(Alkylidyne)tungsten Complexes Anchored to a Planar Tetraoxo Surface: Exhaustive Alkylation of a (Calixarene)tungsten Complex†
Luca Giannini
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Search for more papers by this authorDr. Euro Solari
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Search for more papers by this authorDr. Antonio Zanotti-Gerosa
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Search for more papers by this authorCorresponding Author
Prof. Dr. Carlo Floriani
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905Search for more papers by this authorProf. Dr. Angiola Chiesi-Villa
Dipartimento di Chimica, Università di Parma, Viale delle Scienze, I-43100 Parma (Italy)
Search for more papers by this authorDr. Corrado Rizzoli
Dipartimento di Chimica, Università di Parma, Viale delle Scienze, I-43100 Parma (Italy)
Search for more papers by this authorLuca Giannini
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Search for more papers by this authorDr. Euro Solari
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Search for more papers by this authorDr. Antonio Zanotti-Gerosa
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Search for more papers by this authorCorresponding Author
Prof. Dr. Carlo Floriani
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905
Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH 3307, CH-1015 Lausanne (Switzerland), Fax: Int. code +(21)692-3905Search for more papers by this authorProf. Dr. Angiola Chiesi-Villa
Dipartimento di Chimica, Università di Parma, Viale delle Scienze, I-43100 Parma (Italy)
Search for more papers by this authorDr. Corrado Rizzoli
Dipartimento di Chimica, Università di Parma, Viale delle Scienze, I-43100 Parma (Italy)
Search for more papers by this authorThis work was supported by the Fonds National Suisse de la Recherche Scientifique (Grant. No. 20-40268.94) and Ciba–Geigy SA (Basel, Switzerland).
Graphical Abstract
Anchoring gives stability. The recently synthesized anionic tungsten alkylidynes fixed over a planar tetraoxo surface of calix[4]arene (see picture) can undergo reversible protonation and metalation by carbophilic metals without disturbing the calixarene ligand. R = Ph, nPr, SiMe3.
References
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- 7 Crystal structure analysis of 3: C51H57W·0.5C30H30MgN6·2C5H5N, Mr = 1325.5, monoclinic, space group P21/c, a = 22.038(3), b = 12.415(2), c = 25.171(3) Å, β = 98.74(1)°, V = 6806.9(17) Å3, Z = 4, ρcalcd = 1.293 gcm−3, F(000) = 2740, MoKα radiation (λ = 0.71069 Å), μ(MoKα) = 17.86 cm−1. Crystal dimensions 0.20 × 0.25 × 0.38 mm. The structure was solved by the heavy atom method, and all non-H atoms except those affected by disorder were anisotropically refined. The guest pyridine molecule (C61-C66) and the pyridine solvent molecule of crystallization (N4, C91-C95) were affected by high thermal parameters indicating the presence of disorder. The best fit was found by splitting the atoms over two positions (A and B), which were isotropically refined with site occupation factors of 0.65 and 0.35, respectively, for both molecules. The nitrogen atom in the guest pyridine molecule could not be unambiguosly distinguished. During the refinement the disordered pyridine solvent molecule of crystallization was constrained to be a regular hexagon. All the hydrogen atoms except those related to the disordered pyridine molecules, which were ignored, were located from a difference Fourier map and introduced as fixed contributors in the last stage of refinement (Uiso = 0.08 Å2). For 7981 unique observed reflections [I> 2σ(I)], collected at T = 295 K on a Rigaku AFC6S diffractometer (6° < 2θ <50°) and corrected for absorption, the final R is 0.053 (wR2 = 0.133). All calculations were carried out on a Quansan Personal Computer equipped with an Intel Pentium processor. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-179-127. Copies of the data can be obtained free of charge on application to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: int. code Int. +(1223)336-033; e-mail: [email protected]).
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- 9 A. Zanotti-Gerosa, E. Solari, L. Giannini, C. Floriani, A. Chiesi-Villa, C. Rizzoli, J. Chem. Soc. Chem. Commun. 1996, 119–120.
- 10 No further discussion on the F position is possible due to its low occupancy. The shortest contact distances are between the C61A atom and the B ring of calixarene (range varying from 3.54(3) to 3.88(2) Å) as well as the C66A atom and the C ring (range varying from 3.75(3) to 3.90(2) Å).
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- 12 See ref. [2], p. 189–190.
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