TY - JOUR
T1 - Barium thiolates and selenolates
T2 - Syntheses and structural principles
AU - Ruhlandt-Senge, Karin
AU - Englich, Ulrich
PY - 2000/11/17
Y1 - 2000/11/17
N2 - The synthesis and structural characterization of a family of barium thiolates and selenolates is described. The thiolates were synthesized by metallation of thiols, the selenolates by reductive insertion of the metal into the selenium-selenium bond of diorgano-diselenides. Both reaction sequences were carried out by using barium metal dissolved in ammonia; this afforded barium thiolates and selenolates in good yield and purity. The structural principles displayed in the target compounds span a wide range of solid-state formulations, including monomeric and dimeric species, and separated ion triples, namely [Ba(thf)4(SMes*)2] (1; Mes*=2,4,6-tBu3C6H2), [Ba(thf)4(SeMes*)2] (2), [Ba([18]crown-6)(hmpa)2][(SeMes*)2] (3), the dimeric [{Ba(py)3(thf)(SeTrip)2}2] (4; py=pyridine, Trip=2,4,6-iPr3C6H2), and [Ba([18]crown-6)(SeTrip)2] (5). The full range of association modes is completed by [Ba([18]crown-6)(hmpa)S-Mes*][SMes*] (6) communicated earlier by this group. In the solid state, this compound displays an intermediate ion coordination mode: one anion is bound to the metal, while the second one is unassociated. Together these compounds provide structural information about all three different association modes for alkaline earth metal derivatives. This collection of structural data allows important conclusions about the influence of solvation and ligation on structural trends.
AB - The synthesis and structural characterization of a family of barium thiolates and selenolates is described. The thiolates were synthesized by metallation of thiols, the selenolates by reductive insertion of the metal into the selenium-selenium bond of diorgano-diselenides. Both reaction sequences were carried out by using barium metal dissolved in ammonia; this afforded barium thiolates and selenolates in good yield and purity. The structural principles displayed in the target compounds span a wide range of solid-state formulations, including monomeric and dimeric species, and separated ion triples, namely [Ba(thf)4(SMes*)2] (1; Mes*=2,4,6-tBu3C6H2), [Ba(thf)4(SeMes*)2] (2), [Ba([18]crown-6)(hmpa)2][(SeMes*)2] (3), the dimeric [{Ba(py)3(thf)(SeTrip)2}2] (4; py=pyridine, Trip=2,4,6-iPr3C6H2), and [Ba([18]crown-6)(SeTrip)2] (5). The full range of association modes is completed by [Ba([18]crown-6)(hmpa)S-Mes*][SMes*] (6) communicated earlier by this group. In the solid state, this compound displays an intermediate ion coordination mode: one anion is bound to the metal, while the second one is unassociated. Together these compounds provide structural information about all three different association modes for alkaline earth metal derivatives. This collection of structural data allows important conclusions about the influence of solvation and ligation on structural trends.
KW - Barium
KW - Chalcogens
KW - Coordination chemistry
KW - Structure elucidation
KW - Synthesis design
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U2 - 10.1002/1521-3765(20001117)6:22<4063::AID-CHEM4063>3.0.CO;2-Q
DO - 10.1002/1521-3765(20001117)6:22<4063::AID-CHEM4063>3.0.CO;2-Q
M3 - Article
C2 - 11151839
AN - SCOPUS:0034680523
SN - 0947-6539
VL - 6
SP - 4063
EP - 4070
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 22
ER -