Benzophenone Adduct of Tris(cyclopentadienyl)dysprosium

Zhou, Xiaoyu; Wu, Zhongzhi; You, Xiao‐Zeng; Xu, Zheng; Zhang, Y.; Huang, Xiao‐Ying

doi:10.1107/s0108270196002934

Cited by 7 publications

(2 citation statements)

References 7 publications

(7 reference statements)

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“…Notably, the corresponding cerium complex 4a revealed a much more acute Ce–O–C (carbonyl) bond angle of 154.7°. The C–O bond lengths of the donating ketones average 1.235 Å and are all in good accordance with those of other lanthanide–ketone adduct complexes such as Tb[N(SiMe 3 ) 2 ] 3 (Ph 2 CO),10 DyCp 3 (Ph 2 CO),11 and the urea complex CeCp 3 (NMe 2 CO) 12. The rare‐earth metal complexes [Y(OC 14 H 11 ) 2 (OC 14 H 11 )] 2 (C 13 H 8 O),13 YCp 3 (Ph 2 CO),14 and other X=O→Ln adducts15 also compare well.…”

Section: Resultssupporting

confidence: 76%

Trivalent Cerium and Praseodymium Aromatic Ketone Adducts

2012

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The reactions of the aromatic ketones benzophenone and 9‐fluorenone with trivalent [LnL3] complexes [Ln = Ce, Pr; L = N(SiMe3)2, C5H5 (Cp)] produce highly colored solutions in toluene. Characterization of these complexes by X‐ray diffraction revealed them to be monoadducts of the form [LnL3(ketone)]. The crystallographically determined C–O bonds of these complexes are longer than those of the free ketones. Significant ligand‐to‐metal charge transfer is also indicated by the ν(C=O) vibration of the coordinated ketone, which appears at lower wavelength. Solution‐based 1H NMR spectroscopy showed paramagnetic spectra of complexes Ln[N(SiMe3)2]3(ketone) and Ln(C5H5)3(ketone), which further supports this finding.

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Section: Resultssupporting

confidence: 76%

Trivalent Cerium and Praseodymium Aromatic Ketone Adducts

2012

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“…The Y−O(4) bond to the ketone is longer than the others in the molecule at 2.444(2) Å, in line with the dative nature of this bond. A comparison with the related complexes Cp* 2 YCl(OCPh 2 ), [Tb{N(SiMe 3 ) 2 } 3 (OCPh 2 )], and [DyCp 3 (OCPh 2 )], which are suitable for comparison due to the similar ionic radii of Y, Dy, and Tb (0.893, 0.908, and 0.923 Å, respectively), reveals that the M−O ketone bond distances for these complexes are shorter (Y, 2.312(2) Å; Tb, 2.305(9) Å; Dy, 2.384(3) Å) than Y−O ketone in [L 2 Y(OCHPh 2 )(OCPh 2 )]. This is reflective of the more severe steric environment in [L 2 Y(OCHPh 2 )(OCPh 2 )].…”

Section: Resultsmentioning

confidence: 99%

Organometallic Complexes of Scandium and Yttrium Supported by a Bulky Salicylaldimine Ligand

et al. 2002

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Organometallic derivatives of scandium and yttrium supported by a bulky salicylaldiminato ligand were prepared from the tris(alkyl) precursors [M(CH2SiMe2R)3(THF)2] (M = Sc, 1-Sc R ; M = Y, 1-Y R ; R = CH3, Ph) via alkane elimination. The new precursors 1-M Ph are convenient alternatives to the 1-M Me derivatives, due to their higher thermal stability and crystallinity; 1-Sc Ph has been characterized crystallographically. Reaction of these compounds with 1 equiv of protio ligand gives isolable mono(ligand) bis(alkyl) derivatives only for 1-Y; for other derivatives 1-Sc, mixtures were obtained. The products of the former reaction retain either two (2-Y Ph ) or one (3-Y Ph ) THF ligands; both of these compounds have been characterized crystallographically. In solution, both exhibit fluxional exchange between two geometric isomers which were characterized by variable-temperature NMR spectroscopy. Heating solutions of either compound leads to facile ligand redistribution. Reactions of tris(alkyls) 1 with 2 equiv of protio ligand gives the five-coordinate, THF-free bis(ligand) mono(alkyl) complexes 4-M R . These compounds are highly thermally stable, decomposing at temperatures above 140 °C via a pathway involving metalation of one of the N-aryl isopropyl methyl groups. The derivatives 4-Sc Me and 4-Y Ph have been structurally characterized, as well as the product of thermolysis of 4-Sc Me , the nonorganometallic four-coordinate complex 5-Sc. Both 4-Sc Me and 4-Y Ph react slowly but cleanly with H2. The former yields a product, 7-Sc, derived from transfer of the in situ formed scandium hydride to the aldimine carbon of one of the ligands. The yttrium product, however, is the D 2-symmetric dimeric μ-hydride complex 6-Y, characterized by spectroscopic and crystallographic methods. A survey of 6-Y’s reactivity toward deuterated solvents, d 2 -6-Y, ethylene, (trimethylsilyl)acetylene, [HB(C6F5)2]2, benzophenone, pyridine, and THF suggests that it does not dissociate into a monomeric hydride but reacts as a dimer. Nonetheless, products from the reactions of (trimethylsilyl)acetylene, [HB(C6F5)2]2, benzophenone, pyridine, and THF were isolated and characterized spectroscopically and, in the case of the product from the benzophenone reaction, crystallographically. Finally, reactions of mono(alkyls) 4-Sc Me and 4-Y Ph with a further 1 equiv of protio ligand gave nonorganometallic tris(ligand) coordination complexes, both of which were structurally and spectroscopically characterized. The scandium derivative 8-Sc contained an O-bound κ1-salicylaldiminato ligand, while for 8-Y, containing the larger Y nucleus, all three ligands were chelating in the normal κ2 bonding mode.

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Complexes of Group 3 and Lanthanide Elements

Edelmann

2007

Comprehensive Organometallic Chemistry III

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Benzophenone Adduct of Tris(cyclopentadienyl)dysprosium

Abstract: The title compound, (benzophenone-O)tris(r/5-cylopentadienyl)dysprosium, [Dy(CsHs)3(CI3HI00)], is a distorted tetrahedral coordination complex. The central dysprosium ion is r/5-bonded to three cyclopentadienyl (Cp)

Cited by 7 publications

References 7 publications

Trivalent Cerium and Praseodymium Aromatic Ketone Adducts

Trivalent Cerium and Praseodymium Aromatic Ketone Adducts

Organometallic Complexes of Scandium and Yttrium Supported by a Bulky Salicylaldimine Ligand

Complexes of Group 3 and Lanthanide Elements

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