The synthesis and characterization of the monomeric magnesium thiolate Mg{SC 6H 3-2,6-Trip 2} 2 ( 1) (Trip 2,4,6-i-Pr 3C 6H 2 −), the new selenol HSeC 6H 3-2,6-Trip 2 ( 2), three of its alkali metal derivatives (MSeC 6H 3-2,6-Trip 2) (MK, 3·PhMe, 3·Et 2O, Rb, 4·PhMe) and the heterometallic thiolate RbAlMe 2(SC 6H 3-2,6-Trip 2) 2 ( 5) are described. Compound 1 was synthesized by the reaction of commercially available ‘MgBu 2’ with 2 equiv. of HSC 6H 3-2,6-Trip 2. The new selenol 2 was obtained from the reaction of elemental selenium with LiC 6H 3-2,6-Trip 2. 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 AlMe 3. 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 SMgS angle of 166.8(2)°. Compounds 3·PhMe and 4·PhMe crystallize as isomorphous dimers with M 2Se 2 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·Et 2O is obtained by recrystallization of 3·PhMe from diethyl ether. Metal acryl interactions also are observed in the rubidium aluminate 5 which crystallizes with a planar RbAlS 2 core. Crystal data at 130 K are as follows: Mg(SC 6H 3-2,6-Trip 2) 2 ( 1), a = 10.417(1), b = 11.644(1), c = 14.545(2) A ̊ , α = 69.536(8), β = 75.91(1), γ = 80.26(1)°, V = 1596.2(3) A ̊ 3 , space group P 1 , Z = 1, R 1 = 0.043; (KSeC 6H 3-2,6-Trip 2) 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 P 1 , Z = 2, R 1 = 0.090; (RbSeC 6H 3-2,6-Trip 2) 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 P 1 , Z = 2, R 1 = 0.050; RbAlMe 2(SC 6H 3-2,6-Trip 2) 2·C 6H 14 ( 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, R 1 = 0.047.