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

Reactions in the gas phase of the 13‐ and 15‐electron radical anions [Cr(CO) 3 ] − ˙ and [Cr(CO) 4 ] − ˙ 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) 3 ] − ˙ systems with the latter reaction also common to the RCHO/[Cr(CO) 4 ] − ˙ systems. While [Cr(CO) 4 ] − ˙ was generally unreactive towards ketones R · R'CO, the principal products identified for [Cr(CO) 3 ] − ˙ /ketone reactions were the metal‐decarbonylated species, respectively [R · R'CO · Cr(CO) x ] − ˙ with x = 0–3, and [R · (R' ‐ H 2 )CO · Cr(CO) 2 ] − ˙ . The reaction of [Cr(CO) 3 ] − ˙ with esters RCOOR' proceeds via metal insertion into the alkoxy CO bond to give end products of the type [R'O · Cr · R(CO) 2 ] − and [R'OCr(CO) 3 ] − while the sole ionic products of dialkyl ether/[Cr(CO) 3 ] − ˙ reactions were identified as the alkoxytricarbonylchromium species [RO · Cr(CO) 3 ] − .