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Courtney, D,Cromhout, NL,Cunningham, D,Gallagher, JF,Manning, AR,McArdle, P,Pratt, SI
2002
January
Inorganica Chimica Acta
Main group derivatives of a cyclometallated iron carbonyl anion. Crystal structures of Fe(CO)(2){P(OPh)(3)}{(PhO)(2)POC6H4}(SnPh3) and two isomers of Fe(CO)(2){P(OPh)(3)}{(PhO)(2)POC6H4}(I)
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crystal structures iron complexes ferrate anion complexes phosphite complexes tin complexes lead complexes LIGAND SUBSTITUTION PROCESSES COMPLEXES
327
98
107
The iron hydrido complex HFe(CO)(2){P(OPh)(3)}{(PhO)(2)POC6H4} (1), was rapidly deprotonated by DBU or [BzMe(3)N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)(2){P(OPh)(3)}{(PhO)(2)POC6H4}](-) ([2](-)), containing an ortho-metallated triphenyl phosphite figand. Complex [2]- reacted with triorganostannyl and plurnbyl salts and with halogens to give the octahedral Fe-II compounds Fe(CO)(2){P(OPh)(3)} {PhO)(2)POC6H4}(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 P-III-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, P-31 and C-13 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 = 1) 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 = 1), with cis P atoms and cis CO groups were isolated from the reactions of [2]- with Br, and 1,, 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. 0 2002 Elsevier Science B.V.. All rights reserved.
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