Ligand exchange between arylcopper compounds and bis(hypersilyl)tin or bis(hypersilyl)lead: Synthesis and characterization of hypersilylcopper and a stannanediyl complex with a Cu-Sn bond
J. Klett et al., Ligand exchange between arylcopper compounds and bis(hypersilyl)tin or bis(hypersilyl)lead: Synthesis and characterization of hypersilylcopper and a stannanediyl complex with a Cu-Sn bond, CHEM-EUR J, 5(9), 1999, pp. 2531-2536
Bis(hypersilyl)tin (1) and bis(hypersilyl)lead (2) [hypersilyl= Hyp = tris(
trimethylsilyl)silyl] undergo ligand exchange reactions with other carbene
homologues to yield heteroleptic distannenes or diplumbenes. Here we report
the extension of this reaction principle to coordinatively unsaturated ary
lcopper(I) compounds. The primary reaction products are probably adducts wi
th the carbene homologues as Lewis base and the arylcopper compounds as Lew
is acids. This is followed by rearrangement to the adducts HypCu-E-(Hyp)Ar*
(E = Sn (6) and Pb (7); Ar* = C(6)H(3)Mes(2)-2,6,) of hypersilylcopper (9)
and the heteroleptic stannanediyl or plumbanediyl. The complex may be the
final product or may dissociate into its component parts, free hypersilylco
pper (9) and the appropriate heteroleptic carbene homologue. The colorless
hypersilylcopper forms a trimer (9), in the solid state with short Cu Cu co
ntacts (238.4-241.5 pm). All observed Cu-Si bonds are relatively long. Howe
ver, shorter distances (234.9-237.4pm) alternate with longer ones (249.2 pm
), such that quasi-monomeric hypersilylcopper units can be identified. The
dark green complex 6 exhibits a shorter Cu-Si bond (227.3 pm), The Sn-Cu bo
nd length was determined to be 249.9 pm. The turquoise plumbanediyl Pb(Hyp)
Ar* (8) is the first strictly monomeric mixed aryl silyl derivative, even i
n the solid state. The steric repulsions are obviously less than in the par
ent homoleptic compounds because the Pb-C bond in 8 is shorter (229.0 pm) a
nd the C-Pb-Si angle (109.2 degrees) is markedly smaller.