Mono(cyclopentadienyl) complexes of calcium, strontium, and barium, {[C-5(SiMe3)(3)H-2](Ca,Sr,Ba)I(thf)(n)}(x). Influence of alkali-metal cations on ligand exchange reactions
Mj. Harvey et Tp. Hanusa, Mono(cyclopentadienyl) complexes of calcium, strontium, and barium, {[C-5(SiMe3)(3)H-2](Ca,Sr,Ba)I(thf)(n)}(x). Influence of alkali-metal cations on ligand exchange reactions, ORGANOMETAL, 19(8), 2000, pp. 1556-1566
Reaction of the alkali-metal cyclopentadienide MCp' with an alkaline-earth
dihalide (AeX(2)) in ethers is usually an efficient route to group 2 cyclop
entadienyl complexes Cp'(n)AeX(2-n). This is not true for every Cp'/Ae comb
ination, however, and the precipitation of an insoluble MX halide may not a
lways be an adequate driving force for ligand exchange. As examples of this
, [1,2,4-tris(trimethylsilyl)cyclopentadienyl]metal iodides (Cp-3Si)AeI(thf
)(n) (Ae = Ca, n = 1; Ae = Sr, Ba, n = 2) are isolated from the 1:1 reactio
n of K[Cp-3Si] and AeI(2) in THF, but the yields range from very good (79%)
when Ae = Ca to poor (26%) when Ae = Ba. In the case of Ae = Sr, Ba, subst
antial amounts of K[Cp-3Si] are recoverable at the end of the reaction. No
redistribution of (Cp-3Si)AeI(thf)(n) into (Cp-3Si)(2)Ae and AeI(2)(thf)(n)
is observed in either THF or aromatic solvents at room temperature. Both (
Cp-3Si)CaI(thf) and (Cp-3Si)SrI(thf)(2) crystallize from THF/toluene as iod
ide-bridged dimers, [(Cp-3Si)Ae(mu-I)(thf)(n)](2), with eta(5)-[Cp-3Si](-)
ligands and one or two terminal thf's on each metal atom. The Ca-I and Ca-I
' distances are nearly equal at 3.066(4) and 3.102(4) Angstrom; the Sr-I an
d Sr-I' distances, at 3.278(3) and 3.355(3) Angstrom, are only slightly asy
mmetric. Unlike the two lighter homologues, the organobarium complex (Cp-3S
i)BaI(thf)(2) crystallizes from THF/toluene as a coordination polymer conta
ining both linear and near-linear (177.8 degrees) Ba-I-Ba links in a zigzag
motif; this is an unprecedented arrangement for bridging iodide ligands. T
reatment of (Cp-3Si)CaI(thf) with various alkalimetal-containing reagents y
ields primarily the group 1 cyclopentadienides (M[Cp-3Si]): e.g., the react
ion of (Cp-3Si)CaI(thf) with LiI forms Li[Cp-3Si], the use of Na[N(SiMe3)(2
)] generates Na[Cp-3Si], and the reaction with KCp* produces K[Cp-3Si]. Mod
els of the reaction of Cp'CaI with LiI were studied with density functional
theory calculations, which indicate that the formation of THF-solvated CaI
2 is an important driving force for this system.