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Gas-phase chemistry of electron deficient organometallic anions: the reactions of [Cr(CO)3]− ˙ and [Cr(CO)4]− ˙ with aldehydes, ketones, esters and ethers

✍ Scribed by I. K. Gregor


Publisher
John Wiley and Sons
Year
1989
Tongue
English
Weight
432 KB
Volume
24
Category
Article
ISSN
1076-5174

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✦ Synopsis


Reactions in the gas phase of the 13-and lklectron radical anions [Cr(CO),]-' and [Cr(CO),]-* with a series of 27 aldehydes, ketones, esters and ethers have been examined. Sequential alkane eliminations and metal-bonded CO ligand displacements were the principal reactions identified for the RCHO/[Cr(CO),] -' systems with the latter reaction also common to the RCHO/[Cr(CO),]-' systems. While [Cr(CO),]-* was generally unreactive towards ketones R -RCO, the principal products identified for [Cr(CO),]-'/ketone reactions were the metaldecarbonylated species, respectively m-RCO. Cr(CO),]-' with x = 0-3, and [R * ( R -H,)CO *Cr(CO),l-'. The reaction of [Cr(CO),]-' with esters RCOOR' proceeds via metal insertion into the alkoxy C -0 bond to give end products of the type [RO.Cr-R(CO),]-and [RO-Cr(CO),]-; while the sole ionic products of dialkyl ether/[Cr(CO),]-' reactions were identified as the alkoxytricarbonylchromium species [RO * Cr(CO),l-.