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Platinum in the Unusual Oxidation State + 2.75: A Linear Tetranuclear Complex with the Model Nucleobase 1‐Methylthymine

1990; Wiley; Volume: 29; Issue: 1 Linguagem: Inglês

10.1002/anie.199000841

1521-3773

Oliver Renn, Bernhard Lippert, Alberto Albinati,

Metal-Catalyzed Oxygenation Mechanisms

Angewandte Chemie International Edition in EnglishVolume 29, Issue 1 p. 84-85 Communication Platinum in the Unusual Oxidation State + 2.75: A Linear Tetranuclear Complex with the Model Nucleobase 1-Methylthymine† Dipl.-Chem. Oliver Renn, Dipl.-Chem. Oliver Renn Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG)Search for more papers by this authorProf. Dr. Bernhard Lippert, Corresponding Author Prof. Dr. Bernhard Lippert Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG) Bernhard Lippert, Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG) Alberto Albinati, Istituto Chimico Farmaceutico della Università di Milano Viale Abruzzi, 42, I-20131 Milano (Italy)Search for more papers by this authorProf. Dr. Alberto Albinati, Corresponding Author Prof. Dr. Alberto Albinati Istituto Chimico Farmaceutico della Università di Milano Viale Abruzzi, 42, I-20131 Milano (Italy) Bernhard Lippert, Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG) Alberto Albinati, Istituto Chimico Farmaceutico della Università di Milano Viale Abruzzi, 42, I-20131 Milano (Italy)Search for more papers by this author Dipl.-Chem. Oliver Renn, Dipl.-Chem. Oliver Renn Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG)Search for more papers by this authorProf. Dr. Bernhard Lippert, Corresponding Author Prof. Dr. Bernhard Lippert Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG) Bernhard Lippert, Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG) Alberto Albinati, Istituto Chimico Farmaceutico della Università di Milano Viale Abruzzi, 42, I-20131 Milano (Italy)Search for more papers by this authorProf. Dr. Alberto Albinati, Corresponding Author Prof. Dr. Alberto Albinati Istituto Chimico Farmaceutico della Università di Milano Viale Abruzzi, 42, I-20131 Milano (Italy) Bernhard Lippert, Fachbereich Chemie, Lehrstuhl III Anorganische Chemie der Universität, Postfach 50 05 00, D-4600 Dortmund 50 (FRG) Alberto Albinati, Istituto Chimico Farmaceutico della Università di Milano Viale Abruzzi, 42, I-20131 Milano (Italy)Search for more papers by this author First published: January 1990 https://doi.org/10.1002/anie.199000841Citations: 22 † This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation 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 Graphical Abstract PtPtClPtPt plus ligand—this epitomizes the structure of the cation of the title compound: cis-[{(NH3)2Pt(MeT)2PtCl2}2]Cl2⊕; MeT is thereby the anion of 1 -methylthymine. This novel mixed valence platinum(2.75) complex formally contains three PtIIIcenters and one PtIIcenter. A PtPt unit together with ligands and bridging chlorine atom is pictured on the right. References 1 K. Krogmann, Angew. Chem. 81 (1969) 10; Angew. Chem. Int. Ed. Engl. 8 (1969) 35. 2For example R. J. H. Clark, V. B. Croud, H. M. Dawes, M. B. Hursthouse, J. Chem. Soc. Dalton Trans. 1986, 403, and references cited therein. 3For example (a) R. J. H. Clark, M. Kurmoo, H. M. Dawes, M. B. Hurst-house, Inorg. Chem. 25 (1986) 409; (b) L. G. Butler, M. Heinrichs Zietlow, C.-M. Che, W. P. Schaefer, S. Sridhar, P. J. Grunthaner, B. I. Swanson, R. J. H. Clark, H. B. Gray, J. Am. Chem. Soc. 110 (1988) 1155. 4 J. K. Barton, H. N. Rabinowitz, D. J. Szalda, S. J. Lippard, J. Am. Chem. Soc. 99 (1977) 2827. 5 K. Matsumoto, K. Fuwa, J. Am. Chem. Soc. 104 (1982) 897. 6(a) B. Lippert, D. Neugebauer, Inorg. Chem. 21 (1982) 451; (b) P. K. Mascharak, I. D. Williams, S. J. Lippard, J. Am. Chem. Soc. 106 (1984) 6428; (c) B. Lippert, H. Schöllhorn, U. Thewalt, Inorg. Chem. 26 (1987) 1736; (d) W. Micklitz, J. Riede, B. Huber, G. Müller, B. Lippert, Inorg. Chem. 27 (1988) 1979. 7 K. Sakai, K. Matsumoto, J. Am. Chem. Soc. 111 (1989) 3074. 8 W. Micklitz, G. Müller, B. Huber, J. Riede, F. Rashwan, J. Heinze, B. Lippcrt, J. Am. Chem. Soc. 110 (1988) 7084. 9 J. P. Davidson, P. J. Faber, R. G. Fischer, Jr., S. Mansy, H. J. Peresie, B. Rosenberg, I. van Camp, Cancer Chemother. Rep., Part I 59 (1975) 287. 10 E° (1/1 a) 560mV (vs. Ag/AgCl); E° (la/lb) 720mV. For details of the methods see [6d]: λmax(1 a) 740 nm, ε = 24100cm−1M−1. 11 From the shape and width of the 480-nm absorption it can be assumed that this is possibly an overlap of two bands, whereby an absorption in the range 510–520 nm would be expected for a [Pt(2.5)]2 compound. Cf. B. Lippert, New J. Chem. 12 (1988) 715. 12 W. Micklitz, O. Renn, H. Schöllhorn, U. Thewalt, B. Lippert, Inorg. Chem., in press. 13 Crystal structure analysis: CAD-4 diffractometer, MoKα, radiation, room temperature. — 4 with cation 2c: monoclinic, space group P21/n, a = 13.562(2), b = 11.058(3), c = 18.728(3) Å, β = 105.60(2)°, V = 2705(2) Å3, Z = 4, ω/2θ scan with 2θ ≤ 50.0°, 4717 reflections (corrected for absorption and decay), 3298 observed reflections with F ≥ 2.5 σ (F), Patterson and Fourier methods, anisotropic temperature factors for heavy atoms except water of crystallization oxygen atoms, R = 0.037 (observed reflections). Bridge Cl atoms (C11) and Pt3 (PtCl anion of 4) on crystallographic inversion center (1), therefore only half a tetramer unit and half an anion independent, one H2O molecule disordered, refined with occupation factors 0.5—5 with cation 2d: monoclinic, space group C2/c a = 23.874(3), b = 19.144; 4.78(2) Å, β = 123.18(4)°, V = 5538(3)Å3,Z = 8, 2θ ≤ 45.0°, 4852 observed reflections with F0 ≥ σ(F0), heavy atoms refined with anisotropic temperature factors, R = 0.064 (observed reflections). Water of crystallization, water bound to Pt, and Cl disordered, possible models for the refinement in progress. Further details of the crystal structure investigations are available on request from the Fachinformationszentrum Karlsruhe. Gesellschaft für wissenschaftlich-technische Information mbH, D-7514 Eggenstein-Leopolashafen 2 (FRG), on quoting the depository number CSD-54 140, the names of the authors, and the journal citation. 14 B. Lippert, H. Schöllhorn, U. Thewalt, Inorg. Chem. 25 (1986) 407. 15 For comparison: Na2PtCl6 is not reduced under the given reaction conditions (pH 3). Citing Literature Volume29, Issue1January 1990Pages 84-85 ReferencesRelatedInformation