Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2

Weber L, Misiak H, Buchwald S, Stammler H-G, Neumann B (1994)
Organometallics 13(6): 2194-2204.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Metallodiphosphenes (eta5-C5R5) (CO)2M-P=P-Mes* (C5R5 = C5Me5, C5Me4Et, 1,2,4-iPr3CrH2, 1,3-tBu2C5H3,1,3-(Me3Si)2C5H3; M = Fe,Ru) undergo reaction with anhydrous hexafluoroacetone to afford either the five-membered metallaheterocycles (eta5-C5R5)(CO)M-P(=PMes*)OC-(CF3)2C(O) or metalated 1-oxa-2,3-diphosphetanes (eta5-C5R5)(CO)2M-P-P(Mes*)OC(CF3)2. It is demonstrated that the l-oxa-2,3-diphosphetanes result from an intramolecular rearrangement of the metallaheterocycles. The course of the reaction and the nature of the products is largely influenced by the basicity of the cyclopentadienylmetal fragment. The molecular structures of (eta5-C5Me5) (CO)Fe-P(=PMes*)OC(CF3)2C(O) (9a) (P2(1)/c, a = 21.809(4) angstrom, b = 10.066(2) angstrom, c = 16.250(3) angstrom, beta = 95.87(1)-degrees, (eta5-C5Me5)(CO)Ru-P=P(Mes*)OC(CF3)2C(O) (10a) (P2(1)/c, a = 22.308(8) angstrom, b = 10.174(4) angstrom, c = 16.014(10) angstrom, beta = 96.62(4)-degrees), (eta5-1,2,4-iPr3C6H2)(CO)Ru-P-(=PMes*)OC(CF3)2C(O) (10c) (P1BAR, a = 9.416(5) angstrom, b = 9.784(6) angstrom, c = 24.40(2) angstrom, alpha = 92.74(5)-degrees, beta = 98.42(5)-degrees, gamma = 117.37(4)-degrees), and (eta5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2 (11a) (C2/c, a = 46.79(3) angstrom, b = 9.316(5) angstrom, c = 16.611(5) angstrom, beta = 101.52(3)-degrees) were determined by single-crystal X-ray analyses.
Erscheinungsjahr
1994
Zeitschriftentitel
Organometallics
Band
13
Ausgabe
6
Seite(n)
2194-2204
ISSN
0276-7333
eISSN
1520-6041
Page URI
https://pub.uni-bielefeld.de/record/1774693

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Weber L, Misiak H, Buchwald S, Stammler H-G, Neumann B. Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2. Organometallics. 1994;13(6):2194-2204.
Weber, L., Misiak, H., Buchwald, S., Stammler, H. - G., & Neumann, B. (1994). Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2. Organometallics, 13(6), 2194-2204. doi:10.1021/om00018a012
Weber, L., Misiak, H., Buchwald, S., Stammler, H. - G., and Neumann, B. (1994). Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2. Organometallics 13, 2194-2204.
Weber, L., et al., 1994. Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2. Organometallics, 13(6), p 2194-2204.
L. Weber, et al., “Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2”, Organometallics, vol. 13, 1994, pp. 2194-2204.
Weber, L., Misiak, H., Buchwald, S., Stammler, H.-G., Neumann, B.: Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2. Organometallics. 13, 2194-2204 (1994).
Weber, Lothar, Misiak, Hanns, Buchwald, Susanne, Stammler, Hans-Georg, and Neumann, Beate. “Studies on the Reactivity of Metallodiphosphenes (η5-C5R5)(CO)2M-P=P-Mes* of Iron and Ruthenium towards Hexafluoroacetone. X-ray Structure Analyses of (η5-C5Me5)(CO)M-P(=PMes*)OC(CF3)2C(O) (M = Fe, Ru), (η5-1,2,4-iPr3C5H2)(CO)Ru-P(=PMes*)OC(CF3)2C(O), and (η5-C5Me5)(CO)2Fe-P-P(Mes*)OC(CF3)2”. Organometallics 13.6 (1994): 2194-2204.
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