TY - JOUR
T1 - Structural trends in alkaline earth and rare earth metal 3,5-diisopropylpyrazolates
AU - Hitzbleck, Julia
AU - Deacon, Glen B.
AU - Ruhlandt-Senge, Karin
PY - 2007
Y1 - 2007
N2 - A series of 3,5-diisopropylpyrazolates of magnesium, calcium, and strontium in addition to a divalent europium analog continues our investigation on the differences and similarities between the alkaline earth and divalent rare earth metal elements. The alkane elimination reaction between dibutylmagnesium and excess 3,5-diisopropylpyrazole (iPr2pzH) in toluene afforded the dinuclear magnesium pyrazolate [{Mg(iPr2pz)2(iPr 2pzH)}2] (1). [{Ca(iPr2pz)2(iPr 2pzH)2}2] (2) and [{Eu(iPr2pz) 2(iPr2pzH)2}2] (3) were obtained as the product of redox-transmetallation/ligand-exchange reactions between an excess of the corresponding metal, 2 equiv. of iPr2pzH, and Hg(C 6F5)2 in toluene. This reaction with Sr metal led to the isolation of a unique byproduct, [Hg3(iPr 2pz)4-(C6F5)2] (4). High-temperature direct metallation of barium with iPr2pzH afforded [{Ba(iPr 2pz)2(py)3)2] (5) upon treatment of the hydrocarbon-insoluble homoleptic [{Ba(iPr2pz)2}n] with pyridine (py). X-ray crystal structure analyses revealed dinuclear structures for compounds 1-3 and 5 with μ-ηn:ηm bridging pyrazolato ligands, including the new μ-η1:η5 linkage, and further stabilization of 1-3 by intramolecular hydrogen bonding between the terminal pyrazole donor and terminal 1 or bridging pyrazolato ligands in 2 and 3. The trinuclear 4 displays the first example of a complex with an open, triangular Hg3 unit. It has μ-η1: η1 bridging pyrazolato ligands and terminal pentafluorophenyl groups.
AB - A series of 3,5-diisopropylpyrazolates of magnesium, calcium, and strontium in addition to a divalent europium analog continues our investigation on the differences and similarities between the alkaline earth and divalent rare earth metal elements. The alkane elimination reaction between dibutylmagnesium and excess 3,5-diisopropylpyrazole (iPr2pzH) in toluene afforded the dinuclear magnesium pyrazolate [{Mg(iPr2pz)2(iPr 2pzH)}2] (1). [{Ca(iPr2pz)2(iPr 2pzH)2}2] (2) and [{Eu(iPr2pz) 2(iPr2pzH)2}2] (3) were obtained as the product of redox-transmetallation/ligand-exchange reactions between an excess of the corresponding metal, 2 equiv. of iPr2pzH, and Hg(C 6F5)2 in toluene. This reaction with Sr metal led to the isolation of a unique byproduct, [Hg3(iPr 2pz)4-(C6F5)2] (4). High-temperature direct metallation of barium with iPr2pzH afforded [{Ba(iPr 2pz)2(py)3)2] (5) upon treatment of the hydrocarbon-insoluble homoleptic [{Ba(iPr2pz)2}n] with pyridine (py). X-ray crystal structure analyses revealed dinuclear structures for compounds 1-3 and 5 with μ-ηn:ηm bridging pyrazolato ligands, including the new μ-η1:η5 linkage, and further stabilization of 1-3 by intramolecular hydrogen bonding between the terminal pyrazole donor and terminal 1 or bridging pyrazolato ligands in 2 and 3. The trinuclear 4 displays the first example of a complex with an open, triangular Hg3 unit. It has μ-η1: η1 bridging pyrazolato ligands and terminal pentafluorophenyl groups.
KW - Alkaline earth metals
KW - Coordination modes
KW - Lanthanoids
KW - N ligands
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U2 - 10.1002/ejic.200600767
DO - 10.1002/ejic.200600767
M3 - Article
AN - SCOPUS:34250889376
SN - 1434-1948
SP - 592
EP - 601
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 4
ER -