Unprecedented Transformation of a Hydrotris(pyrazolyl)borate Ligand at a Metal Center:  Synthesis and Rearrangement of the First Mixed Tp/Cp Lanthanide Complex, Sm(TpMe2)2(Cp)

Lopes, Irène; Lin, Guanyang; Domingos, Ângela; McDonald, Robert; Marques, Noémia; Takats, Josef

doi:10.1021/ja984227u

Cited by 46 publications

(30 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Compounds 1, 2, 4 and 5 as well as the ''optical empty'' reference compounds [La(C 5 H 4 SiMe 3 ) 3 ] and [La(C 5 H 4 tBu) 3 (THF)] were synthesized by adopting the procedures of Wayda, [21] Lopes et al, [32] Birmingham et al, [70] Fischer et al [71] and Stults et al [72] The absorption spectra of compounds 1 and 2 were recorded by means of KBr pellets, and those of adducts 3 and 4 (dissolved in a mixture of MeTHF/THF in the ratio 3:1) as well as those of complex 5 (dissolved in a mixture of methylcyclohexane/toluene in the ratio 3:1) as glassy frozen solutions, making use of a Cary 5e instrument. The luminescence spectra of compounds 1, 2, 4 and 5 were run as powders (and that of 1 additionally as methylcyclohexane solution) by means of a Raman spectrometer (JobinϪYvon, model U 1000) equipped with an Ar ϩ laser (Coherent model Innova 70).…”

Section: Methodsmentioning

confidence: 99%

“…A single-crystal X-ray study of complex 2 revealed a symmetrical η 5 -bonding of the Cp ring and an η 3 -as well as an η 2 -bonding mode of the two Tp Me 2 ligands [32] (Figure 1). from a single-crystal analysis [32] In order to simplify the parametrization of the experimentally derived energy level scheme of this low symmetric compound, we adopt the following two approaches: in analogy with our previous treatments of the CF splitting patterns of [Ln(COT)(Tp Me 2)] (Ln ϭ Pr, Nd, Sm) [16Ϫ19] we only consider the influence of the Cp ligand, which leads to C 5v symmetry.…”

Section: General Symmetry Considerations Selection Rules and The Phementioning

confidence: 99%

“…from a single-crystal analysis [32] In order to simplify the parametrization of the experimentally derived energy level scheme of this low symmetric compound, we adopt the following two approaches: in analogy with our previous treatments of the CF splitting patterns of [Ln(COT)(Tp Me 2)] (Ln ϭ Pr, Nd, Sm) [16Ϫ19] we only consider the influence of the Cp ligand, which leads to C 5v symmetry. Alternatively, we approximate the real molecular geometry by a pentagonal sandwich complex (D 5h symmetry of the effective CF).…”

Section: General Symmetry Considerations Selection Rules and The Phementioning

confidence: 99%

See 2 more Smart Citations

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

et al. 2003

View full text Add to dashboard Cite

The absorption and luminescence spectra of pseudo (ψ) trigonal planar [Sm(η5‐C5H4tBu)3] (1), low symmetric [Sm(η5‐Cp)(η3‐Tp)(η2‐Tp)] (Cp = η5‐cyclopentadienyl; Tp = hydrotris(3,5‐dimethylpyrazolyl)borato) (2) as well as ψ trigonal pyramidal [Sm(η5‐C5H4tBu)3(THF)] (3), [Sm(η5‐Cp)3(THF)] (4) and [Sm(η5‐Cp)3(CNC6H11)] (5) have been measured at room and low temperatures. From the spectra obtained, truncated crystal field (CF) splitting patterns of these compounds could be derived, and simulated by fitting the parameters of a phenomenological Hamiltonian. On the basis of the CF parameters used, the global CF strengths experienced by the Sm3+ central ions of complexes 1−5, as well as the individual CF strength associated with one C5H4tBu− ligand are estimated. The obtained Slater parameters F2 and the spin‐orbit coupling parameters ζ4f allow the insertion of compounds 1−5 into truncated nephelauxetic and relativistic nephelauxetic series. Besides, the experimentally based non‐relativistic and relativistic molecular orbital schemes (in the f range) of complexes 1 and, partly, 3 are set up and compared with the results of quantum chemical model calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

show abstract

Section: Methodsmentioning

confidence: 99%

Section: General Symmetry Considerations Selection Rules and The Phementioning

confidence: 99%

Section: General Symmetry Considerations Selection Rules and The Phementioning

confidence: 99%

See 1 more Smart Citation

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

et al. 2003

View full text Add to dashboard Cite

show abstract

“…The synthesis of the unprecedented cyclopentadienylbis(pyrazolyl)borate ligand in the coordination sphere of samarium, which was reported by Marques and Takats et al,22 was certainly not anticipated. Despite its insolubility in the usual organic solvents the samarium( II ) complex [Sm(Tp

^{Me_{2}}

) 2 ] ( 34 ) is highly reactive 23.…”

Section: New Ligandsmentioning

confidence: 99%

Versatile Scorpionates—New Developments in the Coordination Chemistry of Pyrazolylborate Ligands

Edelmann

2001

Angew. Chem. Int. Ed.

View full text Add to dashboard Cite

Much more versatile than previously anticipated are the coordination modes of tris(pyrazolyl)borate ligands (scorpionates). Recent contributions in this area not only lead to a new understanding of the electronic effects, but for the first time report unusually high and low hapticities as well as novel coordination modes such as the π coordination of a pyrazolyl ring to potassium (see structure). Potentially useful new ligands have been made available through innovative synthetic routes.

show abstract

“…Sicher nicht vorhersagbar war die Synthese eines bisher beispiellosen Cyclopentadienylbis(pyrazolyl)borat‐Liganden in der Koordinationssphäre von Samarium, über die Marques, Takats et al berichteten 22. Trotz seiner Unlöslichkeit in gängigen Lösungsmitteln ist der Samarium( II )‐Komplex [Sm(Tp

^{Me_{2}}

) 2 ] 34 hochreaktiv 23.…”

Section: Neue Ligandenunclassified

Vielseitige Skorpionate - neue Möglichkeiten in der Koordinationschemie der Polypyrazolylborat-Liganden

Edelmann

2001

Angew. Chem.

View full text Add to dashboard Cite

Vielseitiger als bisher bekannt sind die Koordinationsmöglichkeiten von Tris(pyrazolyl)borat‐Liganden (Skorpionaten). Aktuelle Arbeiten auf diesem Gebiet liefern nicht nur neue Erkenntnisse zu den elektronischen Effekten, sondern belegen auch erstmals hohe und niedrige Haptizitäten sowie neuartige Koordinationsweisen, wie die π‐Koordination eines Pyrazolylrings an Kalium (siehe Struktur). Durch originelle Synthesewege konnte darüber hinaus das Spektrum nützlicher Liganden beträchtlich erweitert werden.

show abstract

Unprecedented Transformation of a Hydrotris(pyrazolyl)borate Ligand at a Metal Center: Synthesis and Rearrangement of the First Mixed Tp/Cp Lanthanide Complex, Sm(Tp^Me_²)₂(Cp)

Cited by 46 publications

References 26 publications

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

Versatile Scorpionates—New Developments in the Coordination Chemistry of Pyrazolylborate Ligands

Vielseitige Skorpionate - neue Möglichkeiten in der Koordinationschemie der Polypyrazolylborat-Liganden

Contact Info

Product

Resources

About