Organotin Compounds as Reagents for the Synthesis of Lanthanoid Complexes by Redox Transmetallation Reactions

Beaini, Samar; Deacon, Glen B.; Hilder, Matthias; Junk, Peter Courtney; Turner, David R.

doi:10.1002/ejic.200600045

Cited by 31 publications

(49 citation statements)

References 39 publications

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“…With [M(ttfpz) 2 (thf) 4 ] [13] (M = Yb, Ca, Sr, Ba) complexes, M-N adjacent to CF 3 is shorter, whereas in [M(ttfpz) 2 -(dme) 2 ] [13] (M = Yb, Ca, Sr) and [Ba(ttfpz) 2 (dme) 3 ], [13] either M-N adjacent to CF 3 is longer (Yb, Ba) or the coordination is symmetrical. Comparing fac-2 with mer-[Sm(Ph 2 pz) 3 (thf) 3 ]·3thf, [19] the average Sm-N bond lengths are comparable (2.46 Å to 2.44 Å, respectively) despite the stereochemical difference, but the range of bond lengths is somewhat larger in 2, presumably a result of the unsymmetrical substitution.…”

Section: 3mentioning

confidence: 81%

“…In meridional 3, only thf molecule O(2) is transoid with a cen{N(3)N(4)}-Tb(1)-O(2) angle of 162.2° (Table 2), leading to elongation of the Tb(1)-O(2) bond compared with the Tb(1)-O(1/3) bonds (Table 2). On the other hand, ϽSm-OϾ of 2 (2.48 Å) is less than that (2.54 Å) of [Sm(Ph 2 pz) 3 (thf) 3 ]·3thf, [19] perhaps indicative of the greater [24] (RE = La, Pr, Nd, Gd, Er; dbp = 2,4-di-tert-butylphenolate) complexes, where a meridional arrangement is observed for RE = LaGd, the larger lanthanoid metals, but a facial arrangement for Er.…”

Section: 3mentioning

confidence: 88%

“…Elemental or metal analyses confirmed the proposed stoichiometries in all cases, except for 3 where the microanalysis fitted for the loss of lattice solvent and 9 where the metal analysis indicated the loss of two molecules of dme from the structural formula derived from X-ray crystallography. 19 F NMR measurements revealed one resonance at around -59 to -60 ppm for the freely rotating CF 3 group for all compounds. The effect of paramagnetism on 2 was negligible.…”

Section: Syntheses and Characterisationsmentioning

confidence: 98%

“…A trans-cen(NN)-RE-cen(NN) and a transoid OLn-O angle are observed only in 3 ( Table 2). Related Ph 2 pz complexes [Ln(Ph 2 pz) 3 (thf) 3 ] (Ln = Nd, Sm) [18,19] display a meridional arrangement of the ligands, in contrast to 1 and 2 (Scheme 2).…”

Section: 3mentioning

confidence: 98%

“…[14,15] ), weak C-F-M interactions [16][17][18] or even C-F activation. [19] In the event, the domination of η 2 -binding for these elements [1,2] was not subverted, and asymmetric chelation occured. Furthermore, interesting differences to the corresponding Ph 2 pz complexes were observed.…”

Section: Introductionmentioning

confidence: 97%

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Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

2011

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Trivalent rare earth complexes of the unsymmetrical 3-(2Ј-thienyl)-5-(trifluoromethyl)pyrazolate (ttfpz) ligand, namely [RE(ttfpz) 3 (thf) 3 ]·nsolv, where thf = tetrahydrofuran [RE = La, solv = PhMe, n = 0.5 (1); RE = Sm, n = 0 (2); RE = Tb, solv = thf, n = 1 (3)], [RE(ttfpz) 3 (thf) 2 ] [RE = Y (4), Ho (5), Lu (6), Sc (7)] and [RE(ttfpz) 3 (dme) 2 ]·nsolv, where dme = 1,2-dimethoxyethane [RE = La, n = 0 (8a); RE = La, solv = Et 2 O, n = 0.5 (8b); RE = Eu, solv = dme, n = 1 (9)], were prepared, mainly by redox transmetallation/protolysis from the free metal, Hg(C 6 F 5 ) 2 and ttfpzH, and structurally characterised. In the nine-coordinate, pseudo-octahedral complexes 1 and 2, η 2 -

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Section: 3mentioning

confidence: 81%

Section: 3mentioning

confidence: 88%

Section: Syntheses and Characterisationsmentioning

confidence: 98%

Section: 3mentioning

confidence: 98%

Section: Introductionmentioning

confidence: 97%

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Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

2011

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Mono‐, Di‐, Tri‐ and Tetranuclear Rare Earth Complexes Obtained Using a Moderately Bulky Aryloxide Ligand

Deacon

Junk

Moxey

2009

Chemistry An Asian Journal

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Redox transmetallation ligand exchange reactions involving a rare earth metal, 2,4,6-trimethylphenol (HOmes), and a diarylmercurial afford rare earth aryloxo complexes, which are structurally characterized. Both the lanthanoid contraction and the identity of the reaction solvent are found to influence the outcome of the reactions. Using THF in the reaction affords a dinuclear species [Ln2(Omes)6(thf)4].2THF (Ln=La 1, Nd 2) for the lighter rare earth metals, while a mononuclear species [Ln(Omes)3(thf)3] (Ln=Sm 3, Tb 5, Er 6, Yb 7, Y 8) is obtained for the heavier rare earth elements. Surprisingly, there is no change in metal coordination number between the two structural motifs. A divalent trinuclear linear complex [Eu3(Omes)6(thf)6] 4 is obtained for Eu, and features solely bridging aryloxide ligands. Using DME as the reaction solvent affords [La(Omes)3(dme)2] 9 from the reaction mixture, and [Ln2(Omes)6(dme)2].PhMe (La 10, Nd 11) and [Y(Omes)3(dme)2] 14 following crystallization of the crude product from toluene. The dinuclear species [Eu2(Omes)4(dme)4] 12 contains two unidentate and two chelating DME ligands, and contrasts the linear structure of 4. Treatment of HOmes and HgPh2 with Yb metal in DME affords the mixed valent Yb(II/III) complex [Yb2(Omes)5(dme)2] 13, which is stabilized by an intramolecular pi-Ph-Yb interaction, and is a rare example of a mixed valent rare earth aryloxide. Treatment of Er metal with HOmes at elevated temperature (solvent free) affords the homoleptic [Er4(Omes)12] 15, which consists of a tetranuclear array of Er atoms arranged in a 'herringbone' fashion; the structure is stabilized by intramolecular pi-Ph-Er interactions. Reaction of La metal with HOmes under similar conditions yields toluene insoluble "La(Omes)3", which affords 1 following extraction with THF.

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Steric Modulation of Coordination Number and Reactivity in the Synthesis of Lanthanoid(III) Formamidinates

Cole

Deacon

Forsyth

et al. 2007

Chemistry A European J

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Reactions of a range of the readily prepared and sterically tunable N,N'-bis(aryl)formamidines with lanthanoid metals and bis(pentafluorophenyl)mercury (Hg(C6F5)2) in THF have given an extensive series of tris(formamidinato)lanthanoid(III) complexes, [Ln(Form)3(thf)n], namely [La(o-TolForm)3(thf)2], [Er(o-TolForm)3(thf)], [La(XylForm)3(thf)], [Sm(XylForm)3], [Ln(MesForm)3] (Ln=La, Nd, Sm and Yb), [Ln(EtForm)3] (Ln=La, Nd, Sm, Ho and Yb), and [Ln(o-PhPhForm)3] (Ln=La, Nd, Sm and Er). [For an explanation of the N,N'-bis(aryl)formamidinate abbreviations used see Scheme 1.] Analogous attempts to prepare [Yb(o-TolForm)3] by this method invariably yielded [{Yb(o-TolForm)2(mu-OH)(thf)}2], but [Yb(o-TolForm)3] was isolated from a metathesis synthesis. X-ray crystal structures show exclusively N,N'-chelation of the Form ligands and a gradation in coordination number with Ln3+ size and with Form ligand bulk. The largest ligands, MesForm, EtForm and o-PhPhForm give solely homoleptic complexes, the first two being six-coordinate, the last having an eta1-pi-Ar--Ln interaction. Reaction of lanthanoid elements and Hg(C6F5)2 with the still bulkier DippFormH in THF resulted in C--F activation and formation of [Ln(DippForm)2F(thf)] (Ln=La, Ce, Nd, Sm and Tm) complexes, and o-HC6F4O(CH2)4DippForm in which the formamidine is functionalised by a ring-opened THF that has trapped tetrafluorobenzyne. Analogous reactions between Ln metals, Hg(o-HC6F4)2 and DippFormH yielded [Ln(DippForm)2F(thf)] (Ln=La, Sm and Nd) and 3,4,5-F3C6H2O(CH2)4DippForm. X-ray crystal structures of the heteroleptic fluorides show six-coordinate monomers with two chelating DippForm ligands and cisoid fluoride and THF ligands in a trigonal prismatic array. The organometallic species [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] (Ln=Nd or Sm) are obtained from reaction of Nd metal, bis(phenylethynyl)mercury (Hg(C[triple chemical bond]CPh)2) and DippFormH, and the oxidation of [Sm(DippForm)2(thf)2] with Hg(C[triple chemical bond]CPh)2, respectively. The monomeric, six-coordinate, cisoid [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] complexes have trigonal prismatic geometries and rare (for Ln) terminal C[triple chemical bond]CPh groups with contrasting Ln--C[triple chemical bond]C angles (Ln=Nd, 170.9(4) degrees; Ln=Sm, 142.9(7) degrees). Their formation lends support to the view that [Ln(DippForm)2F(thf)] complexes arise from oxidative formation and C--F activation of [Ln(DippForm)2(C6F5)] intermediates.

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Organotin Compounds as Reagents for the Synthesis of Lanthanoid Complexes by Redox Transmetallation Reactions

Abstract: Redox transmetallation reactions between trimethyltin com

Cited by 31 publications

References 39 publications

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

Mono‐, Di‐, Tri‐ and Tetranuclear Rare Earth Complexes Obtained Using a Moderately Bulky Aryloxide Ligand

Steric Modulation of Coordination Number and Reactivity in the Synthesis of Lanthanoid(III) Formamidinates

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