Treatment of NaL_OEt(Na[(η⁵-C₅H₅)Co{P(O)(OC₂H₅)₂} ₃]) with 1 equiv. of [Ti(O-i-Pr)₂Cl₂] and HCl in Et₂O gave [L_OEtTiCl₃]. Reaction between [L_OEtTiCl₃] and tetrachlorocatechol (C₆Cl₄(OH)₂) gave [L_OEtTi(Cl)(C₆Cl₄O₂)], which formed mono-μ-oxo complex [{L_OEtTi(C₆Cl₄O₂)}₂(μ-O)] in the presence of base. Reaction of NaL_OEt with titanyl sulfate / zirconyl nitrate and HBF₄ gave [L_OEtTiF₃] or [L_OEtZrF₃] respectively. Reaction between [L_OEtTiCl₃] and HOTf gave [L_OEtTi(OTf)₃] (OTf = triflate), which is an active catalyst for Diels-Alder reaction. [L_OEtTiCl₃] can catalyze solvent-free ring opening of epoxides by Me₃SiN₃. _{OEt OEt 2 2 4 OEt 2 4 2 OEt}...[ Read more ]

Treatment of NaL_OEt(Na[(η⁵-C₅H₅)Co{P(O)(OC₂H₅)₂} ₃]) with 1 equiv. of [Ti(O-i-Pr)₂Cl₂] and HCl in Et₂O gave [L_OEtTiCl₃]. Reaction between [L_OEtTiCl₃] and tetrachlorocatechol (C₆Cl₄(OH)₂) gave [L_OEtTi(Cl)(C₆Cl₄O₂)], which formed mono-μ-oxo complex [{L_OEtTi(C₆Cl₄O₂)}₂(μ-O)] in the presence of base. Reaction of NaL_OEt with titanyl sulfate / zirconyl nitrate and HBF₄ gave [L_OEtTiF₃] or [L_OEtZrF₃] respectively. Reaction between [L_OEtTiCl₃] and HOTf gave [L_OEtTi(OTf)₃] (OTf = triflate), which is an active catalyst for Diels-Alder reaction. [L_OEtTiCl₃] can catalyze solvent-free ring opening of epoxides by Me₃SiN₃.

Depending on the conc. Of sulfuric acid, reaction between NaL_OEt and titanyl sulfate gave [(L_OEtTi)₂(μ-O)₂(μ-SO₄)] or [(L_OEtTi)₂(μ-O)(μ-SO₄)₂]. Reaction of NaL_OEt with titanyl sulfate in the presence of Na₄P₂O₇, Na₃PO₄ or Na₂Cr₂O₇ gave [(L_OEtTi)₂(μ-O)(μ₄-P₂O₇)₂], [(L_OEtTi)₃(μ-O)₃(μ₃-PO₄)] or [(L_OEtTi)₂(μ-CrO₄)₃] respectively. [(L_OEtTi)₂(μ-CrO₄)₃] can oxidize cyclohexanol to cyclohexanone. Interaction between [(L_OEtTi)₂(μ-O)₂(μ-SO₄)] and [NEt₄] [Cr₂O₇] gave trinuclear [(L_OEtTi)₃(μ-O)₃(μ₃-SO₄)][HCrO₄]. Treatment of [(L_OEtTi)₂(μ-O)₂(μ-SO₄)] with AgOTf gave [(L_OEtTi)₃(μ-O)₂(μ₃-O)(μ₃-SO₄)(AgOTf)][OTf]. Zine reduction of [(L_OEtTi)₂(μ-O)₂(μ-SO₄)] in TsOH gave a Ti(III) aqua complex [L_OEtTi(OTs)₂(H₂O)] (OTs^- = tosylate).

Interaction between zirconyl nitrate and NaL_OEt followed by extraction with CH₂Cl₂ gave tetranuclear [(L_OEtZr)₄(H₂O)₂(μ-OH)₄(μ₃-O)₂][NO₃]₄. Reaction of zirconyl nitrate with NaL_OEt in 6.5 wt % HNO₃ gave [L_OEtZr(NO₃)₃]. Reaction between zirconyl nitrate with two equiv. of NaL_OEt gave [(L_OEt)₂Zr(NO₃)][NO₃]. Treatment of zirconyl nitrate with NaL_OEt in H₂SO₄ gave [(L_OEt)₂Zr(NO₃)][L_OEtZr(NO₃)(SO₄)]. Treatment of ZrCl₄ with NaL_OEt in H₂SO₄ gave dinuclear [{(L_OEtZr)(H₂O)( SO₄}₂(μ-SO₄)] . Reaction of zirconyl nitrate with NaL_OEt in the presence of Na₃PO₄ gave [(L_OEtZr)₃(μ-OH)₃(μ-O)(PO₄)][NO₃]. Reaction of [(L_OEtZr)₄(H₂O)₂(μ-OH)₄(μ₃-O)₂][NO₃]₄ with bis(4-nitrophenyl)phosphate gave nitrophenol and [(L_OEtZr)₄(μ₃-PO₄)₄].

[(L_OEt)₂CeL₂](L=H₂PO₄^-, NO₃^-, 1/2SO₄^2-[P(O)₂(OPh)]^- and [P(O)₂(OC₆H₄NO₂-p)₂]^-) and [(L_OEt)₂CeCl] have been synthesized. Interaction between NaL_OEt and C(H)₂(Ph)₂(CrCl₂O₂)₂ gave [L_OEtCr(H₂O)(Cl)(CrO₃Cl)]. 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][BF₄] and Br₂.

A structurally characterized C₃-symmetric chiral tripod ligand L_S-BINOL^-([(η⁵-C₅H₅)Co(P(O)(S-BINOL))₃]^-)(S-BINOL = (S)-1,1'bi-(2-naphtholate)) was synthesized from [CpCoI₂(CO)] and NaP(O)(S-BINOL). Structurally characterized [(L_S-BINOL)Cu(RC≡CR')] were synthesized from [Cu(MeCN)₄][BF₄], L_S-BINOL^- and RC≡CR' (R = Ph, Me₃Si; R' = H, Me3_si) respectively. Treatment of L_S-BINOL^- with [Cu(MeCN)₄][BF₄] gave [(L_S-BINOL)Cu(MeCN)], which can catalyze asymmetric aziridination of olefins. A fluorinated tripod ligand [C₅H₅Co(P(O)(OCH₂CF₃))₃]^- has been synthesized from [CpCoI₂(CO)] and Na[P(O)(OCH₂CF₃)].