Insight in cyclopentadienyl metal complexes with superbulky ligands: The crystal structure of [CpBIGK]∞

Harder, Sjoerd; Ruspic, Christian

doi:10.1016/j.jorganchem.2008.09.073

Cited by 18 publications

(30 citation statements)

References 36 publications

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“…Cp BIGi-Pr H was further re-crystallized from acetone, Cp BIGn-Bu H was re-crystallized from n-hexane:isopropanol 1:10 and Cp BIGt-Bu H was re-crystallized from toluene:methanol 1:1. Cp BIGn-Bu Na 7 [58] and Cp BIGn-Bu K 8 [16] were previously reported, but analytical details ( 1 H, 13 C, EA, XRD) were only given for 8. NMR spectra were recorded on a Bruker Avance 300 spectrometer at 25 °C at 300 MHz ( 1 H), 75 MHz ( 13 C), 117 MHz ( 7 Li), 79 MHz ( 23 Na), 122 MHz ( 31 P), 98 MHz ( 87 Rb) and 39 MHz ( 133 Cs) and referenced to internal toluene-d8 ( 1 H:  = 2.08 ppm; 13 133Cs: δ = 0 ppm).…”

Section: Methodsmentioning

confidence: 99%

“…[14,15] Unfortunately, their applicability in organic reactions is sometimes hampered by their low solubility in organic solvents. A promising method to overcome this experimental problem is the use of para-alkyl-substituted pentaarylcyclopentadienyl ligands C5(p-alkyl-Ph)5 [16][17][18][19] such as pentakis-(4-n-butylphenyl)cyclopentadienyl (Cp Big = C5(p-n-Bu-Ph)5) [16] as well as the corresponding pentakis-(4-ethylphenyl)cyclopentadienyl (C5(p-Et-Ph)5) and pentakis-(4-ipropylphenyl)cyclopentadienyl derivatives (C5(p-i-Pr-Ph)5). [20] In addition, the introduction of (bulky) substituents in para-position furthermore enhances the steric bulk of the ligand.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

et al. 2019

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Cs) NMR spectroscopy is reported. In addition, the solid-state structures of 5, 10, 11, and 13 were determined by single crystal X-ray diffraction, revealing the formation of infinite one-dimensional chain structures in the solid state (5, 10) or solvents-separated ion pairs (11, 13). Salt elimination reactions of Cp BIGt-Bu K 13 with ECl3 yielded the monosubstituted cyclopentadienyl compounds Cp BIGt-Bu ECl2 (E = P 16, As 17, Sb 18, Bi 19), which were characterized by elemental analysis, IR, and heteronuclear ( 1 H, 13 C, 31 P) NMR spectroscopy and single crystal X-ray diffraction (17).

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

et al. 2019

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“…[3] For this reason we recently reintroduced the superbulky metallocene ligand (4-nBuphenyl) 5 C 5 , [3b] which we have abbreviated throughout our work as Cp BIG . [4][5][6][7] Introduction of this ligand in lanthanide (Ln) chemistry led to surprising observations. Whereas half-sandwich complexes can be obtained simply by reaction of tris-A C H T U N G T R E N N U N G (benzyl)lanthanide precursors (Ln = Y, Dy, Nd, Tm) with Cp BIG H (Scheme 1), the attempted syntheses of such complexes for Yb and Sm instead led to spontaneous reduction of the lanthanide metal and the isolation of Ln II metallocenes.…”

Section: Introductionmentioning

confidence: 99%

Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [Eu^II(Cp^BIG)₂] (Cp^BIG=(4‐nBu‐C₆H₄)₅‐Cyclopentadienyl)

Harder

Naglav

Ruspic

et al. 2013

Chemistry A European J

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The superbulky deca-aryleuropocene [Eu(Cp(BIG))2], Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl, was prepared by reaction of [Eu(dmat)2(thf)2], DMAT = 2-Me2N-α-Me3Si-benzyl, with two equivalents of Cp(BIG)H. Recrystallizyation from cold hexane gave the product with a surprisingly bright and efficient orange emission (45% quantum yield). The crystal structure is isomorphic to those of [M(Cp(BIG))2] (M = Sm, Yb, Ca, Ba) and shows the typical distortions that arise from Cp(BIG)⋅⋅⋅Cp(BIG) attraction as well as excessively large displacement parameter for the heavy Eu atom (U(eq) = 0.075). In order to gain information on the true oxidation state of the central metal in superbulky metallocenes [M(Cp(BIG))2] (M = Sm, Eu, Yb), several physical analyses have been applied. Temperature-dependent magnetic susceptibility data of [Yb(Cp(BIG))2] show diamagnetism, indicating stable divalent ytterbium. Temperature-dependent (151)Eu Mössbauer effect spectroscopic examination of [Eu(Cp(BIG))2] was examined over the temperature range 93-215 K and the hyperfine and dynamical properties of the Eu(II) species are discussed in detail. The mean square amplitude of vibration of the Eu atom as a function of temperature was determined and compared to the value extracted from the single-crystal X-ray data at 203 K. The large difference in these two values was ascribed to the presence of static disorder and/or the presence of low-frequency torsional and librational modes in [Eu(Cp(BIG))2]. X-ray absorbance near edge spectroscopy (XANES) showed that all three [Ln(Cp(BIG))2] (Ln = Sm, Eu, Yb) compounds are divalent. The XANES white-line spectra are at 8.3, 7.3, and 7.8 eV, for Sm, Eu, and Yb, respectively, lower than the Ln2O3 standards. No XANES temperature dependence was found from room temperature to 100 K. XANES also showed that the [Ln(Cp(BIG))2] complexes had less trivalent impurity than a [EuI2(thf)x] standard. The complex [Eu(Cp(BIG))2] shows already at room temperature strong orange photoluminescence (quantum yield: 45 %): excitation at 412 nm (24,270 cm(-1)) gives a symmetrical single band in the emission spectrum at 606 nm (νmax =16495 cm(-1), FWHM: 2090 cm(-1), Stokes-shift: 2140 cm(-1)), which is assigned to a 4f(6)5d(1) → 4f(7) transition of Eu(II). These remarkable values compare well to those for Eu(II)-doped ionic host lattices and are likely caused by the rigidity of the [Eu(Cp(BIG))2] complex. Sharp emission signals, typical for Eu(III), are not visible.

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“…The lower solubility of the Pr* framework as compared to Dipp‐functionalized complexes presumably arises from the numerous phenyl moieties in Pr*. This effect has been observed for other types of ligands, such the decreased solubility of pentaphenylcyclopentadienyl as compared to cyclopentadienyl, encouraging the development of alkyl‐substituted versions such as Cp BIG 19…”

Section: Resultsmentioning

confidence: 97%

Bisimido Molybdenum Complexes of the Extremely Bulky Pr* Framework

Hering

Варга

Würtemberger

et al. 2015

Zeitschrift anorg allge chemie

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Synthesis and characterization of molybdenum bisimido complexes featuring the extremely bulky Pr* framework [Pr* = 2,6‐bis(diphenylmethyl)‐4‐methylphenyl] are reported. The octahedral halide complex [Mo(NPr*)2Cl2(THF)2] (1) is readily available from ammonium dimolybdate and the amine Pr*NH2, and features two THF molecules in the coordination sphere of molybdenum. The chloride ligands in 1 may be exchanged with methyl or benzyl groups using Grignard reagents. The resulting complexes [Mo(NPr*)2Me2] (2) and [Mo(NPr*)2Bz2] (3) are monomeric and, in contrast to 1, do not coordinate further neutral two‐electron donor ligands in neither the solid state nor in solution.

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Insight in cyclopentadienyl metal complexes with superbulky ligands: The crystal structure of [CpBIGK]∞

Cited by 18 publications

References 36 publications

Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [Eu^II(Cp^BIG)₂] (Cp^BIG=(4‐nBu‐C₆H₄)₅‐Cyclopentadienyl)

Bisimido Molybdenum Complexes of the Extremely Bulky Pr* Framework

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Insight in cyclopentadienyl metal complexes with superbulky ligands: The crystal structure of [CpBIGK]∞

Cited by 18 publications

References 36 publications

Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

Synthesis and Structures of s- and p-Block Metal Complexes Containing Sterically Demanding Pentaarylcyclopentadienyl Substituents

Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [EuII(CpBIG)2] (CpBIG=(4‐nBu‐C6H4)5‐Cyclopentadienyl)

Bisimido Molybdenum Complexes of the Extremely Bulky Pr* Framework

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Physical Properties of Superbulky Lanthanide Metallocenes: Synthesis and Extraordinary Luminescence of [Eu^II(Cp^BIG)₂] (Cp^BIG=(4‐nBu‐C₆H₄)₅‐Cyclopentadienyl)