TY - JOUR
T1 - From neutral to ionic species
T2 - Syntheses and X-ray crystallographic and multinuclear NMR spectroscopic studies of Li⋯P(SiMe3)- PtBu2 and Its Solvent Complexes
AU - Sattler, Ewald
AU - Matern, Eberhard
AU - Rothenberger, Alexander
AU - Okrut, Alexander
AU - Bombicz, Petra
AU - Fernández, Ignacio
AU - Kovács, Ilona
PY - 2014/1
Y1 - 2014/1
N2 - Li(THF)3P(SiMe3)-PtBu2 (1, THF = tetrahydrofuran) has been prepared by the reaction of (Me3Si) 2P-PtBu2 with n-butyllithium in THF and isolated in good yields. Compound 1 eliminates THF in vacuo to yield the dimeric [Li(THF)P(SiMe3)-PtBu2]2 (2). By metalation of H(SiMe3)P-PtBu2 with n-butyllithium in hexane, the solvent-free derivative [Li(Me3Si)P-PtBu2]4 (3) has been prepared. Compounds 1-3 form the ionic species [Li(TMEDA) 2]+[(Me3Si)P-PtBu2]- [4, TMEDA = Me2N(CH2)2NMe2] and [Li(12-crown-4)2]+[(SiMe3)P-PtBu 2]- (5) with TMEDA and 12-crown-4, respectively, in solution. The molecular structures of 1-5 were established by single-crystal X-ray diffraction. Compound 3 forms a cyclic tetramer with a flat butterfly geometry. Extensive solution NMR spectroscopic investigations have shown that all species except for 3 exist in the same form in solution as in the solid state. Moreover, multinuclear variable-temperature NMR studies showed that 2 is involved in a rapid conversion between conformers at 298 K, which can be slowed down on the NMR timescale at 183 K.
AB - Li(THF)3P(SiMe3)-PtBu2 (1, THF = tetrahydrofuran) has been prepared by the reaction of (Me3Si) 2P-PtBu2 with n-butyllithium in THF and isolated in good yields. Compound 1 eliminates THF in vacuo to yield the dimeric [Li(THF)P(SiMe3)-PtBu2]2 (2). By metalation of H(SiMe3)P-PtBu2 with n-butyllithium in hexane, the solvent-free derivative [Li(Me3Si)P-PtBu2]4 (3) has been prepared. Compounds 1-3 form the ionic species [Li(TMEDA) 2]+[(Me3Si)P-PtBu2]- [4, TMEDA = Me2N(CH2)2NMe2] and [Li(12-crown-4)2]+[(SiMe3)P-PtBu 2]- (5) with TMEDA and 12-crown-4, respectively, in solution. The molecular structures of 1-5 were established by single-crystal X-ray diffraction. Compound 3 forms a cyclic tetramer with a flat butterfly geometry. Extensive solution NMR spectroscopic investigations have shown that all species except for 3 exist in the same form in solution as in the solid state. Moreover, multinuclear variable-temperature NMR studies showed that 2 is involved in a rapid conversion between conformers at 298 K, which can be slowed down on the NMR timescale at 183 K.
KW - Donor ligands
KW - Lithium
KW - NMR spectroscopy
KW - P ligands
KW - Structure elucidation
UR - http://www.scopus.com/inward/record.url?scp=84891622763&partnerID=8YFLogxK
U2 - 10.1002/ejic.201301189
DO - 10.1002/ejic.201301189
M3 - Article
AN - SCOPUS:84891622763
SN - 1434-1948
SP - 221
EP - 232
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 1
ER -