Unsaturated Organometallic Intermediates: Electronic Structure and Structural Dynamics of (η 5 ‐C 5 H 5 )Mn(CO) 2
1977; Wiley; Volume: 16; Issue: 8 Linguagem: Inglês
10.1002/anie.197705361
ISSN1521-3773
Autores Tópico(s)Rare-earth and actinide compounds
ResumoAngewandte Chemie International Edition in EnglishVolume 16, Issue 8 p. 536-537 Communication Unsaturated Organometallic Intermediates: Electronic Structure and Structural Dynamics of (η5-C5H5)Mn(CO)2† Dr. Peter Hofmann, Corresponding Author Dr. Peter Hofmann Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-8520 ErlangenInstitut für Organische Chemie der Universität Erlangen-Nürnberg Henkestrasse 42, D-8520 ErlangenSearch for more papers by this author Dr. Peter Hofmann, Corresponding Author Dr. Peter Hofmann Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestrasse 42, D-8520 ErlangenInstitut für Organische Chemie der Universität Erlangen-Nürnberg Henkestrasse 42, D-8520 ErlangenSearch for more papers by this author First published: August 1977 https://doi.org/10.1002/anie.197705361Citations: 71 † This work was supported by the Deutsche Forschungsgemeinschaft. 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 Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract “Half-sandwich” molecular fragments of the type (CnHn)ML2 having only 16 electrons in their valence shell are important intermediates. The questions of “planar” (1a) or “pyramidal” ground state geometry (1b) and of energy barriers are examined for the model system CpMn(CO)2. References 1 Review: H. Brunner, Fortschr. Chem. Forsch. 56, 67 (1975). 2 P. S. Braterman, J. D. Black, J. Organomet. Chem. 39, C 3 (1972). 3 MO calculations of extended-Hückel type: R. Hoffmann, J. Chem. Phys. 39, 1397 (1963); R. Hoffmann, W. N. Lipscomb, J. Chem. Phys. 36, 2179, 3489 (1962); J. Chem. Phys. 37, 2872 (1962). Manganese parameters: 3d functions: J. W. Richardson, W. C. Nieuwpoort, R. R. Powell, W. F. Edgell, At. Data Nucl. Data Tables 36, 1057 (1962); 4s, 4p functions: R. H. Summerville, R. Hoffmann, J. Am. Chem. Soc. 98, 7240 (1976). The Hii parameters are taken from a SCC calculation with quadratic charge dependence 4 on CpMn (CO)3. 4 H. Basch, A. Viste, H. B. Gray, Theor. Chim. Acta 3, 458 (1965). 5 The MOs of the fragment (4b) are of significance in connection with the extensively utilized ability of the CpMn(CO)2 group to stabilize unusual ligands. 6 Concerning the fragment view of organometallic systems, cf. M. Elian, R. Hoffmann, Inorg. Chem. 14, 1058 (1975); R. Hoffmann, P. Hofmann, J. Am. Chem. Soc. 98, 598 (1976); J. W. Lauher, R. Hoffmann, J. Am. Chem. Soc. 98, 1729 (1976). 7 For a qualitative derivation of the MOs of a C2v-M(CO)2 fragment, cf. J. K. Burdett, J. Chem. Soc. Faraday Trans. 2 1974, 1599. 8 The motion of the model corresponds to variable ϕ (cf. Fig. 1, right-hand third) and constant angle between the z axis and the MnCO vectors. 9 Cf. the MO analysis of inversion of XR3: C. C. Levin, J. Am. Chem. Soc. 97, 5649 (1975). Citing Literature Volume16, Issue8August 1977Pages 536-537 ReferencesRelatedInformation
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