SYNTHESIS AND CHARACTERIZATION OF THE MONOMERIC DIARYLS M(C6H3-2,6-MES(2))(2) (M=GE, SN, OR PB MES=2,4,6-ME3C6H2-) AND DIMERIC ARYL-METAL CHLORIDES [M(CL)(C6H3-2,6-MES(2))](2) (M=GE OR SN)
Rs. Simons et al., SYNTHESIS AND CHARACTERIZATION OF THE MONOMERIC DIARYLS M(C6H3-2,6-MES(2))(2) (M=GE, SN, OR PB MES=2,4,6-ME3C6H2-) AND DIMERIC ARYL-METAL CHLORIDES [M(CL)(C6H3-2,6-MES(2))](2) (M=GE OR SN), Organometallics, 16(9), 1997, pp. 1920-1925
The reaction of 2 equiv of LiC6H3-2,6-Mes(2) (Mes = 2,4,6-Me3C6H2-) wi
th GeCl2 . dioxane, SnCl2, or PbCl2 in ether solution has resulted in
the isolation of rare examples of monomeric, sigma-bonded, diaryl deri
vatives M{C6H3-2,6-Mes(2)}(2) (M = Ge (1), Sn (2), or Pb (3)). The com
pounds 1-3 are thermally stable, purple, crystalline solids with V-sha
ped geometries and remarkably wide (ca. 114.5 degrees) interligand bon
d angles. The monoaryl metal chloride derivatives [M(Cl){C6H3-2,6-Mes(
2)}](2) (M = Ge (4) or Sn (5)) were isolated by treatment of the appro
priate dichlorides with either 1 equiv of LiC6H3-2,6-Mes(2) or 1 equiv
of the diaryls 1 or 2. The orange germanium compound 4 has a dimeric
structure in which the monomers are linked by a relatively weak, 2.443
(2) Angstrom, Ge-Ge interaction. In sharp contrast, its yellow tin ana
logue 5 has a dimeric structure in which three-coordinate tin centers
are associated by asymmetrically bridging chlorides. The compounds 1-3
constitute a unique, structurally characterized diaryl series for Ge,
Sn, and Pb and display evidence of steric crowding that is significan
tly greater than that observed in previously known sigma-bonded diorga
no group 14 derivatives. The compounds 4 and 5 are the first fully str
ucturally characterized organometal halide derivatives of Ge or Sn in
which the organic ligand is monodentate, purely sigma-bonded, and nonc
helating.