Reaction of (L
OEt)
2Ti
2(O)
2(SO
4) ((L
OEt- = [CpCo{P(O)(OEt)
2}
3]
-) with Ba(NO
3)
2 in water led to formation of tetranuclear (L
OEt)
4Ti
4(O)
6 (3), which has an adamantane-like Ti
4O
6 core. Treatment of L
OEtZr(OTf)
3 (OTf
- = triflate) (2) in wet CH
2Cl
2 afforded dinuclear [{L
OEtZr(H
2O)
2}
2(μ-OH)
2][OTf]
4 (4) whereas that with Na
2WO
4•xH
2O in CH
2Cl
2 afforded trinuclear [{L
OEtZr(H
2O)(μ-OH)}
3(μ
3-O)][OTf]
4 (5). Treatment of 5 in acetone with H
2O or NaOH afforded tetranuclear [{L
OEtZr}
4(μ-OH)
6(μ
4-O)][OTf]
4 (6). 4, 5 and 6 can be inter-converted to each other in acetone/H
2O by addition of triflic acid or bases.
Treatment of L
OEtZrF
3 with three equiv. of Me
3SiOTf and CH
3CO(OSiMe
3) in CH
2Cl
2 afforded L
OEtZr(OTf)
3 and L
OEtZr(CH
3CO
2)
3 (13), respectively. Treatment of L
OEtZrF
3 with three equiv. of (Me
3SiO)
2SO
2 in CH
2Cl
2 afforded H
2[(L
OEtZr)(SO
4)
2]
2 (11). Treatment of 11 with Et
3N afforded [Et
3NH][(L
OEtZr)(H
2O)(κ
1-SO
4)(κ
2-SO
4)] (12). Treatment of {L
OEtZr(κ
2-SO
4)(H
2O)}
2(μ
2-SO
4) with AgOTf afforded [{L
OEtZr(κ
2-SO
4)(H
2O)}
3(μ
3-SO
4)]OTf (10). Treatment of L
OEtZrF
3 with one or two equiv. of Me
3SiOCH
2CO(OSiMe
3) afforded [L
OEtZrF(OCH
2COO
2)]
2 (14) or [L
OEtZr(OCH
2CO
2)(HOCH
2CO
2)] (15). Treatment of L
OEtMF
3 (M = Ti, Zr) with x equiv. of ReO
3(OSiMe
3) in CH
2Cl
2 afforded L
OEtMF
(3-x)(ReO
4)
x (x = 1, 2 and 3). These perrhenato complexes can catalyze the sulfide oxidation with t-butyl hydroperoxide (TBHP). The reaction of (L
OEtTi)
2(μ-O)
2(μ-SO
4) with [Ru(dtbpy)(PPh
3)
2Cl
2]
2 (dtbpy = 4,4’-di-tert-butyl-2,2’-dipyridyl), RuH(PPh
3)
3(CO)Cl or in the presence of Ag(OTf) afforded the Ti(IV)-Ru(IV) [{(L
OEt)
2Ti
2(μ-O)}(μ
3-SO
4)(μ-O)
2{Ru-(dtbpy)(PPh
3)}][OTf]
2 (13) and Ti(IV)-Ru(II) [{(L
OEt)
2Ti
2(μ-O)}(μ
3-SO
4)(μ-O)
2{Ru(CO)(PPh
3)
2}] (14), respectively.
(L
OEt)
2Ce(Cr
2O
7) (24), (L
OEt)
2Ce(NOsO
3)
2 (25) and (L
OEt)
2Ce(ReO
4)
2 (24) were synthesized by reaction of (L
OEt)
2Ce(NO
3)
2 with Na
2Cr
2O
7, KOsO
3N and KReO
4 in water, respectively. Treatment of (L
OEt)
2Ce(NO
3)
2 with KMnO
4 in water resulted in a purple solid, which decomposed in CH
2Cl
2/hexane at -18 ℃ to give dinuclear [{(L
OEt)Ce}
2(μ-L')
2][MnO
4]
2 ([L']
2- = [CpCo{P(O)(OEt)
2}{P(O)
2(OEt)}]
2-) (27). Treatment of (L
OEt)
2Ce(NO
3)
2 with (NH
4)
6Mo
7O
24 in water afforded the Ce(IV)-containing polyoxometalate (POM) H
4[(L
OEtCe)
6(MoO
4)
8(MoO
6)] (30) and [(L
OEt)
2Ce]
2(Mo
8O
26) (31). Treatment of (L
OEt)
2Ce(NO
3)
2 with KRuO
4 and K
2[Os(O)
2(OH)
4] led to green and grey precipitates, respectively, which can catalyze oxidation of alcohols by N-methyl morpholine N-oxide.
L
OEtCe(NO
3)
3 (33) was synthesized by the reaction of (NH
4)
2Ce(NO
3)
6 with NaL
OEt in CH
2Cl
2 . Substitution of 33 with Ktpip
- (tpip
- = [N(Ph
2PO)
2]
-) afforded L
OEtCe(NO
3)
2(tpip) (34). Treatment of (L
OEt)
2Ce(NO
3)
2 with NaH
2PO
4 and Na
4H
2P
2O
7 in water afforded the phosphato (L
OEt)
2Ce(PO
4H
2)
2 (35) and pyrophosphate (L
OEt)
2Ce(κ
2-H
2P
2O
7) (36) complexes, respectively. 33 can hydrolyze bis-(p-nitrophenyl) phosphate (BNPP) in acetone/water. 33 decomposed rapidly in water to give (L
OEt)
2Ce(NO
3)
2 and unidentified Ce(NO
3)
4(H
2O)
x species.
Treatment of Ktpip with TiCl
2(O
iPr)
2 and L
OEtTi(OTf)
3 in CH
2Cl
2 afforded cis-Ti(tpip)
2Cl
2 (39) and [L
OEtTi(tpip)(OTf)]OTf (41), respectively. Reduction of 39 with Na/Hg afforded the Ti(III) complex Ti(tpip)
3 (40). Treatment of 41 with CsOH afforded [L
OEtTi(tpip)(OH)]OTf (42). Treatment of L
OEtTi(OTf)
3 with S-binapO
2 in CH
2Cl
2 afforded [L
OEtTi{S-binapO
2}(OH)]OTf (43) (S-binapO
2 = S-(-)-2,2'-bis(diphenylphosphinoyl)-1,1'-binaphthyl). Treatment of Ktpip and V(O)SO
4 in EtOH afforded V(O)(tpip)
2 (44). Recrystallization of 44 from unpurified Et
2O resulted in [{V(O)}
3(μ-tpip)
3(μ-O)
3] (45).
Treatment of NaL
OEt with [n-Bu
4N][Ru(N)Cl
4] in CH
3CN/Et
2O afforded L
OEtRu(N)Cl
2 (50). Treatment of L
OEtRu(N)Cl
2 with PPh
3, Et
3NO and Na
2S
2O
3 gave L
OEtRu(NX)Cl
2 (X = PPh
3, (51), O (52), S (56)). Treatment of Ag(OTf) with 52 afforded [52⋅Ag(OTf)]
2 (53), that reacted with dtbpy and PPh
3 in CH
3CN to give [52⋅Ag(dtbpy)(OTf)] (54) and [52⋅Ag(PPh
3)(OTf)] (55), respectively.
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