Synthesis of a new stable, neutral organothulium(<scp>ii</scp>) complex by reduction of a thulium(<scp>iii</scp>) precursor

Jaroschik, Florian; Nief, François; Ricard, Louis

doi:10.1039/b514818a

Cited by 52 publications

(70 citation statements)

References 19 publications

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“…Even after refluxing for several days, the starting materials were isolated from the reaction mixtures in nearly quantitative yields. The similar situation was previously described by Nief and co‐workers for the synthesis of Cp ttt 2 TmI, which could be performed in a good yield only in toluene, while the reaction in THF even after continuous heating resulted in the mixture of the product and the starting reagents …”

Section: Resultssupporting

confidence: 57%

“…The similars ituation was previously described by Nief andc o-workers for the synthesis of Cp ttt 2 TmI, which could be performed in ag ood yield only in toluene,w hilet he reaction in THF even after continuous heatingr esulted in the mixture of the product and the startingr eagents. [8] Complex 1 was also unexpectedly obtaineda sap roduct of the oxidationo f( tBu 4 Carb) 2 Sm (3)b yC uI in THF (Scheme 2) instead of (tBu 4 Carb) 2 SmI. The reaction of complex 2 with equimolar amount of CuI (THF,2 0 8 C) lead to the immediate appearanceo fadeep-blue color of the solution,w hile the quantitative precipitation of metallicC ug ave evidence for completion of oxidation.…”

Section: Resultsmentioning

confidence: 99%

“…Molecular structure of complex 5.E llipsoids are set at 30 %p robability.All hydrogen atoms, carbon atomso ftBu-groups, and carbon atoms of THF are omitted for clarity.S electedb ond distances []a nd angles[8]: Sm1-Carb centr 2.6498(8), Sm1-N12.720(2), Sm1-C12.797(2), Sm1-C6 3.029(2),S m1-C73 .068(2), Sm1-C12 2.911(2), Sm1-C29 2.667(2), Sm1-N2 2.713(2),S m1-O12 .554(2), Sm1-O22.557(2),S m1-C30 2.949(2),S m1-C35 2.983(2); C29-Sm1-N26 4.026, C29-Sm1-N1117.78(6), N1-Sm1-N21 28.73(5).Scheme5.Recations of 3 with H 2 and PhSiH 3 .…”

mentioning

confidence: 99%

“…Molecular structure of complex 6.E llipsoids are set at 30 %p robability.All hydrogen atoms, carbon atomso ftBu-groups, and carbon atoms of DME are omitted for clarity.S elected bond distances []and bond angles[8]: Sm1-Carb centr 2.6560(8), Sm1-N1 2.697(2), Sm1-C12.836(2), Sm1-C12 2.848(2), Sm1-C63 .083(2), Sm1-C73 .094(2), Sm1-N22 .414(2), Sm1-O1 2.579(2), Sm1-O22 .618(2), Sm1-Si2 3.471(2);Cp centr -Sm1-N2 141.0(2),Sm1-N2-Si21 14.19(9),Sm1-N2-Si1 118.54(9).…”

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confidence: 99%

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Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu₄Carb)₂Sm

Selikhov

Mahrova

Cherkasov

et al. 2016

Chemistry A European J

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The half-sandwich tetra-tert-butylcarbazol-9-yl iodo complex [(tBu Carb)Sm(μ-I)(THF) ] (1) was synthesized by the salt metathesis reaction of tBu CarbK and SmI (THF) in THF. Complex 1 along with metallic Cu was also isolated from the oxidation reaction of (tBu Carb) Sm by CuI. The formation of stable radical tBu Carb was detected in this non-conventional process, indicating preferential oxidation of anion tBu Carb vs. Sm . The treatment of 1 with two equivalents of dibenzo-18-crown-6 resulted in heterolytic dissociation of a η -bond Sm-tBu Carb and afforded an ionic compound [tBu carb ][SmI(crown)(THF) ] (4). Alkylation of 1 with o-NMe C H CH K (1:2 molar ratio) in THF allowed for the synthesis of half-sandwich Sm alkyl complex (tBu Carb)SmCH (o-NMe C H CH )(THF) (5) in 55 % yield. The amido complex (tBu Carb)SmN(SiMe ) (DME) (6) was obtained by the reaction of 1 with two molar equivalents of NaN(SiMe ) in THF in 89 % yield.

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Section: Resultssupporting

confidence: 57%

Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu₄Carb)₂Sm

Selikhov

Mahrova

Cherkasov

et al. 2016

Chemistry A European J

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“…The calculated data in the series of 2a – 2d might also indicate, in agreement with the previously suggested relationship of bond lengths, some covalency in the bonding character (Figure 4 ). 39 …”

Section: Results and Discussionmentioning

confidence: 99%

Open-Shell Lanthanide(II+) or -(III+) Complexes Bearing σ-Silyl and Silylene Ligands: Synthesis, Structure, and Bonding Analysis

et al. 2015

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Complexes featuring lanthanide (Ln)–Si bonds represent a highly neglected research area. Herein, we report a series of open-shell LnII+ and LnIII+ complexes bearing σ-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the LnIII+ complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dianion [(18-cr-6)KSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2K(18-cr-6)] (1) selectively afford the corresponding metallacyclopentasilane salts [Cp2Ln({Si(SiMe3)2SiMe2}2)]−[K2(18-cr-6)2Cp]+ [Ln = Tm (2a), Ho (2b), Tb (2c), Gd (2d)]. Complexes 2a–2d represent the first examples of structurally characterized Tm, Ho, Tb, and Gd complexes featuring Ln–Si bonds. Strikingly, the analogous reaction of 1 with the lighter element analogue Cp3Ce affords the acyclic product [Cp3CeSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2-Cp3Ce]2–2[K(18-cr-6)]+ (3) as the first example of a complex featuring a Ce–Si bond. In an alternative synthetic approach, the aryloxy-functionalized benzamidinato NHSi ligand Si(OC6H4-2-tBu){(NtBu)2CPh} (4a) and the alkoxy analogue Si(OtBu){(NtBu)2CPh} (4b) were reacted with Cp*2Sm(OEt2), affording, by OEt2 elimination, the corresponding silylene complexes, both featuring SmII+ centers: Cp*2Sm ← :Si(O–C6H4-2-tBu){(NtBu)2CPh} (6) and Cp*2Sm ← :Si(OtBu){(NtBu)2CPh} (5). Complexes 5 and 6 are the first four-coordinate silylene complexes of any f-block element to date. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analysis. In the series 2a–2d, a linear correlation was observed between the Ln–Si bond lengths and the covalent radii of the corresponding Ln metals. Moreover, in complexes 5 and 6, notably long Sm–Si bonds are observed, in accordance with a donor–acceptor interaction between Si and Sm [5, 3.4396(15) Å; 6, 3.3142(18) Å]. Density functional theory calculations were carried out for complexes 2a–2d, 5, and 6 to elucidate the bonding situation between the LnII+ or LnIII+ centers and Si. In particular, a decrease in the Mayer bond order (MBO) of the Ln–Si bond is observed in the series 2a–2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln–Si bond. In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) .

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Lanthanides: Divalent Organometallic Chemistry

Nicholas

Mills

2017

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This article focuses on the chemistry of Ln 2+ (Ln = lanthanide) complexes that exhibit at least one Ln–C bond. We include the group 3 elements Sc, Y, and La for completeness due to their chemical similarity, though strictly they are not part of the lanthanide series. The vast majority of complexes discussed contain one or more of the classical divalent lanthanides (Sm, Eu, or Yb) because the divalent organometallic chemistry of these elements has been known for nearly 50 years. Ln 2+ organometallic chemistry for the other lanthanides is underdeveloped since, as a result of their larger standard reduction potentials, they are more difficult to access. Therefore, this article gives a historical perspective, together with state‐of‐the‐art results from the last 20 years to show the current vibrancy of this research field. As the ligand environment is the most vital factor for the stabilization of the lanthanide +2 oxidation state, sections are divided according to the supporting ligand: substituted cyclopentadienyls (CpR, C5R5; R = H, alkyl, silyl), phospholyls (PC4R5; R = H, alkyl, silyl), alkyls, aryls, and alkynides. Common synthetic routes are outlined throughout, together with a discussion of how the stability and reactivity profiles of Ln 2+ organometallic complexes change depending on the supporting ligand environment. Divalent organolanthanide chemistry is dominated by substituted Cp ligands, thus these are discussed first. The early development of classical Ln 2+ organometallic chemistry using the Cp* (C5Me5) ligand is outlined, followed by a discussion of contemporary non‐classical divalent lanthanide CpR chemistry, which has utilized bulky alkyl and silyl substituents to stabilize Ln 2+ ions for all lanthanides save Pm. Phospholyls are covered next as they have similar electronic properties to CpR. Phospholyl ligands with bulky alkyl and silyl substituents stabilize Ln 2+ ions analogously to CpR ligands with similar steric properties, hence divalent Sm, Eu, Yb, and Tm phospholyl complexes are presented. Alkyl complexes are the next most common family of classical Ln 2+ complexes. These vary in size and complexity from monodentate silyl‐ and alkyl‐stabilized examples to multidentate bis(iminophopshorano)methanide ligands. Classical divalent lanthanide aryl complexes are less numerous than alkyls, but synthetic routes to these complexes are presented herein as these are also useful starting materials. Finally, classical divalent lanthanide alkynide chemistry, the least developed of all ligand systems discussed in this article, is covered for completeness.

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Synthesis of a new stable, neutral organothulium(ii) complex by reduction of a thulium(iii) precursor

Cited by 52 publications

References 19 publications

Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu₄Carb)₂Sm

Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu₄Carb)₂Sm

Open-Shell Lanthanide(II+) or -(III+) Complexes Bearing σ-Silyl and Silylene Ligands: Synthesis, Structure, and Bonding Analysis

Lanthanides: Divalent Organometallic Chemistry

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Synthesis of a new stable, neutral organothulium(ii) complex by reduction of a thulium(iii) precursor

Cited by 52 publications

References 19 publications

Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu4Carb)2Sm

Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu4Carb)2Sm

Open-Shell Lanthanide(II+) or -(III+) Complexes Bearing σ-Silyl and Silylene Ligands: Synthesis, Structure, and Bonding Analysis

Lanthanides: Divalent Organometallic Chemistry

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Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu₄Carb)₂Sm

Half‐Sandwich Alkyl, Amido, and Iodo Samarium(II) Complexes: Non‐Conventional Sterically Governed Oxidation of (tBu₄Carb)₂Sm