Synthesis and reactivity of bis(heptamethylindenyl) yttrium (Ind*2Y) complexes containing alkyl and hydride ligands: crystal structure of Ind*2YCl(THF)

Gavenonis, John; Tilley, T. Don

doi:10.1016/j.jorganchem.2003.11.033

Cited by 25 publications

(10 citation statements)

References 38 publications

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“…Although the 1 H NMR spectrum generated from the crystals of 2-Y / 3-Y in deuterated tetrahydrofuran (THF- d 8 ) is complicated, the resonance of the hydride ligand could be identified as a doublet centered at 7.81 ppm. The J YH = 93 Hz coupling constant is larger than, but consistent with, the J YH = 74.8, 81.7, and 82.0 Hz coupling constants reported for the terminal hydride complexes [(C 5 Me 4 SiMe 3 ) 2 YH(THF)], [(C 5 Me 5 ) 2 YH(THF)], and [(C 9 Me 7 ) 2 YH(THF)], respectively. In contrast, for μ 2 -hydride complexes, J YH coupling constants have been reported in the range of 21.3–35 Hz. − The J YH coupling constants for μ 3 -hydrides are 16.3–18 Hz, − and they are 12.5 and 15.3 Hz for μ 4 -hydrides. , A 89 Y– 1 H heteronuclear multiple quantum coherence (HMQC) experiment showed a correlation between the hydride resonance at 7.81 ppm with a 89 Y resonance at −138.0 ppm in the 89 Y NMR spectrum of 2-Y / 3-Y .…”

Section: Resultssupporting

confidence: 83%

Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C–H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

et al. 2018

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[Y(N(SiMe3)2)3] reacts with (Ad,MeArOH)3mes to form the Y3+ complex [((Ad,MeArO)3mes)Y], 1-Y. This complex reacts with potassium metal in the presence of 2.2.2-cryptand to give a cocrystallized mixture of [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Y], 2-Y, and [K(2.2.2-cryptand)][((Ad,MeArO)3mes)YH], 3-Y. The electron paramagnetic resonance spectrum of this crystalline mixture exhibits an isotropic signal at 77 K (g iso = 2.000, W iso = 1.8 mT), suggesting that 2-Y is best described as a Y3+ complex of the tris(aryloxide)mesitylene radical ((Ad,MeArO)3mes)4–. Evidence of the hydride ligand in 3-Y was obtained by 89Y–1H heteronuclear multiple quantum coherence NMR spectroscopy, and a coupling constant of J YH = 93 Hz was observed. A single crystal of 3-Y was also obtained in pure form and structurally characterized for comparison with the crystal data on the mixed component 2-Ln/3-Ln crystals. The origin of the hydride in 3-Ln is unknown, but further studies of the reduction of 1-La, previously found to form 2-La, revealed a possible source. Ligand-based C–H bond activation and loss of hydrogen can occur under reducing conditions to form a tetraanionic ligand derived from ((Ad,MeArO)3mes)3–, as observed in [K(2.2.2-cryptand)][((Ad,MeArO)3(C6Me3(CH2)2CH)La], 4-La.

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Section: Resultssupporting

confidence: 83%

Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C–H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

et al. 2018

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“…In this case, synthesis of rare examples of terminal hydride complexes was achieved by hydrogenolysis of cationic alkyl species in THF. The 1 H NMR spectrum of the yttrium complex exhibited a characteristic doublet signal for the terminal hydrido ligand with a large YH coupling constant of 1 J YH =73.4 Hz, which is comparable to those found in [(η 5 ‐C 5 Me 5 ) 2 YH(THF)] ( 1 J YH =81.7 Hz),44 [(Ind*) 2 YH(THF)] ( 1 J YH =82.0 Hz, Ind*=heptamethylindenyl),45 and [(η 5 ‐C 5 Me 4 SiMe 3 ) 2 YH(THF)] ( 1 J YH =74.8 Hz) 46. Recrystallization of these complexes from chlorobenzene permitted the isolation of dimeric species featuring two bridging hydrido ligands, which could be transformed back into their mononuclear analogues upon dissolution in THF (Scheme ).…”

Section: Cationic Rare‐earth‐metal Hydridessupporting

confidence: 65%

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

et al. 2014

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Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

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“…[18,24,[47][48][49] In an effort to generate highly active monomeric hydrido species we treated complex 11 in . Our efforts to isolate the THF adduct failed because of its low stability in solution.…”

mentioning

confidence: 99%

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

Trifonov¹,

Скворцов²,

Lyubov³

et al. 2006

Chemistry A European J

104

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The new family of Lewis base free hydrido complexes of rare‐earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] (Ln=Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single‐crystal X‐ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal‐atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol−1 atm−1 h−1, respectively).

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Synthesis and reactivity of bis(heptamethylindenyl) yttrium (Ind2Y) complexes containing alkyl and hydride ligands: crystal structure of Ind2YCl(THF)

Cited by 25 publications

References 38 publications

Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C–H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C–H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

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Synthesis and reactivity of bis(heptamethylindenyl) yttrium (Ind*2Y) complexes containing alkyl and hydride ligands: crystal structure of Ind*2YCl(THF)

Cited by 25 publications

References 38 publications

Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C–H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

Using Diamagnetic Yttrium and Lanthanum Complexes to Explore Ligand Reduction and C–H Bond Activation in a Tris(aryloxide)mesitylene Ligand System

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

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Synthesis and reactivity of bis(heptamethylindenyl) yttrium (Ind2Y) complexes containing alkyl and hydride ligands: crystal structure of Ind2YCl(THF)

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization