Rare Earth Phenyltellurolates: 1D Coordination Polymers

Khasnis, Dilip V.; Brewer, Meggan; Lee, Jongseong; Emge, Thomas J.; Brennan, John G.

doi:10.1021/ja00095a016

Cited by 39 publications

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“…There is no apparent reaction of 1 with excess dipyridyl disulfide, and both 1 and dipyridyl disulfide can be isolated from metathesis reactions using Ce(IV) starting materials. Reductive elimination of REER has considerable precedence as a decomposition pathway in redox-active Ln(ER) x chemistry, and the stability of cerium(IV) isopropoxide but not cerium(IV) pyridinethiolate can be attributed to the strength of the S−S bonds (66 kcal/mol in HSSH 17 ) relative to the weaker O−O bonds (51(1) kcal/mol in HOOH 17 ) that would be produced in reductive elimination processes.…”

Section: Resultsmentioning

confidence: 99%

Early- and Late-Lanthanide Pyridinethiolates: Synthesis, Redox Stability, and Structure

et al. 1997

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The early and late lanthanides form stable complexes with the pyridinethiolate (2-S-NC(5)H(4), or SPy) ligands. The Ce compound Ce(SPy)(3) is relatively insoluble in neutral organic donor solvents such as THF or pyridine but can be solubilized by the addition of [PEt(4)][SPy] to form the orange homoleptic cerium thiolate [PEt(4)][Ce(SPy)(4)] (1). Low-temperature structural characterization of 1 showed that the complex is isostructural with the known Eu(III) derivative. Further oxidation of Ce(III) with dipyridyl disulfide does not occur. Molecular 1 is colored due to a low-energy f(1)-to-d(1) promotion. As the size of the lanthanide ion decreases, the solubility of neutral Ln(SPy)(3) appears to increase. Colorless [PEt(4)][Ln(SPy)(4)] (Ln = Ho (2), Tm (3)) can also be isolated by fractional crystallization, and the compounds are isostructural with the Ce and Eu derivatives. The neutral complexes of Ho and Tm are also slightly soluble in acetonitrile and dimethoxyethane and very soluble in pyridine. Both divalent and trivalent Yb complexes of the pyridinethiolate ligand dissolve in and crystallize from pyridine. Divalent Yb(SPy)(2) crystallizes as the pentagonal bipyramidal molecule (py)(3)Yb(SPy)(2) (4). One pyridine nitrogen and the four donor atoms of the two pyridinethiolate ligands are bound in equatorial positions, and two neutral pyridine ligands occupy the axial sites. The Yb(III) compound crystallizes readily from pyridine as molecular 8-coordinate (py)(2)Yb(SPy)(3) (5). Compounds 4 and 5 are intensely colored; 4 has a visible Yb(II)-to-pyridine charge transfer excitation that is virtually identical in energy to the analogous excitation in SmI(2)(py)(4), while 5 has a visible S-to-Yb charge transfer absorption. Crystal data (Mo Kalpha, 153(5) K) are as follows: 1, monoclinic space group P2/n, a = 15.118(6) Å, b = 16.117(4) Å, c = 26.443(7) Å, beta = 90.14(3) degrees, Z = 4; 4, monoclinic space group Cc, a = 10.588(1) Å, b = 16.810(3) Å, c = 14.833(5) Å, beta = 109.12(2) degrees, Z = 4; 5, monoclinic space group P2(1)/n, a = 9.672(2) Å, b = 16.293(4) Å, c = 19.214(3) Å, beta = 101.51(2) degrees, Z = 4.

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Section: Resultsmentioning

confidence: 99%

Early- and Late-Lanthanide Pyridinethiolates: Synthesis, Redox Stability, and Structure

et al. 1997

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“…Phosphido complexes are of interest because of the way they differ electrostatically from the corresponding amido species. Also, in light of an increasing recent interest in the synthesis of lanthanide chalcogenolate complexes − for use as precursors to materials which are dilute magnetic semiconductors, our results provide new opportunities for the formation of novel mixed lanthanide/main group element species.…”

Section: Introductionmentioning

confidence: 86%

Lanthanide Phosphido Complexes: A Comparison of the Divalent Homoleptic Species Ln[(μ-P^tBu₂)₂Li(thf)]₂ (Ln = Yb, Eu, Sm) Including the Structural Characterization and a Europium-151 Mössbauer Spectrum of Eu[(μ-P^tBu₂)₂Li(thf)]₂¹

1997

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A comparison of the three isostructural homoleptic lanthanide phosphide species Ln[(&mgr;-P(t)Bu(2))(2)Li(thf)](2) [Ln = Yb (1), Eu (2), Sm (3)] is reported. Eu(OSO(2)CF(3))(3) reacts with 5 equiv of LiP(t)Bu(2) in tetrahydrofuran to give the europium complex Eu[(&mgr;-P(t)Bu(2))(2)Li(thf)](2) (2) in 50% yield plus 0.5 equiv of (t)Bu(2)P-P(t)Bu(2). 2 crystallizes in space group P2(1)/c. Crystal data for 2 at 248 K: a = 21.740(3) Å, b = 12.345(1) Å, c = 20.633(2) Å, beta = 109.13(1) degrees; V = 5231.5(10) Å(3); Z = 4; D(calcd) = 1.131 g cm(-)(3); R(F)() = 3.29%. The molecular structure shows the four-coordinate europium atom in a distorted tetrahedral environment. A main feature of the crystal structure of 2 is the shortest Eu-P distance [3.034(1) Å] of divalent europium reported so far. A (151)Eu Mössbauer spectrum at 4.2 K is reported exhibiting an isomer shift of -11.7 mm/s.

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“…In the first compound, one Se ligand bonds η 3 and the other bonds η 2 to the Sm center. Furthermore, only recently have rare-earth to chalcogenide bonds been observed and structurally characterized. − Considerable work has evolved toward stabilizing those bonds with the use of bulky substituents on the rare-earth atom, the chalcogen atom, or both. ,,,− , Note that whereas some of the more attractive molecular precursors for solid-state rare-earth oxides are metal β-diketonates, useful precursors to solid-state rare-earth chalcogenides are very limited. Given the similarity of the imidodiphosphinochalcogenido ligand to the well-developed bidentate oxide ligands, its rare-earth complexes are possible candidates as precursors.…”

Section: Introductionmentioning

confidence: 99%

Bis(cyclopentadienyl)yttrium Complexes of the Ligand [N(QPPh₂)₂]^- (Q = S, Se): Synthesis, Structure, and NMR Properties of Cp₂Y[η³-N(QPPh₂)₂]

Pernin

Ibers

1999

Inorg. Chem.

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The compounds Cp(2)Y[eta(3)-N(QPPh(2))(2)] (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reaction between Cp(3)Y and HN(QPPh(2))(2) in tetrahydrofuran. In both compounds, the [N(QPPh(2))(2)](-) ligand is bound eta(3) to the Y center which, in 1, represents the first example of that mode of binding for the sulfur-containing ligand. The Y atom is also coordinated to two (C(5)H(5))(-) ligands and so is formally 9-coordinate. Both 1 and 2 are stable in inert environments for prolonged periods of time. Each is soluble in THF and CH(2)Cl(2). (1)H, (31)P, (77)Se, and (89)Y NMR data were collected to lend insight into the solution properties of these molecules. Crystallographic data for 1 (-120 degrees C): C(34)H(30)NP(2)S(2)Y, triclinic, P&onemacr;, a = 9.685(5) Å, b = 12.176(6) Å, c = 13.978(7) Å, alpha = 87.382(9) degrees, beta = 87.358(9) degrees, gamma = 68.689(9) degrees, V = 1533(1) Å(3), Z = 2, and R(1)(F) = 0.047 for the 4023 reflections with I > 2sigma(I). Crystallographic data for 2 (-120 degrees C): C(34)H(30)NP(2)Se(2)Y, triclinic, P&onemacr;, a = 9.745(5) Å, b = 12.222(6) Å, c = 13.930(7) Å, alpha = 88.024(9) degrees, beta = 87.380(9) degrees, gamma = 69.137(9) degrees, V = 1548(1) Å(3), Z = 2, and R(1)(F) = 0.056 for the 4324 reflections with I > 2sigma(I).

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Rare Earth Phenyltellurolates: 1D Coordination Polymers

Cited by 39 publications

References 0 publications

Early- and Late-Lanthanide Pyridinethiolates: Synthesis, Redox Stability, and Structure

Early- and Late-Lanthanide Pyridinethiolates: Synthesis, Redox Stability, and Structure

Lanthanide Phosphido Complexes: A Comparison of the Divalent Homoleptic Species Ln[(μ-P^tBu₂)₂Li(thf)]₂ (Ln = Yb, Eu, Sm) Including the Structural Characterization and a Europium-151 Mössbauer Spectrum of Eu[(μ-P^tBu₂)₂Li(thf)]₂¹

Bis(cyclopentadienyl)yttrium Complexes of the Ligand [N(QPPh₂)₂]^- (Q = S, Se): Synthesis, Structure, and NMR Properties of Cp₂Y[η³-N(QPPh₂)₂]

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Rare Earth Phenyltellurolates: 1D Coordination Polymers

Cited by 39 publications

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Early- and Late-Lanthanide Pyridinethiolates: Synthesis, Redox Stability, and Structure

Early- and Late-Lanthanide Pyridinethiolates: Synthesis, Redox Stability, and Structure

Lanthanide Phosphido Complexes: A Comparison of the Divalent Homoleptic Species Ln[(μ-PtBu2)2Li(thf)]2 (Ln = Yb, Eu, Sm) Including the Structural Characterization and a Europium-151 Mössbauer Spectrum of Eu[(μ-PtBu2)2Li(thf)]21

Bis(cyclopentadienyl)yttrium Complexes of the Ligand [N(QPPh2)2]- (Q = S, Se): Synthesis, Structure, and NMR Properties of Cp2Y[η3-N(QPPh2)2]

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Lanthanide Phosphido Complexes: A Comparison of the Divalent Homoleptic Species Ln[(μ-P^tBu₂)₂Li(thf)]₂ (Ln = Yb, Eu, Sm) Including the Structural Characterization and a Europium-151 Mössbauer Spectrum of Eu[(μ-P^tBu₂)₂Li(thf)]₂¹

Bis(cyclopentadienyl)yttrium Complexes of the Ligand [N(QPPh₂)₂]^- (Q = S, Se): Synthesis, Structure, and NMR Properties of Cp₂Y[η³-N(QPPh₂)₂]