Characterization of a novel [Sm(HMPA)4I2]I complex by positive ion fast atom bombardment and high resolution mass spectrometry

Cabrera, Armando; Salmón, Manuel; Rosas, N.; Pérez‐Flores, Javier; Velasco, Luis; Espinosa‐Pérez, Georgina; Arias, José L.

doi:10.1016/s0277-5387(97)00237-4

Cited by 16 publications

(12 citation statements)

References 8 publications

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“…The Sm–Sm distance (3.5057(4) Å) is close to those found in other dinuclear Sm(III) complexes . The terminal Sm–I bonds in 2a (3.1437(5) and 3.1688(6) Å) are comparable to those found in other six-coordinated Sm(III) complexes {such as [OC(Ph) 2 CH{CH = N( t Bu)}N( t Bu)]Li} 2 SmI(THF) (3.1372(6) Å) and [Sm(HMPA) 4 I 2 ]I (3.146(3) Å, HMPA = hexamethylphosphoric triamide), but they are considerably shorter than those reported in other six-coordinated Sm(II) complexes (Tp t BuMe)SmI(THF) 2 (3.1908(9) Å, Tp = pyrazolylborate ligand) and [SmI(μ-I)( N -MeIm) 3 ] 2 (3.237(1) Å, N -MeIm = N -methylimidazole) . These contrasts point to the possibility of a +3 oxidation state of two samarium centers in 2a .…”

Section: Resultssupporting

confidence: 73%

2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins

Zheng

Cao

et al. 2020

J. Am. Chem. Soc.

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While reduction reactions are ubiquitous in chemistry, it is very challenging to further reduce electron-rich compounds, especially the anionic ones. In this work, the reduction of 1,3-butadienyl dianion, the anionic conjugated olefin, has been realized by divalent rare-earth metal compounds (SmI2), resulting in the formation of novel 2-butene tetraanion bridged disamarium(III) complexes. Density functional theory (DFT) analyses reveal two features: (i) the single electron transfer (SET) from 4f atomic orbitals (AOs) of each Sm center to the antibonding π*-orbitals of 1,3-butadienyl dianion is feasible and the new HOMO formed by the bonding interaction between Sm 5d orbitals (AOs) and the π*-orbitals of 1,3-butadienyl dianion can accept favorably 2e– from 4f AOs of Sm(II); (ii) the 2-butene tetraanionic ligand serves as a unique 10e– donating system, in which 4e– act as two σ-donation bonding interactions while the rest 6e– as three π-donation bonding interactions. The disamarium(III) complexes represent a unique class of the bridged bis-alkylidene rare-earth organometallic complexes. The ligand-based reductive reactivity of 2-butene tetraanion bridged disamarium(III) complexes demonstrates that 2-butene tetraanionic ligand serves as a 3e– reductant toward cyclooctatetraene (COT) to provide doubly COT-supported disamarabutadiene complexes. The reaction of the disamarium(III) complexes with Cp*Li produces the doubly Cp*-coordinated Sm(III) complexes via salt metathesis. In addition, the reaction with Mo(CO)6 affords the oxycyclopentadienyl dinuclear complex via CO insertion.

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Section: Resultssupporting

confidence: 73%

2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins

Zheng

Cao

et al. 2020

J. Am. Chem. Soc.

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“…The Sm−I bond lengths for the other two complexes were determined to be 3.246(1) Å and 3.235(1) Å, respectively. The Sm−I bond distance in the [SmI 2 (HMPA) 4 ] structure reported by Hou is 3.390(2) Å. 7a,b …”

Section: Discussionmentioning

confidence: 90%

“…Information on the solution structure will provide insight into how a reducible ligand may interact with the complex. Recently, Hou and co-workers published the solid-state structures of two Sm(II) complexes produced by the ligation of HMPA with SmI 2 . In one experiment, 10 equiv of HMPA were placed in a solution of SmI 2 in THF.…”

Section: Discussionmentioning

confidence: 99%

“…Although numerous crystal structures are available for various Sm−HMPA coordination compounds, relatively little is known about the solution structures of these complexes. A detailed understanding of the structure and energetics of the interaction between HMPA and SmI 2 in THF would provide considerable insight into the reactivity of the complex.…”

Section: Introductionmentioning

confidence: 99%

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Structure and Energetics of the Samarium Diiodide−HMPA Complex in Tetrahydrofuran

1999

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The role of HMPA as a ligand for SmI2 and the stoichiometry and energetics of formation for the SmI2−HMPA complex in THF were investigated employing UV−vis spectroscopy, isothermal titration calorimetry (ITC), and vapor pressure osmometry (VPO). The aggregation number for SmI2 in THF was found to be 0.98 ± 0.09 over the entire concentration range studied (6.71−84.0 mM), indicating that SmI2 is monomeric. The UV−vis data suggest that four HMPA ligands coordinate to SmI2, and this was supported by ITC experiments. The combined results are consistent with [SmI2(HMPA)4] being the reductant responsible for the unique reactivity exhibited by SmI2−HMPA cosolvent combinations.

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“…[38–40, 83, 91–116] While these complexes ranged in nuclearity, the majority were monomers adopting a 2IS/1OS arrangement [(L) x LnI 2 ](I)[38, 40, 91–96, 106, 111, 117] (where L = neutral ligand or organic solvents such as: Pr i OH,[38] THF,[106, 117] and py[38, 106]) or the 3IS arrangement that utilizes combinations of bulky neutral ligands,[83, 95, 107, 110, 114, 118] THF,[98, 100, 102, 113] or Pr i OH [39] to fill the coordination sphere. However, no structure reports of the LaI 3 •MeOH derivatives have been previously reported.…”

Section: Resultsmentioning

confidence: 99%

Structural characterization of methanol substituted lanthanum halides

Boyle¹,

Ottley²,

Alam³

et al. 2010

Polyhedron

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The first study into the alcohol solvation of lanthanum halide [LaX 3 ] derivatives as a means to lower the processing temperature for the production of the LaBr 3 scintillators was undertaken using methanol (MeOH) Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. NIH Public Access Author ManuscriptPolyhedron. Author manuscript; available in PMC 2011 May 10. NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author Manuscript indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR ( 139 La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 -6 were slightly higher in comparison to their hydrated counterparts.

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Characterization of a novel [Sm(HMPA)4I2]I complex by positive ion fast atom bombardment and high resolution mass spectrometry

Cited by 16 publications

References 8 publications

2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins

2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins

Structure and Energetics of the Samarium Diiodide−HMPA Complex in Tetrahydrofuran

Structural characterization of methanol substituted lanthanum halides

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