ISSN:
0009-2940
Keywords:
Ruthenacycloalkanes
;
Osmacycloalkanes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXIV1. - Preparation and Investigations about the Reactivity of η2-Olefin Complexes and Four- to Six-Membered Metallacycloalkanes of Ruthenium and OsmiumThe olefin complexes (η2-CH2=CHR)M(CO)4 (3a, b, 5a, b) [R = H (3), CH3 (5); M = Ru (a), Os (b)] and four- to six-membered metallacycloalkanes (7a, b, 9b) [R = H (7), CH3 (9)], (11a, b, 15a, b) [n = 2 (11), 3 (15)], (13a, b) are obtained by nucleophilic elimination-cycloaddition on the alkanediyl bis(trifluoromethanesulfonates) YCH2CHRY [R = H (2), CH3 (4)], (YCH2)2CR2 [R = H (6), CH3 (8)], Y—[CH2]n—Y [n = 4 (10), 5 (14)], cyclo-C6H10(YCH2)2 (12) (Y = CF3SO2O) with the divalent anions [M(CO)4]2- (1a,b). The corresponding osmium compounds are much more stable than their lower ruthenium homologues. On the basis of the 1H-NMR spectrum 7b has a planar conformation. According to an X-ray structural analysis 15b crystallizes in the triclinic space group P1¯ with Z = 2 and has a chair conformation. Heating of 7b results in the formation of cyclopropane (16). Under argon the ruthena- and osmacycloalkanes 11a, b and 15a, b decompose with formation of the olefins 17-23. In the presence of CO from 7b, 11a, b and 15b the three- to six-membered cycloalkanones 24-27 are isolated at elevated temperatures.
Notes:
Die Olefin-Komplexe (η2-CH2=CHR)M(CO)4 (3a, b, 5a, b) [R = 1H (3), CH3 (5); M = Ru (a), Os (b)] und vier- bis sechsgliedrigen Metallacycloalkane (7a, b, 9b) [R = H(7), CH3 (9)], (11a, b, 15a, b) [n = 2 (11), 3 (15)], (13a, b) erhält man durch nucleophile Eliminierungs-Cycloaddition an den Alkandiylbis(trifluormethansulfonate) YCH2CHRY [R = H (2), CH3, (4)], (YCH2)2CR2 [R = H (6), CH3 (8)], Y—[CH2]n—Y [n = 4 (10), 5 (14)], cyclo-C6H10(YCH2)2 (12) (Y = CF3SO2O) mit den zwei-wertigen Anionen [M(CO)4]2- (1a, b). Die entsprechenden Osmiumverbindungen sind viel stabiler als ihre niedrigeren Rutheniumhomologen. Aufgrund des 1H-NMR-Spektrums hat 7b eine planare Konformation. 15b kristallisiert nach einer Röntgenstrukturanalyse in der triklinen Raumgruppe P1¯ mit Z = 2 und besitzt Sesselkonformation. Beim Erhitzen von 7b bildet sich Cyclopropan (16). Unter Argon zersetzen sich die Ruthena- und Osmacycloalkane 11a, b und 15a, b unter Bildung der Olefine 17-23. In Gegenwart von CO isoliert man aus 7b, 11a, b und 15b bei höheren Temperaturen die drei- bis sechsgliedrigen Cycloalkanone 24-27.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19891220804
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