q CASPubMedWeb of Science®Google Scholar 5bB. De Bruin, M. J. Boerakker, J. A. W. Verhagen, R. De Gelder, J. M. M. Smits, A. W. Gal, Chem. Eur. J. 2000, 6, 298. 10.1002/(SICI)1521-3765(20000117)6:2 3.0.CO;2-Z CASPubMedWeb of Science®Google Scholar 6T. C. Flood, M. Iimura, J. M. Perotti, A. L. Rheingold, T. E. Concolino, Chem. Commun. 2000, 1681. 10.1039/b002079f CASWeb of Science®Google Scholar 7 7aT. Sciarone, J. Hoogboom, P. P. J. Schlebos, P. H. M. Budzelaar, R. de Gelder, J. M. M. Smits, A. W. Gal, Eur. J. Inorg. Chem. 2002, 457; 10.1002/1099-0682(20022)2002:2 3.0.CO;2-P CASWeb of Science®Google Scholar 7bB. De Bruin, J. A. Brands, J. J. J. M. Donners, M. P. J. Donners, R. De Gelder, J. M. M. Smits, A. W. Gal, A. L. Spek, Chem. Eur. J. 1999, 5, 2921. 10.1002/(SICI)1521-3765(19991001)5:10 3.0.CO;2-1 CASWeb of Science®Google Scholar 8 8aM. Krom, T. P. J. Peters, R. G. E. Coumans, T. J. J. Sciarone, J. Hoogboom, S. I. ter Beek, P. P. J. Schlebos, J. M. M. Smits, R. de Gelder, A. W. Gal, Eur. J. Inorg. Chem. 2003, 1072. 10.1002/ejic.200390139 CASWeb of Science®Google Scholar 9V. W. Day, W. G. Klemperer, S. P. Lockledge, D. J. Main, J. Am. Chem. Soc. 1990, 112, 2031. 10.1021/ja00161a076 CASWeb of Science®Google Scholar 10W. H. Knoth, Inorg. Chem. 1973, 12, 38. 10.1021/ic50119a010 CASWeb of Science®Google Scholar 113D Search and Research using the Cambridge Structural Database, F. H. Allen, O. Kennard, Chem. Des. Auto. News 1993, 8, 31. Google Scholar 12Crystal data for 2⋅3 C7H8: C40H44N6O2Rh2⋅3 C7H8, Mr=1123.04, prismatic crystal (0.16×0.05×0.05 mm), triclinic, space group P, a=9.7616(11), b=11.5598(13), c=12.4273(14) Å, α=86.458(2), β=68.865(2), γ=87.552(2)°, V=1305.2(3) Å−3, Z=1, ρcalcd=1.429 g cm−3, F(000)=582.0, T=100(2) K, MoKα radiation (λ=0.71073 Å, μ=0.682 mm−1). Data collected with a Bruker SMART APEX CCD diffractometer. Of 15 557 measured reflections (2θ: 3.5–55°, ω scans 0.3°), 5903 were unique (Rint=0.0406); a multiscan absorption correction was applied (SADABS program) with min./max. transmission factors of 0.932/0.955. Structure solved by Patterson and difference-Fourier maps; refined using SHELXTL. A disordered toluene molecule was found in the asymmetric unit. Final agreement factors were R1=0.0506 (5226 obs. reflections, F2>4σ(F2)) and wR2=0.1086; data/restrains/parameters 5903/0/454; GOF=1.112. CCDC-258836 (2) and CCDC-258837 (3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Google Scholar 13Crystal data for 3: C20H22N3ORh, Mr=423.31, monoclinic, space group P21/n, a=10.7068(11), b=16.5017(18), c=40.470(4) Å, β=95.299(2)°, V=7119.7(13) Å−3, Z=16, ρcalcd=1.580 g cm−3, F(000)=3456, T=100(2) K, MoKα radiation (λ=0.71073 Å, μ=0.972 mm−1). Data collected as described for 2 with an irregular prism (0.084×0.054×0.054 mm). Of 38 220 measured reflections (2θ: 2–50°), 12 544 were unique (Rint=0.1048); a multiscan absorption correction was performed (SADABS program) with min./max. transmission factors of 0.923/0.942. Structure solution and refinement as described for 2. Two independent, but chemically equivalent, dimeric complexes were found in the asymmetric unit. Final agreement factors were R1=0.068 (6315 observed reflections) and wR2=0.1737. Data/restrains/parameters 12 544/42/901; GOF=0.998. All residual peaks above 1 e Å−3 were found in close proximity to the rhodium metal and have no chemical sense. Google Scholar 14P. Piraino, G. Tresoldi, F. Faraone, J. Organomet. Chem. 1982, 224, 305. 10.1016/S0022-328X(00)85843-X CASWeb of Science®Google Scholar 15F. J. Lahoz, A. Tiripicchio, M. Tiripicchio-Camellini, L. A. Oro, M. T. Pinillos, J. Chem. Soc. Dalton Trans. 1985, 1487. 10.1039/DT9850001487 CASWeb of Science®Google Scholar 16TRC Thermodynamic Tables, Vol. VIII, p. Kb-3290. Google Scholar Citing Literature Volume117, Issue21May 20, 2005Pages 3331-3335 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. ReferencesRelatedInformation