ISSN:
0009-2940
Keywords:
Diphosphamanganacyclopropanes
;
Alkyne insertion
;
Alkyne addition
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Metal-;Containing Heterocycles: Preparation, Properties, Reactions, LXXX. - Insertion and Addition Reactions on Diphosphamanganacyclopropanes with Activated AlkynesThe thermally and kinetically stable diphosphamanganabicyclooctadienones 3a - e [R2 = tBu: R1 = iPr (a), nPr (b), Ph (c); R2 = Cy: R1 = nPr (d), Ph (e)] are obtained by the reaction of the alkyne (CCO2Me)2 with the diphosphamanganacyclopropanes (OC)4Mn-PR12=PR2 (2a - e). Depending on steric factors the formation of 3a - e occurs in two different ways. In a first step the alkyne is inserted into the P - P bond of 2a - e to give the kinetically labile five-membered rings 1a - e. Subsequently another alkyne is added to the PR2 and a CO group of 1a - e to give 3a - e. In an alternative way the alkyne is added first to the PR2 and a CO group of 2a with formation of the diphosphamanganabicyclohexenone 4a. Insertion of a second alkyne into the P - P bond of 4a affords the bicyclooctadienone 3a. Compound 2a, 3c, and 4a have been characterized by X-ray structural analyses.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260105
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