SmCl
3(THF)
3 (THF =tetrahydrofuran) reacts with anionic dialkylamidesR
2N
- [R = Cy (cyclohexyl),i-Pr(isopropyl), Ph (phenyl)] to give different products, depending on thenature of the R substituents. Reaction withCy
2NLi in a 1:2 molar ratio formed[(Cy
2N)
2Sm(
mages/entities/mgr.gif">-Cl)(THF)]
2(
1) in 80% yield, whereas reaction with(i-Pr)
2NLiunder similar conditions gave[(i-Pr
2N)
2SmCl
3(Li(TMEDA))
2](
2). Partial loss of THF from complex
1reorganizedthe molecule into the tetranuclear(Cy
2N)
6Sm
4Cl
6(THF)
2(
3). Attempts to reduce complex
1 with anumber ofreagents gave[(Cy
2N)
3SmTHF]·toluene(
5), while[(Cy
2N)
4SmLi(THF)] (
4)was isolated upon alkylation reactionscarried out with either NpLi or NfLi [Np =CH
2C(CH
3)
3; Nf =CH
2C(CH
3)
2Ph]. Directsynthesis of Sm(II)amides from SmI
2(THF)
2 starting
materialwas successful only in the case of diphenylamide anion(Ph
2N
-).Depending on the stoichiometry, -ate(Ph
2N)
4Sm[Na(TMEDA)]
2(
6) or neutral[(Ph
2N)
2Sm(THF)
4]·THF(
7) wasobtained. The crystal structures of
1-
7were demonstrated by X-ray diffraction analysis. Crystal data areasfollows.
1:C
56H
105N
4O
2Sm
2Cl
2,triclinic,
Pmages/entities/one
macr.gif">,
a = 14.344(1) Å,
b = 23.897(2) Å,
c = 10.2031(9)Å,
mages/gifchars/alpha.gif" BORDER=0> =88.479(9)
mages/entities/deg.gif">,
mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 121.83(1)
mages/entities/deg.gif">,
mages/gifchars/gam
ma.gif" BORDER=0 > = 93.73(1)
mages/entities/deg.gif">,
Z = 2.
2:C
24H
60N
6SmCl
3Li
2triclinic,
Pmages/entities/one
macr.gif">,
a = 11.552(1) Å,
b =15.483(1) Å,
c = 11.330(1) Å,
mages/gifchars/alpha.gif" BORDER=0> =101.69(1)
mages/entities/deg.gif">,
mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 106.13(1)
mages/entities/deg.gif">,
mages/gifchars/gam
ma.gif" BORDER=0 > = 88.89(2)
mages/entities/deg.gif">.
3:C
80H
148N
6Cl
6O
2Sm
4,triclinic,
Pmages/entities/one
macr.gif">,
a = 16.508(1) Å,
b= 16.7795(9) Å,
c = 16.4030(8) Å,
mages/gifchars/alpha.gif" BORDER=0> =89.794(1)
mages/entities/deg.gif">,
mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 88.688(2)
mages/entities/deg.gif">,
mages/gifchars/gam
ma.gif" BORDER=0 > =79.531(1)
mages/entities/deg.gif">,
Z = 2.
4:C
56H
106N
4O
2LiSm,orthorhombic,
Pna2
1,
a =16.6145(9) Å,
b = 17.5858(9) Å,
c= 19.7754(9) Å,
V = 5778.0(9) Å
3,
Z = 4.
5:C
47H
82N
3OSm, monoclinic,
P2
1/
c,
a =10.250(2) Å,
b = 23.305(2) Å,
c =19.088(1) Å,
mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 100.90(1)
mages/entities/deg.gif">,
Z = 4.
6:C
60H
72N
8SmNa
2,tetragonal,
I4
1/
acd,
a =18.0004(9) Å,
c = 34.106(1) Å,
Z= 8.
7:C
44H
60N
2O
5Sm,monoclinic,
C2,
a = 19.066(1) Å,
b = 11.932(1) Å,
c = 9.200(1) Å,
mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 93.89(1)
mages/entities/deg.gif">,
Z = 2.