The synthesis, characterization, and reactivities of iron carbonyl complexes containing bismuth or antimony

[摘要] When (Et$sb4$N) $sb3$(Bi${$Fe(CO)$sb4}sb4$) is treated with main group metal halides complicated disproportionation reactions occur. The reaction with BiCl$sb3$ in MeCN yields (Et$sb4$N) (BiFe$sb3$(CO)$sb{10}$), (Et$sb4$N) $sb2$(Bi$sb2$Fe$sb4$(CO)$sb{13}$), and (Et$sb4$N) $sb2$(Bi$sb4$Fe$sb4$(CO)$sb{13}$) while treatment with SnEt$sb2$Cl$sb2$ or CBr$sb4$ gives the oxidation product (Et$sb4$N) $sb2$(Bi$sb4$Fe$sb4$(CO)$sb{13}$) in high yield. Oxidation of (Et$sb4$N) $sb3$(Bi${$Fe(CO)$sb4}sb4$) with 2 equivalents of (Cu(MeCN)$sb4$) (BF$sb4$) or MeI affords (Et$sb4$N) (BiFe$sb3$(CO)$sb{10}$).(Et$sb4$N) $sb2$(Bi$sb2$Fe$sb4$(CO)$sb{13}$) is oxidized by (Cu(MeCN)$sb4$) (BF$sb4$) forming Bi$sb2$Fe$sb3$(CO)$sb9$ and reacts with CO (850 psi) to produce (Et$sb4$N) $sb2$(Bi$sb4$Fe$sb4$(CO)$sb{13}$). Bi$sb2$Fe$sb3$(CO)$sb9$ is reduced readily with Na/Hg forming one- and two-electron-reduction products. Two-electron-reduction can also be achieved by treating Bi$sb2$Fe$sb3$(CO)$sb9$ with 2 equivalents of cobaltocene in CH$sb2$Cl$sb2$. The elemental analyses and spectroscopic data for the two-electron-reduction product support the formulation as (Cp$sb2$Co) $sb2$(Bi$sb2$Fe$sb3$(CO)$sb9$). The (Bi$sb2$Fe$sb3$(CO)$sb9$) $sp{2-}$ anion can be reconverted to Bi$sb2$Fe$sb3$(CO)$sb9$ in 90% spectroscopic yield when treated with (Cu(MeCN)$sb4$) (BF$sb4$).The reaction of (Et$sb4$N) $sb2$(Fe$sb2$(CO)$sb8$) with BiCl$sb3$ or SbCl$sb3$ forms compounds proposed to be (Et$sb4$N) (EFe$sb3$(CO)$sb{12}$) (E = Bi, Sb) based on elemental analyses and spectroscopic data. The treatment of (Et$sb4$N) (BiFe$sb3$(CO)$sb{12}$) or (Et$sb4$N) (SbFe$sb3$(CO)$sb{12}$) with Cr(CO)$sb5$(THF) produces (Et$sb4$N) (EFe$sb3$Cr(CO)$sb{17}$) (E = Bi, Sb), respectively, while methylation of (Et$sb4$N) (BiFe$sb3$(CO)$sb{12}$) afford Bi$sb2$Fe$sb2$(CO)$sb8$Me$sb2$. Oxidation of (Et$sb4$N) (BiFe$sb3$(CO)$sb{12}$) with (Cu(MeCN)$sb4$) (BF$sb4$) yields Bi$sb2$Fe$sb3$(CO)$sb9$ whereas the same reaction using of (Et$sb4$N) (SbFe$sb3$(CO)$sb{12}$) gives Sb$sb2$Fe$sb6$(CO)$sb{22}$. Refluxing (Et$sb4$N) (BiFe$sb3$(CO)$sb{12}$) or (Et$sb4$N) (SbFe$sb3$(CO)$sb{12}$) in acetonitrile produces (Et$sb4$N) $sb2$(Bi$sb2$Fe$sb4$(CO)$sb{13}$) and (Et$sb4$N) $sb2$(Sb$sb2$Fe$sb5$(CO)$sb{17}$), respectively.(Et$sb4$N) (EFe$sb3$Cr(CO)$sb{17}$) (E = Bi, Sb), Bi$sb2$Fe$sb2$(CO)$sb8$Me$sb2$, (Et$sb4$N) $sb2$(Sb$sb2$Fe$sb5$(CO)$sb{17}$), and Sb$sb2$Fe$sb6$(CO)$sb{22}$ have been crystallographically characterized. (Et$sb4$N) (EFe$sb3$Cr(CO)$sb{17}$) (E = Bi, Sb) displays a central main group atom bonded to one Fe$sb2$(CO)$sb8$ unit, one Cr(CO)$sb5$ ligand, and one Fe(CO)$sb4$ moiety. Bi$sb2$Fe$sb2$(CO)$sb8$Me$sb2$ contains a Bi$sb2$Fe$sb2$ parallelogram. A Me group is bonded to each pyramidal bismuth atom and the iron atoms are pseudooctahedrally coordinated. (Et$sb4$N) $sb2$(Sb$sb2$Fe$sb5$(CO)$sb{17}$) has a square-planar Sb$sb2$Fe$sb3$ core geometry, with the external Fe(CO)$sb4$ group bonded to each Sb atom. Sb$sb2$Fe$sb6$(CO)$sb{22}$ is composed of an Fe$sb2$(CO)$sb6$ unit bridged by two Sb atoms. The coordination of each antimony atom is completed by bonding to an Fe$sb2$(Co)$sb8$ moiety.

[发布机构] Rice University

[效力级别] chemistry