Facile synthesis of rare-earth pyrazolonates by the reaction of rare-earth metals with 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone. Crystal structures of [Ln(PMIP)3]2 (Ln=Y, Gd, Tb, Er, Tm)

Safronova, A. V.; Bochkarev, L. N.; Malysheva, I. P.; Баранов, Е. В.

doi:10.1016/j.ica.2012.03.032

Cited by 19 publications

(13 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Bond lengths[ ] and angles[8]f or [Yb(DFForm) 3 (CH 3 CN)]: Yb1-N1:2.372(2), Yb1-N2:2.346(2),Yb1-N3:2 .393(2), Yb1-N4:2 .344(2),Y b1-N5:2.403(2),Y b1-N6:2.342(2), Yb1-N7:2 .382(3). C7-Yb1-C20:9 7.24(8), C20-Yb1-C33:1 38.32 (7), C33-Yb1-C7:1 18.95(9), Chem. Eur.J.2016, 22,1 60 -173 www.chemeurj.org X-ray data for tetrameric [{Yb(bda)(DFForm)} 4 ]·C 6 D 6 were solved and refined in the triclinic space group P1 ,w ith half the tetramer and one half C 6 D 6 lattice solventw ithin the asymmetric unit (Figure 12).…”

Section: Oxidation Of [Yb(dfform) 2 (Thf) 3 ](Yb3)mentioning

confidence: 99%

“…(1)] to occurw ith LH = ArOH, [6] and pyrazolines. [7] We have circumvented the lower reactivity of variousp rotic agents (e.g.,p henols, amines, formamidines, and pyrazoles, LH) by use of redox transmetallation/protolysis (RTP), reactions between Ln metals,adiarylmercurial, and LH [Scheme1,E q. (2), n = 2,3] generallyp erformed in tetrahydrofuran (THF) or 1,2-dimethoxyethane( DME).…”

Section: Introductionmentioning

confidence: 99%

“…Molecular structures of [Yb(DFForm) 2 Cl(thf) 2 ](top),a nd [Ti(DF-Form)Cl 2 (thf) 2 ]( Ti1,b ottom).E llipsoids shown at 50 %p robability,hydrogen atoms removed for clarity.Selectedbondlengths [] for [Yb(DF-Form) 2 Cl(thf) 2 ]: Yb1-Cl1:2 .557(3), Yb1-N1:2 .439(7), Yb1-N2:2 .359(7), Yb1-O1: 2.20(2). Selectedb ond lengths [] for TiF1:T i1-Cl1:2 .2383(7), Ti1-N1: 2.1677(14), Ti1-O1:2.0913(16).…”

mentioning

confidence: 99%

See 2 more Smart Citations

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Deacon

Junk

Werner

2015

Chemistry A European J

View full text Add to dashboard Cite

Treatment of N,N'-bis(aryl)formamidines (ArFormH), N,N'-bis(2,6-difluorophenyl)formamidine (DFFormH) or N,N'-bis(2,6-diisopropylphenyl)formamidine (DippFormH), with europium metal in CH3 CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)2 (CH3 CN)2 }2 ] (Eu1) or [Eu(DippForm)2 (CH3 CN)4 ] (Eu2). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg(0) . With DFFormH in CH3 CN, [{Yb(DFForm)2 (CH3 CN)}2 ] (Yb1) was obtained in good yield, and [Yb(DFForm)2 (thf)3 ] (Yb3) was obtained from a synthesis in CH3 CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare-earth formamidinates. Heating Yb1 in PhMe/C6 D6 resulted in decomposition to trivalent products, including one from a CH3 CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb(0) , Hg(R)2 (R=Ph, C6 F5 ), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)2 (thf)3 ] (Yb3), or the first five coordinate rare-earth formamidinate complex [Yb(DippForm)2 (thf)] (Yb4 b), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)3 (thf)] (Yb6). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl4 (thf)2 , Ph3 CCl, C2 Cl6 ) gave [Yb(DFForm)3 (bp)] or [Yb(DFForm)2 Cl(thf)2 ], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare-earth ArForm complexes been achieved in Eu2 and Yb4 b, respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ-1κ(N:N'):2κ(N:N') in Eu1, or the twisted μ-1κ(N:N'):2κ(N':F') DFForm coordination in Yb1, both unprecedented in divalent rare-earth ArForm chemistry and in the wider divalent rare-earth amidinate field.

show abstract

Section: Oxidation Of [Yb(dfform) 2 (Thf) 3 ](Yb3)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Deacon

Junk

Werner

2015

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…In the case of reactions with Nd, Tb, Gd, Dy, Ho, Er and Lu, the lanthanoid metal had to be activated with I 2 (2 %) before a satisfactory reaction could be achieved. This method has previously been utilized in direct reactions of I 2 activated lanthanoids with phenols,[2a], pyrazolones, and to a limited extent with some pyrazoles. [35a], [35b]All reactions mixtures were monitored by 19 F NMR spectroscopy showing consumption of AgC 6 F 5 and formation of C 6 F 5 H [eq.…”

Section: Resultsmentioning

confidence: 99%

Replacing Mercury: Syntheses of Lanthanoid Pyrazolates from Free Lanthanoid Metals, Pentafluorophenylsilver, and Pyrazoles, Aided by a Facile Synthesis of Polyfluoroarylsilver Compounds

et al. 2019

View full text Add to dashboard Cite

The polyfluorophenylsilver complexes [Ag2(C6F4Br‐4)2(py)3] (py = pyridine) (1) and [{Ag2R2(py)2}n] [R = C6F5 (2); C6F4Br‐3 (3); C6F4H‐4 (4)] were prepared in reasonable yields by reactions of silver(I) oxide with the appropriate polyfluorobenzenes in pyridine. This simple and convenient synthesis is selective and does not lead to debromination of C6HF4Br‐(3 or 4). Complex 1 is dinuclear with AgR2 and Ag(py)3 units linked by a bridging polyfluoroaryl group and Ag···Ag interactions, whereas 2–4 are polymeric with alternating AgR2 and Ag(py)2 units similarly linked. The trivalent lanthanoid pyrazolates, [Ln(Ph2pz)3(py)2]·2thf (Ph2pz = 3,5‐diphenylpyrazolate; Ln = Yb, 5, Er, 6, Dy, 7, Lu, 8; thf = tetrahydrofuran), [Ho(Ph2pz)3(py)(thf)] (9), [Ln(Ph2pz)3(py)(dme)]·solv (Ln = Tb, solv = 1.75PhMe, 10, Gd, solv = 1.5dme, 11; dme = 1,2‐dimethoxyethane; PhMe = toluene), [Ln(Ph2pz)3(thf)3] (Ln = La, 12, Ce, 13, Nd, 14), [Ln(tBu2pz)3(py)2] (tBu2pz = 3,5‐di‐tert‐butylpyrazolate; Ln = Yb, 15, Tm, 16, Ho, 17, Dy, 18), [Yb(Phtpz)3(py)2]·PhMe (19) (Phtpz = 3‐Phenyl‐5‐(2′‐thienyl)pyrazolate) and [Nd(ttfpz)3(dme)2] (20) (ttfpz = 3‐(2′‐thienyl)‐5‐(trifluoromethyl)pyrazolate) have been prepared by redox transmetallation/protolysis (RTP) reactions employing lanthanoid metals, pentafluorophenylsilver and the corresponding pyrazoles (pzH) in donor solvents. This is a new synthetic route in which AgC6F5 replaces the more commonly used Hg(C6F5)2 or HgPh2. Yields are good to excellent if long crystallization times are used but the heavier Ln metals require activation with iodine to induce reaction. The monomeric structures exhibit η2‐bound pyrazolate ligands with eight‐coordinate metal atoms for complexes 5–9 and 15–19, nine‐coordinate metal atoms for complexes 10–14, and ten‐coordinate metal atoms for complex 20.

show abstract

“…The pyrazolatolanthanoid(III) complexes,[ Ln(Ph 2 pz) 3 (thf) 3 ]·thf (Ph 2 pz = 3,5-diphenylpyrazolate;L n= La, 1,C e, 2,N d, 3,T b, 4), [Ln 2 (Ph 2 pz) 4 (OMe) 2 (dme) 2 ]·2dme (Ln = Ho,5,E r,6,T m,7,L u,8), [Dy(Ph 2 pz) 3 (dme) 2 ]·2dme (9), [Sm(Ph 2 pz) 3 (dme) 2 ]·dme (10), [Ln(tBu 2 pz) 3 (thf) 2 ]( tBu 2 pz = 3,5-di-tert-butylpyrazolate;L n = La, 11,C e, 12,S m, 13,G d, 14,D y, 15,H o, 16,T m, 17,Y b, 18,L u, 19), [Ln(ttfpz) 3 (thf) 3 ]( ttfpz = 3-(2'-thienyl) -5-(trifluoromethyl) effective.T he reactionm ixturesw erem onitored by 19 FNMR spectroscopy showing consumption of Bi(C 6 F 5 ) 3 and formation of C 6 F 5 Hu pon completion. Good yields of crystalline products were obtained (Table 1) after appropriate crystallization procedures (see Experimental section),e xcept for complex 10.M ostt ris(pyrazolates) (1)(2)(3)(4)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)c rystallized as thf complexes (Table 1) and 1-4 also have lattice thf. However, the products from Ho, Er,T m, Lu, Dy, Sm with Ph 2 pzHw ere obtained as powders from thf, and were crystallized from dme giving [Ln(Ph 2 pz) 3 (dme) 2 ]·n dme (Ln = Dy, n = 2 9;L n = Sm, n = 1 10)b ut [Ln 2 (Ph 2 pz) 4 (m-OMe) 2 (dme) 2 ]·2dme species( Ln = Ho, 5,E r, 6,T m, 7,L u, 8)a rising from cleavage of dme as well as ether exchange [Eq.…”

Section: Resultsmentioning

confidence: 99%

Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?

Guo

Blair

Deacon

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation/protolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr2, and a proligand HL. Thus, the lanthanoid pyrazolates, [Ln(Ph2pz)3(thf)3] (Ph2pz=3,5‐diphenylpyrazolate; Ln=La, 1, Ce, 2, Nd, 3, Tb, 4; thf=tetrahydrofuran), [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (Ln=Ho, 5, Er, 6, Tm, 7, Lu, 8; dme=1,2‐dimethoxyethane), [Ln(Ph2pz)3(dme)2] (Ln=Dy, 9, Sm, 10), [Ln(tBu2pz)3(thf)2] (tBu2pz=3,5‐di‐tert‐butylpyrazolate; Ln=La, 11, Ce, 12, Sm, 13, Gd, 14, Dy, 15, Ho, 16, Tm, 17, Yb, 18, Lu, 19), [Ln(ttfpz)3(thf)3] (ttfpz=3‐(2′‐thienyl)‐5‐(trifluoromethyl)pyrazolate; Ln=La, 20, Sm, 21), and [Er(PhMepz)3(thf)2] 22 (PhMepz=3‐phenyl‐5‐methylpyrazolate) have been prepared in good yields by redox transmetallation/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C6F5)3]⋅0.5 diox (diox=1, 4‐dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C6F5)3 replaces the commonly used Hg(C6F5)2 or HgPh2, and provides proof of concept for the method. [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (5–8) complexes are derived from C−O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide‐bridged species. Other structures are monomeric with η2‐bound pyrazolate ligands and nine‐coordinate metal atoms for complexes 1–4, 9–10 and 20–21, and eight‐coordinate metal atoms for complexes 11–19 and 22.

show abstract

Facile synthesis of rare-earth pyrazolonates by the reaction of rare-earth metals with 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone. Crystal structures of [Ln(PMIP)3]2 (Ln=Y, Gd, Tb, Er, Tm)

Cited by 19 publications

References 9 publications

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Replacing Mercury: Syntheses of Lanthanoid Pyrazolates from Free Lanthanoid Metals, Pentafluorophenylsilver, and Pyrazoles, Aided by a Facile Synthesis of Polyfluoroarylsilver Compounds

Can Bismuth Replace Mercury in Redox Transmetallation/Protolysis Syntheses from Free Lanthanoid Metals?

Contact Info

Product

Resources

About