Valence isomerization in the solid state: From 1,3-diphosphacyclobutane-2,4-diyl to 1,2-dihydro-1,2-diphosphete

Angewandte Chemie - International Edition

Volumn 37, Issue 7, 1998, Pages 949-952

  Schmidt, Olaf ^a   Fuchs, André ^a   Gudat, Dietrich ^a   Nieger, Martin ^a   Hoffbauer, Wilfried ^a   Niecke, Edgar ^a   Schoeller, Wolfgang W ^b  

^a UNIVERSITY OF BONN   (Germany)

^b BIELEFELD UNIVERSITY   (Germany)

Author keywords

Ab initio calculations; Diradicals; NMR spectroscopy; Phosphorus heterocycles; Valence isomerization

Indexed keywords

EID: 0031971664     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980420)37:7<949::AID-ANIE949>3.0.CO;2-H     Document Type: Article

References (28)

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7. 2a: A solution of tBuLi (4.7 mmol, 2.8 mL of a 1.7 M solution in hexane) was added dropwise to a solution of 1 (2.4 g, 9.4 mmol) in THF (100 mL) at -105°C. The reaction mixture was slowly warmed to -80°C and stirred for 4 h. The resulting purple solid was separated by filtration at -80°C to afford 2 a (1.44 g, 70%). 3a: A solution of tBuLi (4.7 mmol, 2.8 mL of a 1.7 M solution in hexane) was added dropwise to a solution of 1 (2.4 g, 9.4 mmol) in THF (100 mL) at -105°C. The reaction mixture was slowly warmed to room temperature under stirring, and the solvents were removed in vacuo. The residue was washed with n-pentane (50 mL). and precipitated LiCl was separated by filtration. Removal of the solvent in vacuo afforded 3a as beige crystals (1.93 g, 93%; m.p. 148-149°C).
8. +]; correct elemental analysis.
9. [9b] Non-hydrogen atoms were refined anisotropically, and H atoms localized by difference electron density and refined with a riding model (wR2 = 0.136, R1 = 0.051. for I > 2σ(I)). An empirical absorption correction on the basis of ψ scans was applied; the absolute structure could not be determined reliably. 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-100757. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
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19. 33 = -185.
20. 33 = -185.
21. The energy optimation at the MP2 level was performed with the Gaussian set of programs: Gaussian94 (Revision D4), M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople, Gaussian Inc., Pittsburgh, PA, 1995.
22. 2 moiety, resulting in five occupied and five antibonding molecular orbitals.
23. 2 moiety, resulting in five occupied and five antibonding molecular orbitals.
24. All stationary points on the electronic hypersurface were characterized by vibrational analysis based on the method of numerical differentiation of the first-order gradients. Consequently, energy minima possess overall positive vibrational frequencies, and the two transition states display one imaginary vibration. Energy values were obtained from the MCSCF energies after zero-point vibrational correction.
25. [4]
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27. E. Niecke, O. Schmidt, W. W. Schoeller, G. Bertrand, unpublished results
28. An alternative synthesis of 3a was recently reported: N. Cēnac, A. Chrostowska, J.-M. Sotiropoulos, B. Bonnadieu, A. Igau, G. Pfister-Guillouzo, J.-P. Majoral, Organometallics 1997, 16, 4551.