ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Carbonyl Insertion Reactions, III. The1H N.M.R. Spectroscopic Study of the Stereospecific Reaction of σ-Alkyltricarbonyl-(π-cyclopentadienyl)molybdenum with Cyanide Ionsπ-C5H5Mo(CO)3R (R = CH2C6H5, C2H5, [CH2]3CN) react with KCN to afford the corresponding acylcyanometallates K[π-C5H5Mo(CO)2(CN)COR] (1-3), which exist as a mixture of cis- and trans-isomers in solution, based on the 1H n.m.r. spectra. On account of the magnetic nonequivalence or the methylene protons in the cis-isomers, it was shown that the insertion reaction of πC5H5Mo (CO)3R with KCN yields stereospecifically the cis-complexes of K[πC5H5Mo(CO)3(CN)COR]. This reaction is followed by a cis- to trans-isomerization. The structures of the compounds are discussed on the basis of i.r. and 1H n.m.r. spectroscopic studies.
Notes:
π-C5H5Mo(CO)3R (R = CH2 C6 H5, C2H5, [CH2]3CN) reagieren mit KCN zu den entsprechenden Acylcyanomolybdaten K[π C5H5Mo(CO)2(CN)COR] (1-3), die in Lösung als cis&470;trans-Isomere vorliegen. Durch die magnetische Nichtäquivalenz von Methylenprotonen in asymmetrischen Molybdän-Komplexen wird nachgewiesen, daß die Komplexe π-C5H5Mo(CO)3R mit KCN in einer stereospezifischen Reaktion primär die cis-Isomeren der Acylcyanomolybdate (1-3) bilden, die zu den trans-Isomeren. umlagern. IR- und 1H-NMR-Spektren der dargestellten Verbindungen sowie ihre Struktur werden diskutiert.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19731061116
