Seidl, Michael and Schiffer, Michael and Bodensteiner, Michael and Timoshkin, Alexey Y. and Scheer, Manfred (2013) Reactivity of Bridged Pentelidene Complexes with Isonitriles: A New Way to Pentel-Containing Heterocycles. CHEMISTRY-A EUROPEAN JOURNAL, 19 (41). pp. 13783-13791. ISSN 0947-6539, 1521-3765
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The reaction of [Cp*E{W(CO)(5)}(2)] (E=P (1a), As (1b); Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with isonitriles RNC (R=tBu, cyclohexyl (Cy), nBu) depends on the steric demand of the substituent at the isonitrile as well as on the stoichiometry of the starting materials. With tBuNC only the Lewis acid/base adducts [Cp*E{W(CO)(5)}(2)(CNtBu)] (E=P (2a), As (2b)) are formed. The use of Cy and n-butylisonitrile leads first to the formation of the Lewis acid/base adduct, but only at low temperatures. At ambient temperatures, a rearrangement occurs and bicyclo[3.2.0]heptane derivatives of the type [{C(Me)C(CH2)C(Me)C(Me)C(Me)}C(NR)- E{W(CO)(5)}(2)] (E=P, As; R=Cy, nBu) (3a-Cy, 3b-Cy, 3a-nBu and 3b-nBu) are obtained. The use of a further equivalent of isonitrile results in products revealing two new structural motifs, the four-membered ring derivatives [C(Cp*)N(R)C(NR)E{W(CO)(5)}(2)] (4: E=P, As; R=Cy, nBu) and the bicyclic complexes [[{C(Me)C- (CH2)C(Me)C(Me)C(Me)}C(NR)(2)- E{W(CO)(5)}(2)] (5: E=As; R=Cy). The reaction pathway depends on the substituent at the isonitrile. By treatment of 1a with two equivalents of CyNC only a 2H-1,3-azaphosphet complex 4a-Cy (E=P; R=Cy) is formed. Treatment of 1b with two equivalents of CyNC exclusively leads to the complex 5b-Cy (E=As; R=Cy). Treatment of 1a with two equivalents of nBuNC results in a mixture of complexes, the 2H-1,3-azaphosphet 4a-nBu (E=P; R=nBu) and the bicyclic complex 5a-nBu (E=P; R=nBu). For the arsenidene complex 1b a mixture of the 2H-1,3-azarsete complex 4b-nBu (E=As; R=nBu) and the bicyclic complex 5b-nBu (E=P, As; R=Cy, nBu) is obtained. Complex 4b-nBu is the first example of a 2H-1,3-azarsete complex. All products have been characterized by using mass spectrometry, NMR spectroscopy, and X-ray diffraction analysis.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | EFFECTIVE CORE POTENTIALS; PHOSPHORUS TRIPLE BOND; PHOSPHINIDENE COMPLEXES; TERMINAL PHOSPHINIDENE; MOLECULAR CALCULATIONS; CRYSTAL-STRUCTURES; STEREOSELECTIVE FORMATION; P-C; METAL; RING; arsenic; heterocycles; isonitriles; pentelidenes; phosphorus; X-ray diffraction |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 27 Mar 2020 15:07 |
| Last Modified: | 27 Mar 2020 15:07 |
| URI: | https://pred.uni-regensburg.de/id/eprint/15860 |
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