197386-73-5Relevant academic research and scientific papers
Synthesis and characterization of some group 1 and 2 metal derivatives of the crowding terphenyl thiolate and selenolate ligands -EC6H3-2,6-Trip2 (E=S or Se; Trip=2,4,6-i-Pr3C6H2-)
Niemeyer, Mark,Power, Philip P.
, p. 201 - 207 (1997)
The synthesis and characterization of the monomeric magnesium thiolate Mg {SC6H3-2,6-Trip2}2 (1) (Trip=2,4,6-i-Pr3C6H2-), the new selenol HSeC6H3-2,6-Trip2 (2), three of its alkali metal derivatives (MSeC6H3-2,6-Trip2) (M=K, 3·PhMe, 3·Et2O, Rb, 4·PhMe) and the heterometallic thiolate RbAlMe2(SC6H3-2,6-Trip2)2 (5) are described. Compound 1 was synthesized by the reaction of commercially available 'MgBu2' with 2 equiv. of HSC6H3-2,6-Trip2. The new selenol 2 was obtained from the reaction of elemental selenium with LiC6H3-2,6-Trip2. The potassium and rubidium derivatives 3 and 4 were isolated by direct reaction of the metals with the selenol whereas 5 is formed by an exchange reaction between the corresponding rubidium thiolate and AlMe3. The compounds were characterized by 1H, 13C and 77Se NMR and IR spectroscopy, and by X-ray crystallography. Compound 1 crystallizes as a unique monomer with an S-Mg-S angle of 166.8(2)°. Compounds 3·PhMe and 4·PhMe crystallize as isomorphous dimers with M2Se2 cores. In these compounds each potassium or rubidium interacts in a π-fashion with two ortho aryl groups as well as σ-bonding to the chalcogens. The π-interaction is retained even in the presence of donor solvents. Thus, the ether solvate 3·Et2O is obtained by recrystallization of 3·PhMe from diethyl ether. Metal aryl interactions also are observed in the rubidium aluminate 5 which crystallizes with a planar RbAlS2 core. Crystal data at 130 K are as follows: Mg(SC6H3-2,6-Trip2)2 (1), a=10.417(1), b=11.644(1), c=14.545(2) A?, α=69.536(8), δ=75.91(1), γ=80.26(1)°, V=1596.2(3) A?3, space group P1?, Z=1, R1=0.043; (KSeC6H3-2,6-Trip2)2·PhMe (3·PhMe), a=13.842(3), b=15.124(3), c=17.776(3) A?, α=83.04(2), β=85.62(2), γ=89.64(2)°, V=3683(1) A?3, space group P1?, Z=2, R1=0.090; (RbSeC6H3-2,6-Trip2)2·PhMe (4·PhMe), a=13.959(2), b=15.179(1), c=17.713(2) A?, α=97.636(7), β=93.320(8), γ=90.462(8)°, V=3713.3(6) A?3, space group P1?, Z=2, R1=0.050; RbAlMe2(SC6H3-2,6-Trip2) 2·C6H14 (5), a=26.610(5), b=13.142(1), c=21.575(5) A?, β=99.37(2)°, V=7444(3) A?3, space group C2/c, Z=4, R1=0.047.
