Syntheses of {(MeC5H4)2Ln[OC̄H2]}2 (Ln=Yb, Y, Er) and the X-ray crystal structure of the ytterbium complex

Wang, Yaorong; Shen, Qi; Ling, Wu; Zhang, Yue; Sun, Jing

doi:10.1016/s0022-328x(01)00687-8

Cited by 14 publications

(4 citation statements)

References 30 publications

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“…There are several lanthanide complexes containing nonmultipodal amidate ligands (only one N,O group per ligand) reported in the literature, many containing ancillary cyclopentadienyl groups as supporting coligands, − ,,− ,, for example, the dinuclear complex, [Cp′ 2 SmOC( n Bu)NPh] 2 . However, more relevant non-organolanthanide examples include the Y dinuclear tris(amidate) complex, [Y( t Bu[O,N](CH 3 ) 2 Ph) 3 ] 2 , reported by Schafer and co-workers .…”

Section: Results and Discussionmentioning

confidence: 99%

“…Similar to complexes 1 – 3 , the solid-state molecular structures of 4 and 5 feature a tripodal tris(amidate) ligand with a combination of κ 2 -amidate, μ-O:κ 2 -amidate, and μ-O-amidate ligation modes not observed before with this particular scaffold and the transition metals. Further, the isolation and structural characterization of 4 and 5 demonstrate how a tripodal amidate ligand platform can support unprecedented tetranuclear cluster formation with the lanthanides, that are not formed with non-multipodal amidate ligands. − The absence of a coordinating solvent does not overcome the preference of large Ln(III) ions for higher coordination numbers, and it appears that despite the steric bulk of the tripodal amidate ligands mononuclear complexes are not accessible. In fact, and unpredictably, novel tetranuclear cores are formed instead in 4 and 5 containing two types of Ln(III) coordination environments with different coordination numbers (seven and eight).…”

Section: Results and Discussionmentioning

confidence: 99%

“…Lastly, the average Nd− N bond length (2.56(1) Å) is equivalent to the average Ln−N bond distances observed in 1•C 6 H 14 and 2•C 6 H 14 and is comparable to other reported Nd−N bonding interactions. 45,52,53 There are several lanthanide complexes containing nonmultipodal amidate ligands (only one N,O group per ligand) reported in the literature, many containing ancillary cyclopentadienyl groups as supporting coligands, [21][22][23][24]26,[28][29][30]54,55 for example, the dinuclear complex, [Cp′ 2 SmOC( n Bu)NPh] 2 . 29 However, more relevant non-organolanthanide examples include the Y dinuclear tris(amidate…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…One aspect is to understand trends and changes in speciation and bonding due to the relevance that such knowledge can play in controlling and manipulating f-element behavior in various separation processes. − Rather than designing separation relevant ligands directly, one approach is to define the baseline chemical reactivity, complex structures, and bonding properties of the f-elements with different functional groups or donor types, such that should those chemical functionalities be incorporated into a separation agent or any process in the future then an understanding of the chemical interactions between metal and ligand will already exist. − Mixed N,O donor ligands have attracted recent attention due to their interesting bonding properties with the f-elements. − In this contribution, we focus on exploring the chemistry of several early lanthanide ions in the trivalent oxidation state with mixed N,O donor ligands. Surprisingly, although there are several examples of lanthanide complexes with simple amidate ligands, − the chemistry of the 4f ions with more complex amidate scaffolds has not been explored. We chose to study the tripodal ligand, [N( o -PhNC(O)R) 3 ] 3– (R = alky, aryl), which features an acyl substituted amidate moiety capable of wide synthetic modification and varied coordination chemistry (Chart ).…”

Section: Introductionmentioning

confidence: 99%

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Lanthanide(III) Di- and Tetra-Nuclear Complexes Supported by a Chelating Tripodal Tris(Amidate) Ligand

Brown¹,

Jones²,

Gaunt³

et al. 2015

Inorg. Chem.

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Syntheses, structural, and spectroscopic characterization of multinuclear tris(amidate) lanthanide complexes is described. Addition of K3[N(o-PhNC(O)(t)Bu)3] to LnX3 (LnX3 = LaBr3, CeI3, and NdCl3) in N,N-dimethylformamide (DMF) results in the generation of dinuclear complexes, [Ln(N(o-PhNC(O)(t)Bu)3)(DMF)]2(μ-DMF) (Ln = La (1), Ce (2), Nd(3)), in good yields. Syntheses of tetranuclear complexes, [Ln(N(o-PhNC(O)(t)Bu)3)]4 (Ln = Ce (4), Nd(5)), resulted from protonolysis of Ln[N(SiMe3)2]3 (Ln = Ce, Nd) with N(o-PhNCH(O)(t)Bu)3. In the solid-state, complexes 1-5 exhibit coordination modes of the tripodal tris(amidate) ligand that are unique to the 4f elements and have not been previously observed in transition metal systems.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Lanthanide(III) Di- and Tetra-Nuclear Complexes Supported by a Chelating Tripodal Tris(Amidate) Ligand

Brown¹,

Jones²,

Gaunt³

et al. 2015

Inorg. Chem.

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A single active site metal center of neodymocene chloride for the ring‐opening polymerization of ε‐caprolactone

Hou

Chen

Yan

et al. 2011

J of Applied Polymer Sci

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A germyl‐bridged lanthanocene chloride, Me2Ge(tBu‐C5H3)2LnCl (Ln = Nd; (Cat‐Nd), was prepared and successfully used as single catalyst to initiate the ring‐opening polymerization of ε‐caprolactone (ε‐CL) for the first time. Under mild conditions (60°C,[ε‐CL]/[Ln] = 200, 4 h), Cat‐Nd efficiently catalyzes the polymerization of ε‐CL, giving poly(ε‐caprolactone) (PCL) with high molecular weight (MW) (>2.5 × 104) in high yield (>95%). The effects of molar ratio of [ε‐CL]/Cat‐Nd, polymerization temperature and time, as well as solvent were determined in detail. When the polymerization is carried out in bulk or in petroleum ether, it gives PCL with higher MW and perfect conversion (100%). The higher catalytic activity of this neodymocene chloride could be ascribed to the bigger atom in the bridge of bridged ring ligands. Some activators, such as NaBPh4, KBH4, AlEt3, and Al(i‐Bu)3, can promote the polymerization of ε‐CL by Cat‐Nd, which leads to an increase both in the polymerization conversion and in the MW of PCL. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 1212–1217, 2012

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Reactivity of Lanthanocene Amide Complexes toward Ketenes: Unprecedented Organolanthanide‐Induced Conjugate Electrophilic Addition of Ketenes to Arenes

Liu

Zhang

Zhu

et al. 2006

Chemistry A European J

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This paper presents some unusual types of reactions of lanthanocene amide complexes with ketenes, and demonstrates that these reactions are dependent on the nature of amide ligands and ketenes as well as the stoichiometric ratio under the conditions involved. The reaction of [{Cp(2)LnNiPr(2)}(2)] with four equivalents of Ph(2)CCO in toluene affords the unexpected enolization dearomatization products [Cp(2)Ln(OC{2,5-C(6)H(5)(==CPhCONiPr(2)-4)}==CPh(2))] (Ln = Yb (1 a), Er (1 b)) in good yields, representing an unprecedented conjugate electrophilic addition to a non-coordinated benzenoid nucleus. Treatment of [{Cp(2)LnNiPr(2)}(2)] with four equivalents of PhEtCCO under the same conditions gives the unexpected enolization dearomatization/rearomatization products [{Cp(2)Ln(OC{C(6)H(4)(p-CHEtCONiPr(2))}==CEtPh)}(2)] (Ln = Yb (2 a), Er (2 b), Dy (2 c)). However, reaction of [{Cp(2)YbNiPr(2)}(2)] with PhEtCCO in THF forms only the mono-insertion product [Cp(2)Yb{OC(NiPr(2))==CEtPh}](THF) (3). Hydrolysis of 2 afforded aryl ketone PhEtCHCOC(6)H(4)(p-CHEtCONiPr(2)) (4) and the overall formation of aryl ketone 4 provides an alternative route to the acylation of aromatic compounds. Moreover, reaction of [{Cp(2)LnNHPh}(2)] with excess of PhEtCCO or Ph(2)CCO in toluene affords only the products from a formal insertion of the C==C bond of the ketene into the N--H bond, [(Cp(2)Ln{OC(CHEtPh)NPh})(2)] (Ln = Yb (5 a), Y (5 b)) or [(Cp(2)Er{OC(CHPh(2))NPh})(2)] (6), respectively, indicating that an isomerization involving a 1,3-hydrogen shift occurs more easily than the conjugate electrophilic addition reaction, along with the initial amide attack on the ketene carbonyl carbon. [{Cp(2)ErNHEt}(2)] reacts with an excess of PhEtCCO to give [(Cp(2)Er{PhEtCHCON(Et)COCEtPh})(2)] (7), revealing another unique pattern of double-insertion of ketenes into the metal-ligand bond without bond formation between two ketene molecules. All complexes were characterized by elemental analysis and by their spectroscopic properties. The structures of complexes 1 b, 2 a, 2 b, 5 a, 5 b, 6, and 7 were also determined through X-ray single-crystal diffraction analysis.

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Syntheses of {(MeC5H4)2Ln[OC̄H2]}2 (Ln=Yb, Y, Er) and the X-ray crystal structure of the ytterbium complex

Cited by 14 publications

References 30 publications

Lanthanide(III) Di- and Tetra-Nuclear Complexes Supported by a Chelating Tripodal Tris(Amidate) Ligand

Lanthanide(III) Di- and Tetra-Nuclear Complexes Supported by a Chelating Tripodal Tris(Amidate) Ligand

A single active site metal center of neodymocene chloride for the ring‐opening polymerization of ε‐caprolactone

Reactivity of Lanthanocene Amide Complexes toward Ketenes: Unprecedented Organolanthanide‐Induced Conjugate Electrophilic Addition of Ketenes to Arenes

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