Treatment of NaL
OEt(Na[(η
5-C
5H
5)Co{P(O)(OC
2H
5)
2}
3]) with 1 equiv. of [Ti(O-i-Pr)
2Cl
2] and HCl in Et
2O gave [L
OEtTiCl
3]. Reaction between [L
OEtTiCl
3] and tetrachlorocatechol (C
6Cl
4(OH)
2) gave [L
OEtTi(Cl)(C
6Cl
4O
2)], which formed mono-μ-oxo complex [{L
OEtTi(C
6Cl
4O
2)}
2(μ-O)] in the presence of base. Reaction of NaL
OEt with titanyl sulfate / zirconyl nitrate and HBF
4 gave [L
OEtTiF
3] or [L
OEtZrF
3] respectively. Reaction between [L
OEtTiCl
3] and HOTf gave [L
OEtTi(OTf)
3] (OTf = triflate), which is an active catalyst for Diels-Alder reaction. [L
OEtTiCl
3] can catalyze solvent-free ring opening of epoxides by Me
3SiN
3.
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Treatment of NaL
OEt(Na[(η
5-C
5H
5)Co{P(O)(OC
2H
5)
2}
3]) with 1 equiv. of [Ti(O-i-Pr)
2Cl
2] and HCl in Et
2O gave [L
OEtTiCl
3]. Reaction between [L
OEtTiCl
3] and tetrachlorocatechol (C
6Cl
4(OH)
2) gave [L
OEtTi(Cl)(C
6Cl
4O
2)], which formed mono-μ-oxo complex [{L
OEtTi(C
6Cl
4O
2)}
2(μ-O)] in the presence of base. Reaction of NaL
OEt with titanyl sulfate / zirconyl nitrate and HBF
4 gave [L
OEtTiF
3] or [L
OEtZrF
3] respectively. Reaction between [L
OEtTiCl
3] and HOTf gave [L
OEtTi(OTf)
3] (OTf = triflate), which is an active catalyst for Diels-Alder reaction. [L
OEtTiCl
3] can catalyze solvent-free ring opening of epoxides by Me
3SiN
3.
Depending on the conc. Of sulfuric acid, reaction between NaL
OEt and titanyl sulfate gave [(L
OEtTi)
2(μ-O)
2(μ-SO
4)] or [(L
OEtTi)
2(μ-O)(μ-SO
4)
2]. Reaction of NaL
OEt with titanyl sulfate in the presence of Na
4P
2O
7, Na
3PO
4 or Na
2Cr
2O
7 gave [(L
OEtTi)
2(μ-O)(μ
4-P
2O
7)
2], [(L
OEtTi)
3(μ-O)
3(μ
3-PO
4)] or [(L
OEtTi)
2(μ-CrO
4)
3] respectively. [(L
OEtTi)
2(μ-CrO
4)
3] can oxidize cyclohexanol to cyclohexanone. Interaction between [(L
OEtTi)
2(μ-O)
2(μ-SO
4)] and [NEt
4] [Cr
2O
7] gave trinuclear [(L
OEtTi)
3(μ-O)
3(μ
3-SO
4)][HCrO
4]. Treatment of [(L
OEtTi)
2(μ-O)
2(μ-SO
4)] with AgOTf gave [(L
OEtTi)
3(μ-O)
2(μ
3-O)(μ
3-SO
4)(AgOTf)][OTf]. Zine reduction of [(L
OEtTi)
2(μ-O)
2(μ-SO
4)] in TsOH gave a Ti(III) aqua complex [L
OEtTi(OTs)
2(H
2O)] (OTs
- = tosylate).
Interaction between zirconyl nitrate and NaL
OEt followed by extraction with CH
2Cl
2 gave tetranuclear [(L
OEtZr)
4(H
2O)
2(μ-OH)
4(μ
3-O)
2][NO
3]
4. Reaction of zirconyl nitrate with NaL
OEt in 6.5 wt % HNO
3 gave [L
OEtZr(NO
3)
3]. Reaction between zirconyl nitrate with two equiv. of NaL
OEt gave [(L
OEt)
2Zr(NO
3)][NO
3]. Treatment of zirconyl nitrate with NaL
OEt in H
2SO
4 gave [(L
OEt)
2Zr(NO
3)][L
OEtZr(NO
3)(SO
4)]. Treatment of ZrCl
4 with NaL
OEt in H
2SO
4 gave dinuclear [{(L
OEtZr)(H
2O)( SO
4}
2(μ-SO
4)] . Reaction of zirconyl nitrate with NaL
OEt in the presence of Na
3PO
4 gave [(L
OEtZr)
3(μ-OH)
3(μ-O)(PO
4)][NO
3]. Reaction of [(L
OEtZr)
4(H
2O)
2(μ-OH)
4(μ
3-O)
2][NO
3]
4 with bis(4-nitrophenyl)phosphate gave nitrophenol and [(L
OEtZr)
4(μ
3-PO
4)
4].
[(L
OEt)
2CeL
2](L=H
2PO
4-, NO
3-, 1/2SO
42-[P(O)
2(OPh)]
- and [P(O)
2(OC
6H
4NO
2-p)
2]
-) and [(L
OEt)
2CeCl] have been synthesized. Interaction between NaL
OEt and C(H)
2(Ph)
2(CrCl
2O
2)
2 gave [L
OEtCr(H
2O)(Cl)(CrO
3Cl)]. Treatment of [Mn(CO)
5Br] and NaL
OEt gave [L
OEtMn(CO)
3], which was oxidized to [(L
OEt)
2Mn]
n+ (n = 0, 1) by [NO][BF
4] and Br
2.
A structurally characterized C
3-symmetric chiral tripod ligand L
S-BINOL-([(η
5-C
5H
5)Co(P(O)(S-BINOL))
3]
-)(S-BINOL = (S)-1,1'bi-(2-naphtholate)) was synthesized from [CpCoI
2(CO)] and NaP(O)(S-BINOL). Structurally characterized [(L
S-BINOL)Cu(RC≡CR')] were synthesized from [Cu(MeCN)
4][BF
4], L
S-BINOL- and RC≡CR' (R = Ph, Me
3Si; R' = H, Me3
si) respectively. Treatment of L
S-BINOL- with [Cu(MeCN)
4][BF
4] gave [(L
S-BINOL)Cu(MeCN)], which can catalyze asymmetric aziridination of olefins. A fluorinated tripod ligand [C
5H
5Co(P(O)(OCH
2CF
3))
3]
- has been synthesized from [CpCoI
2(CO)] and Na[P(O)(OCH
2CF
3)].
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