Oxidation of Ce(tipip)
3 [tipip = N(Pr
i2PO)
2] by PhICl
2 afforded Ce(tipip)
3Cl which could also be synthesized by the reaction of [Et
4N]
2CeCl
6 with 3 equivalents of K(tipip). Chloride substitution of Ce(tipip)
3Cl with AgX [X
- = acetate (OAc
-), tosylate (OTs
-), triflate (OTf
-) and N
3-] afforded Ce(tipip)
3X. Treatment of [Et
4N]
2CeCl
6 with 2 equivalents of K(tipip) followed by treatment with Ag
2O resulted in the formation of the μ-oxo complex Ce
2(tipip)
2Cl
2(μ-tipip)
2(μ-O) (12) characterized by X-ray crystallography. The Ce-O average distance and the Ce-O-Ce angle in 12 are 2.087(2) Å and 146.73(11)º, respectively. Treatment of H(tipip) with Ce
2(OPr
i)
8(HOPr
i)
2 or Zr(OBu
t)
4 afforded the dinuclear peroxo complexes [M(tipip)
2(O
2)]
2 (M = Ce or Zr) which have been characterized by X-ray crystallog...[
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Oxidation of Ce(tipip)
3 [tipip = N(Pr
i2PO)
2] by PhICl
2 afforded Ce(tipip)
3Cl which could also be synthesized by the reaction of [Et
4N]
2CeCl
6 with 3 equivalents of K(tipip). Chloride substitution of Ce(tipip)
3Cl with AgX [X
- = acetate (OAc
-), tosylate (OTs
-), triflate (OTf
-) and N
3-] afforded Ce(tipip)
3X. Treatment of [Et
4N]
2CeCl
6 with 2 equivalents of K(tipip) followed by treatment with Ag
2O resulted in the formation of the μ-oxo complex Ce
2(tipip)
2Cl
2(μ-tipip)
2(μ-O) (12) characterized by X-ray crystallography. The Ce-O average distance and the Ce-O-Ce angle in 12 are 2.087(2) Å and 146.73(11)º, respectively. Treatment of H(tipip) with Ce
2(OPr
i)
8(HOPr
i)
2 or Zr(OBu
t)
4 afforded the dinuclear peroxo complexes [M(tipip)
2(O
2)]
2 (M = Ce or Zr) which have been characterized by X-ray crystallography. The titanium oxo [Ti
2(tipip)
4(μ-O)
2] and peroxo [Ti(tipip)
2(η
2-O
2)] complexes have been synthesized from Ti(OPr
i)
2Cl
2 and K(tipip).
Treatment of Ce(tipip)
3Cl with AgMnO
4 or KMnO
4 in MeCN afforded [Ce(tipip)
3]
2[MnO
4]
2 (18), which is stable in MeCN but decomposes readily in non-polar solvents such as CH
2Cl
2 and benzene. 18 can oxidize alkylbenzenes and cyclohexane to give the corresponding alcohol/ketone products. The oxidation of ethylbenzene by 18 showed clean pseudo-first-order kinetics. Treatment of Ce(tipip)
3(OTf) with [
nBu
4N]
2[MoO
4] afforded Ce
2(tipip)
6(μ-MoO
4) which can catalyze the oxidation of organic sulfides with
tBuOOH in high yield and selectivity.
Treatment of BiCl
3 with NaL
OEt [L
OEt- = [(η
5-C
5H
5){CoP(O)(OEt)
2}
3]
-] afforded Bi(L
OEt)Cl
2 which reacted with AgX to give [Bi(L
OEt)X
2]
2 [X
- = tosylate (OTs
-), triflate (OTf
-)]. Treatment of [Bi(L
OEt)(OTs)
2]
2 with Na
2Cr
2O
7 afforded the heterometallic Bi(III)/Cr(VI) oxo cluster [Bi
4(L
OEt)
4(μ
3-Cr
2O
7)
2(μ
3-CrO
4)
2] (31) featuring a novel Bi
4Cr
4O
12 oxometallic core. Treatment of 31 with CrO
3 afforded the trichromate complex Bi
2(L
OEt)
2(μ
2,η
4-Cr
3O
10)
2. Treatment of Bi(L
OEt)Cl
2 with CrO
3 afforded [Bi(L
OEt)(μ-Cl)(CrO
3Cl)]
2. Organobismuth(III) complexes with L
OEt- ligands {(CH
3)N(CH
2C
6H
4)
2}Bi(η
1-L
OEt) have been synthesized.
Reaction of [Ru(PPh
3)
3Cl
2] or [Ru(η
6-cymene)Cl
2]
2 with K(tipip) afforded [Ru(tipip)(PPh
3)
2Cl] and [Ru(η
6-cymene)(tipip)Cl], respectively. Treatment of [Ru(CO)
2Cl
2]
x with K(tipip) afforded [Ru
2(tipip)
2(CO)
2(μ-CO)
2]. Reaction of [Ru(=CHPh)(PCy
3)
2Cl
2] with Tl(tipip) yielded [Ru(=CHPh)(tipip)(PCy
3)Cl] which can catalyze the ring-closing metathesis of diethyl 1,2-diallylmalonate.
Treatment of Li(P,Se) [H(P,Se) = Pr
i2P(Se)NP(H)Pr
i2] with [Rh(COD)Cl]
2 (COD = 1,5-cyclooctadiene), RhCl(PPh
3)
3 and RhCl(CO)(PPh
3)
2 afforded Rh(P,Se)(COD), Rh(P,Se)(PPh
3)
2 and Rh(P,Se)(CO)(PPh
3), respectively. Treatment of Li(P,Se) with [M(COE)Cl]
2 (M = Rh, Ir; COE = cyclooctene) afforded the hydride complexes M(H)(P,Se)
2 which reacted with HBF
4 or HCl to give Rh{H(P,Se)}
2[BF
4] and Ir(H){H(P,Se)}
2Cl
2, respectively.
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