TY - JOUR
T1 - Synthesis of [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)] by Oxidative Chloride Substitution of [Fe3(CO)9(μ3-HBCO)]2-
AU - Crascall, Louise E.
AU - Thimmappa, B. H.S.
AU - Rheingold, Arnold L.
AU - Ostrander, Robert
AU - Fehlner, Thomas P.
PY - 1994/6/1
Y1 - 1994/6/1
N2 - The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)9(μ3-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)9(μ3-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) Å, b = 13.305(4) Å, c = 15.225(4) Å, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) Å3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.
AB - The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)9(μ3-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)9(μ3-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) Å, b = 13.305(4) Å, c = 15.225(4) Å, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) Å3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.
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U2 - 10.1021/om00018a006
DO - 10.1021/om00018a006
M3 - Article
AN - SCOPUS:0346241412
SN - 0276-7333
VL - 13
SP - 2153
EP - 2158
JO - Organometallics
JF - Organometallics
IS - 6
ER -