164072-08-6Relevant academic research and scientific papers
Two counterintuitive routes to an iron alkylidyne complex
Anderson, Stephen,Hill, Anthony F.
, p. 1562 - 1564 (1995)
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.
Carbamoyl (Carboxamido) Complexes as Precursors for Metallaoxetene, Isonitrile, and Aminomethylidyne Complexes of Iron
Anderson, Stephen,Hill, Anthony F.,Ng, Ying Thong
, p. 15 - 21 (2008/10/08)
The reaction of [Fe{C(=O)NiPr2}(CO)4]Li with (CF3CO)2O in diethyl ether followed by triphenylphosphine provides carbamoyl complexes [Fe{η2-OCNiPr2}(CF3)(CO) 2(PPh3)] (1) or [Fe(η2-OCNiPr2)(CO)2(PPh 3)2](O2CCF3) (2a·O2CCF3) depending on the reaction conditions. The same procedure performed in dichloromethane provides the aminomethylidyne complex [Fe(≡CNiPr2)(CO)3(PPh 3)](O2CCF3) (5·O2CCF3) as well as traces of [Fe(η2-OCNiPr2)(CO)2-(PPh 3)2](O2CCF3) (2a·O2CCF3). The reactions of 1 with moist AgBF4 or HBF4 provide [Fe-{η2-OCNiPr2}(CO)3(PPh 3)]BF4 (2b·BF4), via a putative difluorocarbene intermediate, [Fe{η2-OCNiPr2}(=CF2)(CO) 2(PPh3)]BF4. In a similar manner, [Fe(η2-OCNiPr2)(CF3)(CO)(dPPe)] (3) (obtained from 1 and dppe) reacts with HBF4(aq) to provide [Fe{η2-OCNiPr2}(CO) 2(dppe)]-BF4 (4·BF4). A difluorocarbene complex is also implicated in the formation of the ferraoxetene [Fe{κ2-C(NiPr2)OCF 2}(CO){HB(pz)3}] (6) (pz = pyrazol-1-yl), which results from treatment of 1 with K[HB(pz)3] under high dilution. Under more concentrated conditions [Fe{HB(pz)3}2] is obtained. The ferraoxetene undergoes an unusual acid hydrolysis with HBF4(aq)/CO to provide the isonitrile salt [Fe(CNiPr)(CO)2{HB(pz)3}]PF6 (7·PF6). The salt [Fe(≡CNiPr2)-(CO)3(PPh3)]I (5·I) is the product of the reaction of 1 with iodine, via an as yet obscure mechanism, which may however also involve ferraoxetene intermediates.
