The title lead(II) derivative was obtained as
dark blue crystals by treatment of PbCl2 with
(TMEDA =
N,N,N‘,N‘-tetramethylethylenediamine) in tetrahydrofuran and its structure determined by X-ray diffraction. The compound is in effect
the first dialkylead(II) species to be structurally
characterized. The C−Pb−C angle is 117.1(2)°.
Analogous
treatment of SnCl2 yielded a yellow solid, which
was
judged from spectroscopic data to be the TMEDA complex of the analogous stannacycloalkane.
The title compounds have been made by treatment of
SnCl2 or PbCl2 in tetrahydrofuran
with the appropriate reagent LiR, where R =
(PhMe2Si)3C,
(Me3Si)3C, or
(MeOMe2Si)(Me3Si)2C, and their crystal structures determined. In all
four compounds, as in the previously
reported
[Pb{C(SiMe2Ph)3}Cl]2,
the metal atoms are linked by bridging Cl atoms, unsymmetrically except in the case of the trimeric
[Pb{C(SiMe3)3}Cl]3
(in which the six-membered
ring has a distorted boat form).
= Sn or Pb, which are
isomorphous, there are (relatively weak) intramolecular MeO···M
interactions in addition.
The compounds
[Pb{C(SiMe2Ph)3}Cl]2
and
[Pb{C(SiMe3)3}Cl]3
are the only known σ-bonded
mono(organo)lead(II) compounds to have been structurally
characterized, and [Sn{C(SiMe2Ph)3}Cl]2 is only the second
solvent-free mono(alkyl)tin(II) compound. All of
the compounds
are yellow and air-sensitive in the solid and in solution, and the lead
compounds are readily
decomposed in solution by exposure to daylight.
UK B N I 9QJThe title compound, thought to be the first monoorganolead(ii) compound, has been prepared and structurally characterized; the organic ligands are in a trans-disposition and the lone-pair on lead is stereochemically active.
Reaction of the organolithium reagent
(THF = tetrahydrofuran), 1, with LiAlH4 gave the title organotrihydridoaluminate, 2, which is unusual for an alkali metal
organotrihydridoaluminate in being monomeric and in
having the Al linked to the Li not only through hydride
but also through another of its ligands. The corresponding reaction with AlCl3 gave the title organoaluminum
dichloride. The Si−O bonds in 1 and 2 are not significantly lengthened by the O−metal coordination. The
bond from Li to the OMe in 1 oxygen is not significantly
different in length from that to the THF oxygen.
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