415725-05-2Relevant academic research and scientific papers
Main group derivatives of a cyclometallated iron carbonyl anion. Crystal structures of Fe(CO)2{P(OPh)3}{(PhO)2POC6H 4}(SnPh3) and two isomers of Fe(CO)2{P(OPh)3}{(PhO)2POC6H 4}(I)
Courtney,Cromhout,Cunningham,Gallagher,Manning,McArdle,Pratt
, p. 98 - 107 (2008/10/08)
The iron hydrido complex HFe(CO)2{P(OPh)3}{(PhO)2POC6H 4} (1), was rapidly deprotonated by DBU or [BzMe3N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)2{P(OPh)3}{(PhO)2POC6H 4}]- ([2]-), containing an ortho-metallated triphenyl phosphite ligand. Complex [2]- reacted with triorganostannyl and plumbyl salts and with halogens to give the octahedral FeII compounds Fe(CO)2{P(OPh)3}{(PhO)2POC6H 4}(X) (X = SnPh3, 3; SnMe3, 4; PbPh3, 5; PbMe3, 6; Cl, 7; Br, 8; I, 9). The Group 14 complexes 3-6 were obtained in one isomeric form in which the PIII-donor atoms are mutually cis, the carbonyl ligands are cis and the P(OPh)3 and MR3 (M = Sn, Pb; R = Ph, Me) groups are trans as determined by solution-state IR, 31P and 13C NMR spectroscopic data. This geometry was confirmed for 3 by a single crystal X-ray diffraction study. The halide complexes, however, were obtained as a mixture of isomers. The major isomer (7, X = Cl; 8a, X = Br; 9a, X = I) has cis P atoms, trans CO groups and the halide located trans to the phosphorus atom of the ortho-metallated phosphite ligand. The structure of 9a was confirmed by an X-ray diffraction study. Two other isomers, designated 8b (X = Br) and 9b (X = I), with cis P atoms and cis CO groups were isolated from the reactions of [2]- with Br2 and I2, respectively. The structure of the latter was established by X-ray crystallography and is related to 9a by exchange of the P(OPh)3 ligand and a carbonyl group such that the metal-bound C atom of the five-membered metallacycle is trans to CO. The stereo-geometry of 8b could not be unambiguously assigned from the spectroscopic data; however, two of the seven possible geometric isomers were suggested as plausible structures.
