Synthesis and x-ray crystallographic characterization of an oxo-bridged bimetallic organosamarium complex, [(C5Me5)2Sm]2(.mu.-O)

Evans, William J.; Grate, Jay W.; Bloom, Ira; Hunter, William E.; Atwood, Jerry L.

doi:10.1021/ja00288a021

Cited by 163 publications

(114 citation statements)

References 9 publications

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“…The correlation of decreasing maximum out-of-plane displacement with increasing metal size, as observed with the sterically crowded complexes, is found with two series of compounds among the last 33 complexes in 44,45 Nd, 46 La 44 ) complexes, the methyl displacements also decrease with increasing metal radius, but the [(C 5 Me 5 ) 2 U] 2 (µ-O) 29 analogue has a much large displacement, 0.35 Å, than that of [(C 5 Me 5 ) 2 -Sm] 2 (µ-O), 0.22 Å. This is inconsistent with the relative ionic radii.…”

Section: (C 5 Me 4 R) 3 M Complexes With Normal M-c(c 5 Me 4 R) Distamentioning

confidence: 66%

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C₅Me₅)₃M Complexes

Evans

Kozimor

2005

Inorg. Chem.

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The displacements of the methyl substituents away from the metal and out of the cyclopentadienyl ring plane are compared in sterically crowded (C(5)Me(5))(3)M complexes vs sterically normal f-element complexes in an attempt to evaluate the utility of this parameter in predicting unusual (C(5)Me(5))(1-) ring reactivity. The out-of-plane displacements of 16 sterically crowded tris(cyclopentadienyl) complexes of general formula (C(5)Me(5))(3)M, (C(5)Me(4)R)(3)M (R = Et, (i)Pr, (t)()Bu, SiMe(3)), (C(5)Me(5))(3)MX (X = anion), and (C(5)Me(5))(3)ML (L = neutral ligand) are compared with [(C(5)Me(5))(2)U](2)(C(6)H(6)), (C(5)Me(5))(2)Sm(PC(4)H(2)(t)Bu(2)), and 33 representative examples of f-element bis(cyclopentadienyl) complexes with normal cyclopentadienyl behavior and coordination numbers ranging from 6 to 10. In general, the methyl displacement values of sterically crowded complexes overlap with those in the other complexes, which demonstrates that the basis of the structural distortions is complex. However, if the most extreme out-of-plane displacement in each of the sterically crowded complexes is examined vs the analogous maximum out-of-plane displacement in less crowded systems, there appears to be a basis for predicting cyclopentadienyl reactivity.

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Section: (C 5 Me 4 R) 3 M Complexes With Normal M-c(c 5 Me 4 R) Distamentioning

confidence: 66%

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C₅Me₅)₃M Complexes

Evans

Kozimor

2005

Inorg. Chem.

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“…For Ln 4 O containing structures in the Cambridge Structural Database, 77 . 42 In addition to four coordinate Ln-oxo structures, there exist an extraordinary range of additional oxo geometries, from the linear or slightly bent Ln-O-Ln found in numerous bimetallic molecules, [22][23][24][25][26] to trigonal planar, pentagonal bipyramidal, and octahedral bonding environments. A coordination number of 2 results when the ancillary ligands inhibit ligand redistribution processes, i.e., in the [Cp* 2 Ln] 2 O compounds, where disproportionation to give Cp* 3 Ln/[Cp*LnO] is energetically unfavorable because of the ligand-ligand repulsions in Cp* 3 Ln.…”

Section: Discussionmentioning

confidence: 99%

Oxoclusters of the Lanthanides Begin to Resemble Solid-State Materials at Very Small Cluster Sizes: Structure and NIR Emission from Nd(III)

et al. 2007

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The reaction of Nd(SePh)3 with SeO2 and Hg in pyridine gives the dodecanuclear cluster [(py)18Nd12O6Se4(Se2)4(SePh)4(Se2Ph)2Hg2(SePh)4][(Hg(SePh)3]2. In this compound the 12 Nd(III) ions are stacked in four sets of Nd3, with pairs of tetrahedral oxo ligands separating the Nd3 planes and Se, SeSe, SePh, pyridine, and HgSePh groups encapsulating the oxo core. Both the Nd-O bond lengths and the geometries about the oxo ions are remarkably similar to those found in solid-state Nd2O3. Near-IR emission experiments indicate that the cluster emission properties are less intense than those of highly emissive (DME)2Nd(SC6F5)3 or (THF)8Nd8O2Se2(SePh)16 but brighter than the nonemissive solid-state compound Nd2O3. Intensity variations are interpreted in terms of concentration quenching and phonon relaxation.

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“…The oxide can be formed from a variety of sources, such as N 2 0 and 1,2-epoxybutane; however, l ,Zepoxybutane gives the highest yield. 23 Recently, it has been found that a by-product of these reactions is often the THF solvate…”

Section: Synthesis Of [(Cj3)srn(thf)](p-o)mentioning

confidence: 99%

The reactivity of Samarium(II) in a Bis(indenyl) coordination environment

Evans

Gummersheimer

1995

Applied Organom Chemis

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The reactivity of the organosamarium(II) indenyl complex (C9H7)2Sm(THF)x, 1, has been compared with that of (C5Me5)2Sm(THF)2, 2, and (C5Me5)2Sm, 3, by examination of characteristic organosamarium(II) reactions which form trivalent oxide, iodide, cyclo‐octatetraenyl and azobenzene complexes. Complex 1 reacts with excess N2O to form [(C9H7)2Sm(THF)]2(μ‐O), 4, and (C9H7)3Sm(THF), 5, as the major products. Two equivalents of 1 react with one equivalent of 1,2‐di‐iodoethane in THF to give (C9H7)SmI2(THF)2, 6, as well as 5. Complex 1 reacts with 1,3,5,7‐cyclo‐octatetraene in a 2:1 ratio in THF to form 5 and (C9H7)Sm(C8H8)(THF)x, 7, which has been fully characterized as the 2,2′‐bipyridine adduct (C9H7)Sm(C8H8)(C10H8N2), 7a. The reaction of 1 with azobenzene in a 2:1 ratio forms [(C9H7)Sm(N2Ph2)(THF)]x, 8, and 5. Complexes 4–6 and 7a have been definitively identified by X‐ray crystallography. Complex 4 crystallizes from THF in space group P1― [C 11; No. 2] with unit cell parameters at 163 K of a = 8.072(2) Å, b = 9.502(2) Å, c = 12.250(3) Å, α = 101.42(2)°, β = 90.71(2)°, γ = 102.50(2)°, V = 897.7(4) Å3 and Z = 1 for Dcalcd = 1.704 Mgm−3. Least‐squares refinement of the model based on 3924 reflections (|F0|)>3.0 σ (|F0|)) converged to a final RF=2.4%. The geometry around each Sm atom is a distorted tetrahedron and the Sm–O–Sm angle is 180°. Complex 5 crystallizes from THF/hexanes at −35°C in space group P63 [C 66; No. 173] with unit cell parameters at 163 K of a = 11.7370(14) Å, c = 10.1994(12) Å, V = 1216.8(3) Å3 and Z = 2 for Dcalcd = 1.550 Mg m−3. Least‐squares refinement of the model based on 976 reflections (|F0|> 3.0σ (|F0|) converged to a final RF = 2.3%. The three ring centroids and the THF oxygen atom define a distorted tetrahedron around samarium with a (ring centroid)–Sm–(ring centroid) angle of 116.0°. Complex 6 crystallizes from THF/hexanes as the trisolvate (C9H7)SmI2(THF)3, 6a, in space group P21/n [C 2h5; No. 14] with unit cell parameters at 163 K of a = 8.3969(12) Å, b = 17.165(5) Å, c = 33.592(7) Å, β = 96.468(15)°, V = 4811(2) Å3 and Z = 8 for Dcalcd = 2.031 Mg m−3. Least‐squares refinement of the model based on 5664 reflections (|F0|> 2.0 σ (|F0|)) converged to a final RF = 3.3%. The six ligands around Sm in 6a describe a distorted octahedron. The iodide ligands are trans to each other with a 153.8(1)° I–Sm–I angle. Adduct 7a crystallizes from hot THF/toluene in space group P1 [C 11; No. 2] with a unit cell parameters at 163 K of a = 7.886(7) Å, b = 16.72(2) Å, c = 17.48(2) Å, α = 62.96(7)°, β = 85.17(7)°, γ = 85.23(9)°, V = 2042(3) Å3 and Z = 4. The cyclooctateraenyl and indenyl ligands generate a bent metallocene structure for 7a which contains a chelating bipyridyl group in the plane bisecting the two rings.

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Synthesis and x-ray crystallographic characterization of an oxo-bridged bimetallic organosamarium complex, [(C5Me5)2Sm]2(.mu.-O)

Cited by 163 publications

References 9 publications

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C₅Me₅)₃M Complexes

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C₅Me₅)₃M Complexes

Oxoclusters of the Lanthanides Begin to Resemble Solid-State Materials at Very Small Cluster Sizes: Structure and NIR Emission from Nd(III)

The reactivity of Samarium(II) in a Bis(indenyl) coordination environment

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Synthesis and x-ray crystallographic characterization of an oxo-bridged bimetallic organosamarium complex, [(C5Me5)2Sm]2(.mu.-O)

Cited by 163 publications

References 9 publications

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C5Me5)3M Complexes

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C5Me5)3M Complexes

Oxoclusters of the Lanthanides Begin to Resemble Solid-State Materials at Very Small Cluster Sizes: Structure and NIR Emission from Nd(III)

The reactivity of Samarium(II) in a Bis(indenyl) coordination environment

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Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C₅Me₅)₃M Complexes

Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C₅Me₅)₃M Complexes