The reaction of Pb(OAc)\sb2 or PbCl\sb2 with K (HFe(CO)\sb4) results in formation of (Et\sb4N) \sb2 (Pb{\{Fe\sb2(CO)\sb8\}\{Fe(CO)\sb4\}\sb2) in high yield based on iron. This complex has been structurally characterized and contains a central Pb\sp{4+} atom bound to two (Fe(CO)\sb4) \sp{2-} ligands and one (Fe\sb2(CO)\sb8) \sp{2-} group (Fe-Fe = 2.617(5)A). (Et\sb4N) \sb2 (M{\{Fe\sb2(CO)\sb8\}\{Fe(CO)\sb4\}\sb2) reacts with CO and MCl\sb2 with excess K (HFe(CO)\sb4) to yield products which are formulated as (Et\sb4N) \sb2 (M{\{Fe(CO)\sb4\}\sb2) on the basis of analytical and spectroscopic data. GeI\sb2 is unreactive towards K (HFe(CO)\sb4), but when mixed with (Et\sb4N) \sb2 (Fe\sb2(CO)\sb8) formation of the novel complex (Et\sb4N) \sb2 (Fe\sb3(CO)\sb9(\mu\sb3-CO)\{\mu\sb3 - GeFe(CO)\sb4\}) occurs. When GeCl\sb4 is treated with (Et\sb4N) \sb2 (Fe\sb2(CO)\sb8) formation of (Et\sb4N) \sb2 (Fe\sb3(CO)\sb{11}) is observed with no evidence of a germanium-containing cluster. These mixed metal anions are oxidized by (Cu(CH\sb3CN)\sb4) (BF\sb4) to form the corresponding neutral spirocyclic M (Fe\sb2(CO)\sb8) \sb2 (M = Sn, Ge, Pb) species. A single crystal X-ray diffraction structure was obtained for the complex Pb (Fe\sb2(CO)\sb8\rbrack\sb2 (Fe-Fe = 2.90(2)A). Reduction of Ge (Fe\sb2(CO)\sb8\rbrack\sb2 in benzene or CH\sb2Cl\sb2 led to the recovery of (Et\sb4N) \sb2 (Fe\sb3(CO)\sb9(\mu\sb3-CO)\{\mu\sb3-GeFe(CO)\sb4). (Et\sb4N) \sb2 (Pb{\{Fe\sb2(CO)\sb8\}\{Fe(CO)\sb4\}\sb2) or (Et\sb4N) \sb2 (Pb{\{Fe(CO)\sb4\}\sb2) are recovered from reduction of Pb (Fe\sb2(CO)\sb8) \sb2, depending on the solvent used. Periodic trends were examined by utilizing bismuth as the main group element. The reaction of NaBiO\sb3 with K (HFe(CO)\sb4) resulted in isolation of (Et\sb4N) \sb3 (Bi{\{Fe(CO)\sb4\}\sb4) in which a central Bi\sp{5+} atom is tetrahedrally surrounded by four (Fe(CO)\sb4) \sp{2-} ligands. This complex decomposes in the presence of gaseous HCl to produce up to 1 mole of H\sb2 per mole of cluster via intermediate formation of H\sb2Fe(CO)\sb4. Refluxing NaBiO\sb3 with Fe(CO)\sb5 led to the isolation of (Et\sb4N) (BiFe\sb3(CO)\sb9(\mu\sb3-CO)) which is isoelectronic with (Et\sb4N) \sb2 (Fe\sb3(CO)\sb9(\mu\sb3-CO)\{\mu\sb3-GeFe(CO)\sb4\}) and contains a triangle of iron atoms capped by a bismuth atom on one face and a CO group on the other (Fe-Fe = 2.642(7)A). When (Et\sb4N) (BiFe\sb3(CO)\sb9(\mu\sb3-CO)) is treated with CO, an extensive rearrangement occurs leading to formation of (Et\sb4N) \sb2 (Bi\sb4Fe\sb4(CO)\sb{13}) in which there is a central tetrahedron of bismuth atoms attached to iron carbonyl fragments. This complex is the first "Zintl-metal carbonylate" to be reported. (Abstract shortened with permission of author.

Similar works

Full text


DSpace at Rice University

Last time updated on 11/06/2012

This paper was published in DSpace at Rice University.

Having an issue?

Is data on this page outdated, violates copyrights or anything else? Report the problem now and we will take corresponding actions after reviewing your request.