Title: CH Bond Addition to a VNR Bond: Hydrocarbon Activation by a Sterically Crowded Vanadium System
Abstract: Angewandte Chemie International Edition in EnglishVolume 32, Issue 6 p. 903-905 Communication CH Bond Addition to a VNR Bond: Hydrocarbon Activation by a Sterically Crowded Vanadium System Jan de With, Jan de With Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B. B.), P.O. Box 3003, NL-1003 AA Amsterdam (The Netherlands), Telefax : Int. code + (20) 630-8025Search for more papers by this authorDr. Andrew D. Horton, Corresponding Author Dr. Andrew D. Horton Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B. B.), P.O. Box 3003, NL-1003 AA Amsterdam (The Netherlands), Telefax : Int. code + (20) 630-8025Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B. B.), P.O. Box 3003, NL-1003 AA Amsterdam (The Netherlands), Telefax : Int. code + (20) 630-8025Search for more papers by this author Jan de With, Jan de With Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B. B.), P.O. Box 3003, NL-1003 AA Amsterdam (The Netherlands), Telefax : Int. code + (20) 630-8025Search for more papers by this authorDr. Andrew D. Horton, Corresponding Author Dr. Andrew D. Horton Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B. B.), P.O. Box 3003, NL-1003 AA Amsterdam (The Netherlands), Telefax : Int. code + (20) 630-8025Koninklijke/Shell-Laboratorium, Amsterdam (Shell Research B. B.), P.O. Box 3003, NL-1003 AA Amsterdam (The Netherlands), Telefax : Int. code + (20) 630-8025Search for more papers by this author First published: June 1993 https://doi.org/10.1002/anie.199309031Citations: 123AboutPDF 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 Alkanes, alkenes, and benzene are activated by intermediate 1, which has a three-coordinate vanadium center, by the addition of a CH bond to one of the VN bonds. The unstable complex 1 is generated from [RNV(NHR)2R′] on thermolysis. R = tBu3Si. References 1(a) R. F. Jordan, Adv. Organomet. Chem. 1991, 32, 325; (b) X. Yang, C. L. Stern, T. J. Marks, Organometallics 1992, 10, 840; (c) E. B. Coughlin, J. E. Bercaw, J. Am. Chem. Soc. 1992, 114, 7606; (d) B. J. Burger, M. E. Thompson, W. D. Cotter, J. E. Bercaw, J. Am. Chem. Soc. 1990, 112, 1566; (e) G. Jeske, H. Lauke, H. Mauermann, P. N. Swepston, H. Schumann, T. J. Marks J. Am. Chem. Soc. 1985, 107, 8091 2(a) M. E. Thompson, S. M. Baxter, A. R. Bulls, B. J. Burger, M. C. Nolan, B. D. Santarsiero, W. P. Schaefer, J. E. Bercaw, J. Am. Chem. Soc. 1987, 109, 203; (b) P. L. Watson, G. W. Parshall, Ace. Chem. Res. 1985, 18, 51. 3(a) F. J. Feher, R. L. Blanski, J. Am. Chem. Soc. 1992, 114, 5886; (b) D. D. Devore, J. J. Lichtenhan, F. Takusagawa, E. A. Maatta, J. Am. Chem. Soc. 1987, 1090, 7408; (c) F. Preuss, H. Becker, J. Kaub, W. S. Sheldrick, Z. Naturforsch. B 1988, 43, 1195. 4(a) C. C. Cummins, S. M. Baxter, P. T. Wolczanski, J. Am. Chem. Soc. 1988, 110, 8731; (b) C. C. 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Formation of [RN = V(NDR)n(NHR)2-n(C6D5)] (n =1, 2) in C6D12 solution is effectively zero order relative to the concentration of C6D6 for > 5 equivalents C6D6. 8 The following rate constants for CH4 elimination from [RN = V(NHR)2CH3] in C6D6 were obtained: k × 105 =1.15 (60 °C); 5.26 (70 °C); 11.4 (80 °C) 59.4 (90 °C) s−1 9 Rough rate constants at about 25 °C for R′-H elimination from [RN = V(NHR)2R′] in C6D6 (to give [RN = V(NDR)n(NHR)2-n (C6D5)](n =1, 2)) were obtained: k × 107 = 2.5 (3a); 5.0 (3b); 9.0 (3d) s−1. 10 For example, solutions of the alkenyl complex 5a in C6D12 at 25 °C eliminate H2CCH(tBu) with concomitant formation of [RN = V(NHR)3] (40 % conversion after 4 days). Similar hydrocarbon elimination from 4, 5b, c may be responsible for the decomposition observed during attempted crystallizations from alkane solutions. 11 J. H. Freudenberger, R. R. Schrock, Organometallics 1986, 5, 398. 12 After the completion of this work Wolczanski reported the generation of RN = Ti(OR)2, which undergoes a range of addition reactions related to those discussed here: P. T. Wolczanski, 204th ACS National Meeting, Washington, D.C., USA, 1992. 13(a) J. E. Hill, R. D. Profiler, P. E. Fanwick, I. P. Rothwell, Angew. Chem. 1990, 102, 713; Angew. Chem. Int. Ed. Engl. 1990, 29, 664; (b) R. D. Profilet, C. H. Zambrano, P. E. Fanwick, J. J. Nash, I. P. Rothwell, Inorg. Chem. 1990, 29, 4362; (c) D. J. Arney, M. A. Bruck, S. R. Huber, D. E. Wigley, Inorg. Chem. 1992, 31, 3755; (d) Y. Bai, H. W. Roesky, M. Noltemeyer, M. Witt, Chem. Ber. 1992, 125, 825. 14 J. de With, A. D. Horton, A. G. Orpen, Organometallics, in press. Citing Literature Volume32, Issue6June 1993Pages 903-905 ReferencesRelatedInformation
Publication Year: 1993
Publication Date: 1993-06-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 127
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