Nucleophilicities of the metal carbonyl anions: effects of ligands, solvent and countercation

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…= 4) following a nucleophilic displacement reaction, and the nature of ion pairing. Furthermore, in the case of alkyl halides, several studies [18,[21][22][23][24] have confirmed the reactivity trend followed in Table 1.…”

“…Indeed, a small decrease in the rate was exhibited for the more interactive Na cation with the related manganese pentacarbonyl anion used as a model [18]. In this same study, changes in the solvent had little effect on the nucleophilicity of common carbonyl anions.…”

Heterometallic Nitrido-Carbonyl Clusters − Synthesis and Characterization of [Fe5MN(CO)14(C5H5)]2−, [Fe3M3N(CO)18]3− (M = Mo, W) and [HFe5MoN(CO)16]2− and Solid-State Structures of [Fe5MoN(CO)14(C5H5)]2−, [Fe5WN(CO)14(C5H5)]2−, and [Fe3Mo3N(CO)18]3−

“…[10] In contrast, the nitrido species [Fe 4 N(CO) 12 ] Ϫ , because of the low specific charge, reacts only after reduction, possibly through the labilization of a carbonyl ligand. [10] In contrast, the nitrido species [Fe 4 N(CO) 12 ] Ϫ , because of the low specific charge, reacts only after reduction, possibly through the labilization of a carbonyl ligand.…”

“…We have already exploited this approach to obtain [Fe 6 N(CO) 15 ] 3Ϫ [6] and [Fe 5 RhN(CO) 15 ] 2Ϫ . [12] The reaction of [Fe 4 N(CO) 12 ] Ϫ with [Mo(CO) 3 (C 5 H 5 )] Ϫ was performed in MeCN, with both reagents as their tetraethylammonium salts in a 2:1 molar ratio. [12] The reaction of [Fe 4 N(CO) 12 ] Ϫ with [Mo(CO) 3 (C 5 H 5 )] Ϫ was performed in MeCN, with both reagents as their tetraethylammonium salts in a 2:1 molar ratio.…”

Nucleophilic addition versus electron transfer in carbonylmetallate salts. Donor-acceptor interactions in the precursor ion pairs

“…The interconnection between nucleophilicity and electron transfer has been particularly noted in the reactions of carbonylmetallate anions, 11 which are highly reactive nucleophiles, 12,13 (indeed, they are considered to be 'supernucleophiles' 12 ) as well as easily oxidized electron donors. 14,15 These anions are examples of 'soft' nucleophiles (with high-lying HOMOs), 6 which are known to participate in both (two-electron) addition/substitutions and electron transfers.…”