Cyclopentadienyldicarbonyliron derivatives of arsenic, antimony and bismuth with M–Fe σ-bonds (MAs, Sb, Bi)

Abstract

The reactions of MX,(M = As, Sb; X = C1, Br) with [Fe(CO),(n-C,H,)], in CH,Cl, solution give ionic derivatives containing the [X,M (Fe(CO),(n-C,H,) },I+ cation as well as the neutral compounds X,AsFe(CO), (n-C,H,), while similar reactions of SbX, and BiX, (X = C1, Br, I) in C,H, or tetrahydrofuran yield X,MFe ( C0),(n-C5H5) and XSb [Fe ( CO),(n-C,H,)],.

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…Similar structures were reported by Wieber et al, who prepared [{Cp(CO) 2 Fe}Bi(SCSOMe) 2 ] and [{Cp(CO) 2 Fe}Bi(S 2 CNEt 2 ) 2 ], the latter containing two four-membered rings based around the bismuth atom [56]. Mono-iron species have also been reported for the dibromo-, diiodo-, and dimethylbismuth analogues [5,53,56]. The related trimetal species [Cp(CO)(Me 3 P)Fe(BiMe 2 )] 2 Mo(CO) 4 was prepared by Malisch in 1983, by the reaction of [{Cp(CO)(PMe 3 )Fe}BiMe 2 ] with the norbornadiene molybdenum carbonyl complex (Scheme 4) [57].…”

“…3, was first reported in 1971 by Cullen et al, who synthesised a series of molecules containing E-Fe -bonds (E = As, Sb and Bi) [53,5].…”

The crystal and molecular structure of [dicarbonyl(η-cyclopentadienyl)ferrio]triphenylantimony hexafluorophosphate

“…If there were d-d,, bonding between the Sb and Fe atoms a shorter Sb-Fe length would be expected. This is consistent with M6ssbauer studies (Cullen, Patmore, Sams & Scott, 1974) which suggested that the electron distributions in the Sb-Fe and Sn-Fe bonds were similar with very little zr back-donation from the occupied 3d orbitals of Fe to the empty 5d orbitals in the Sb compound.…”

“…Recently there has been interest in transition-metal compounds containing Fe--Sb bonds (Cullen, Patmore, Sams & Scott, 1974). M6ssbauer spectroscopic studies of the cationic species [ XpSb{ Fe(CO)2(hs-CsHs)_}4_p]+ (where X = CI, Br, I, CF3, C6H 5, n-C4H9; p = 1 3)in comparison with the essentially isoelectronic neutral Sn compounds indicated that the positive charge is mainly localized on the Sb atom and that the Fe-Sb bonding is primarily a in character.…”

Spectroscopic Studies of Cationic h5-Cyclopentadienyl Iron Carbonyl Derivatives

“…However, as will be discussed in the ensuing part of this paper, the quadrupole splittings are not helpful in separating o and n effects in this series of compounds. (3,(21)(22)(23), the quadrupole splittings are all 1.8 f 0.1 mm s-I, in the same range as our present splittings. It appears that the bonding properties of both C O and h5-C5H5 change substantially with variations in L to effectively neutralize the changes in electron assymmetry about the iron atom.…”