Structural Aspects of Lithium Arenethiolate Complexes with Intramolecular Coordinating Amine Donors.
Reaction of aryllithium reagents LiR (R = C(6)H(4)((R)-CH(Me)NMe(2))-2 (1a), C(6)H(3)(CH(2)NMe(2))(2)-2,6 (1b), C(6)H(4)(CH(2)N(Me)CH(2)CH(2)OMe)-2 (1c)) with 1 equiv of sulfur (1/8 S(8)) results in the quantitative formation of the corresponding lithium arenethiolates [Li{SC(6)H(4)((R)-CH(Me)NMe(2))-2}](6) (3), [Li{SC(6)H(3)(CH(2)NMe(2))(2)-2,6}](6) (4), and [Li{SC(6)H(4)(CH(2)N(Me)CH(2)CH(2)OMe)-2}](2) (5). Alternatively, 3 can be prepared by reacting the corresponding arenethiol HSC(6)H(4)((R)-CH(Me)NMe(2))-2 (2) with (n)BuLi. X-ray crystal structures of lithium arenethiolates 3 and 4, reported in abbreviated form, show them to have hexanuclear prismatic and hexanuclear planar structures, respectively, that are unprecedented in lithium thiolate chemistry. The lithium arenethiolate [Li{SC(6)H(4)(CH(2)N(Me)CH(2)CH(2)OMe)-2}](2) (5) is dimeric in the solid state and in solution, and crystals of 5 are monoclinic, space group P2(1)/c, with a = 17.7963(9) Å, b = 8.1281(7) Å, c = 17.1340(10) Å, beta = 108.288(5) degrees, Z = 4, and final R = 0.047 for 4051 reflections with F > 4sigma(F). Hexameric 4 reacts with 1 equiv of lithium iodide and 2 equiv of tetrahydrofuran to form the dinuclear adduct [Li(2)(SAr)(I)(THF)(2)] (6). Crystals of 6 are monoclinic, space group P2(1)/c, with a = 13.0346(10) Å, b = 11.523(3) Å, c = 16.127(3) Å, beta = 94.682(10) degrees, Z = 4, and final R = 0.059 for 3190 reflections with F > 4sigma(F).
Janssen
Maurits D.
MD
Debye Institute, Department of Metal-Mediated Synthesis, and Bijvoet Center for Biomolecular Research, Department of Crystal and Structural Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Rijnberg
Evelien
E
de Wolf
Corine A.
CA
Hogerheide
Marinus P.
MP
Kruis
Dennis
D
Kooijman
Huub
H
Spek
Anthony L.
AL
Grove
David M.
DM
van Koten
Gerard
G