The alkyls EuR2 (R =
C(SiMe3)3) and YbR2 (R =
[C(SiMe3)2(SiMe2X)], X = Me,
CHCH2,
or CH2CH2OEt) have been obtained from
reactions between KR and MI2, and the
ytterbium
analogues of Grignard reagents,
Yb[C(SiMe3)2(SiMe2X)]I·OEt2
(X = Me, CH=CH2, Ph or
OMe) from reactions between RI and Yb metal. The compounds
YbR2 and EuR2 crystallize
as solvent-free monomers with C−M−C = 136−137°. The
alkylytterbium iodides crystallize
from diethyl ether as solvated iodide-bridged dimers in which the
coordination at Yb is four
when X = Me but is increased to five by chelation from the group X
when X = OMe. When
X = CHCH2, the Yb···X interaction is weak.
The reaction 2RYbI = R2Yb + YbI2
is not
observed when X = Me, but takes place readily when X = Ph,
CHCH2, or OMe and provides
a route to the dialkyls MR2 when the alkylpotassium KR
cannot be obtained, e.g., when X
= OMe. The dialkyl
Yb[C(SiMe3)2(SiMe2X)]2
with X = Me reacts with ethers R‘OEt (R‘ =
Et, Bu, But) to give ethene and alkoxides RYbOR‘. The
corresponding reaction does not
take place when X = OMe and is very slow when X =
CHCH2.
Crystals of (RMe2Si)&K (R = Me, 1; R = Ph, 2), obtained from MeK and (RMezSi)&H, contain linear chains of alternate potassium cations and planar [(RMe&)&]-anions, with weak interactions between chains; in 1 the central carbon atoms of the anions are midway between the potassium cations, but in 2 cationanion pairs are linked by q6 coordination of phenyl groups.Methylpotassium has been carefully studied by X-ray powder methods and neutron diffraction,lJ but as far as we are aware there has hitherto been nosinglecrystal X-ray investigation of 4 donor-free organopotassium compound. We report the preparation and structures of compounds 1 and 2, which contain bulky organosilyl groups. (Me,Si),CK (PhMe,Si),CK 1 2 compound 1 can be obtained by either of the routeslf The colorless, exceedingly air-and moisture-sensitive +MeLi +KOBut -MeH -LiOBut (Me,Si),CH -(Me,Si),CLi -1 (a) +MeLi +(Messi)sCH -LiOBut -MeH
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