- Dihapto carbamoyl (carboxamide) complexes of iron(II)
-
The carbamoyl ferrate Li[Fe{C(=O)NiPr2}(CO) 4] reacts in diethyl ether with Br2PPh3, I 2PPh3, or I2 followed by triphenylphosphine to provide the complexes [Fe(η2-OCNiPr 2)X-(CO)2(PPh3)] [X = I trans to PPh 3 (1a); Br (1b) two isomers], each of which feature dihaptoC,O carbamoyl coordination. The reactions of 1a or 1b with AgBF4 in the presence of CO provide [Fe(η2-OCNiPr 2)(CO)3(PPh3)]BF4 (2a·BF 4), one carbonyl ligand of which is labile and readily replaced by I-, Br-, or PPh3 to provide 1a, 1b, or [Fe-{η2-OCNiPr2}(CO)2(PPh 3)2]BF4(2b·BF4). The reaction of 1a with dppe leads to a separable mixture of the salt [Fe{η2- OCNiPr2}(CO)2(dppe)]I (3·I) and [Fe{η2-OCNiPr2}I(CO)(dppe)] (4). Successive treatment of Li[Fe{C(=O)NiPr2}(CO)4] with ClSnPh3 and PPh3 provides the stannyl complex [Fe(η2-OCNiPr2)(SnPh3)(CO) 2(PPh3)] (1d). Treating Id with iodine leads to Sn-Fe rather than Sn-C cleavage and formation of 1a. In all the above transformations the integrity of the dihapto carbamoyl coordination is ultimately retained. The crystal structures of 1d and 2b·PF6 are reported.
- Anderson, Stephen,Berridge, Timothy E.,Hill, Anthony F.,Ng, Ying Thong,White, Andrew J.P.,Williams, David J.
-
p. 2686 - 2693
(2008/10/09)
-
- Two counterintuitive routes to an iron alkylidyne complex
-
The cationic aminomethylidyne complex [Fe-(≡CNiPr2)(CO)3(PPh3) + has been prepared by two unexpected routes: (i) Iodination of the carbamoyl complex [Fe(η2-OCNiPr2)(CF3)(CO) 2(PPh3)] and (ii) O-trifluoro-acetylation of the carbamoylate [Fe{C(=O)NiPr2}(CO)4]-Li, a reaction which shows an unusual solvent dependence.
- Anderson, Stephen,Hill, Anthony F.
-
p. 1562 - 1564
(2008/10/09)
-