Synthesis and reactivity of rare-earth-N,N’-(diphenyl)formamidinate and rare-earth-N,N’-bis(2,4-dimethylphenyl)formamidinate complexes

Salehisaki, Mehdi; Rad, N. E.; Deacon, Glen B.; Wang, Jun; Guo, Zhifang; Junk, ‬Peter C.

doi:10.1016/j.ica.2022.120997

Cited by 7 publications

(11 citation statements)

References 57 publications

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“…Only the Lu complex 2e lost water from the single crystal composition under the drying conditions and both coordinated and lattice water was lost. Four complexes had low % C, a frequent problem with rare earth metal-organic compounds, [28][29][30][31][32][33][34] but additional % Ln analyses and TGA data leave little doubt as to the bulk composition.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Synthesis, structure, and corrosion inhibiting properties of RE^III 3-thiophenecarboxylate complexes

et al. 2022

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Section: Synthesis and Characterizationmentioning

confidence: 99%

Synthesis, structure, and corrosion inhibiting properties of RE^III 3-thiophenecarboxylate complexes

et al. 2022

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“…A small resonance at δ =4.72 ppm was detected (Figure S3), which is attributable to H 2 [13] . The identity of 3 was established by X‐ray crystallography (below), but the bulk product was somewhat impure as evident from a low carbon analysis, though this is not uncommon for lanthanoid complexes owing to ease of metal carbide formation during combustion [14] . In the 1 H NMR spectrum, satisfactory integrations could not be obtained, as the effects of paramagnetism were more evident than in the case of 1 .…”

Section: Resultsmentioning

confidence: 99%

“…[13] The identity of 3 was established by X-ray crystallography (below), but the bulk product was somewhat impure as evident from a low carbon analysis, though this is not uncommon for lanthanoid complexes owing to ease of metal carbide formation during combustion. [14] In the 1 H NMR spectrum, satisfactory integrations could not be obtained, as the effects of paramagnetism were more evident than in the case of 1. Thus, the backbone NCHN resonance was further shifted to 12.85 ppm (Figure S4), the aromatic hydrogens of Hbtz at 7.7-8.3 ppm were shifted to an AB doublet at 6.66-6.64 ppm, the CH and CH 3 resonances of DippForm were considerably broadened, as was the shifted thf resonance.…”

Section: Reactions Of [Sm(dippform) 2 (Thf) 2 ] With Trans-azobenzenementioning

confidence: 97%

Reactivity of [Sm(DippForm)₂(thf)₂] with Substrates Containing Azo Linkages

Peedika Paramban,

Guo,

Deacon

et al. 2023

Eur J Inorg Chem

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This paper explores the interaction of divalent [Sm(DippForm)2(thf)2] with substrates containing azo linkages. Treatment of [Sm(DippForm)2(thf)2] with trans‐azobenzene results in formation of mononuclear [Smlll(DippForm)2(Ph2N2)(thf)]·3THF (1) or dinuclear [Smlll(DippForm)(Ph2N2)(thf)]2·2THF (2) and [Sm(DippForm)3] depending on the reaction stoichiometry, where azobenzene has undergone either a one or two electron reduction. These reactions parallel the corresponding reactions of [Sm(C5Me5)2(thf)2], but the coordination of N2Ph2‐ in 1 differs significantly from that of {Sm(C5Me5)2(Ph2N2)(thf)}. On the other hand, the structure of 2 is similar to that of the pentamethylcyclopentadienyl analogue. The reaction of [Sm(DippForm)2(thf)2] with 1H‐1,2,3‐benzotriazole also yielded a trivalent samarium complex containing benzotriazolate (btz), [Smlll(DippForm)2(btz)(thf)]·THF (3), and suggests more utilization of 1H‐1,2,3‐benzotriazole in divalent lanthanoid reduction chemistry is possible.

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“…A comparison of the C–N bond lengths also confirms the reduced nature of the formamidinate fragment because C10–N7 falls between the typical values for C–N single and double bonds [C10–N7 1.326(14) Å ( 3-Dy ) and 1.315(5) Å ( 3-Yb ) vs single (∼1.47 Å) and double (∼1.15 Å) C–N bonds], consistent with delocalization of the N–C–N fragment in 3-Ln . The Ln–N(κ 3 -Tp) bond distances in 3-Ln are consistent with those of 1-Ln , 2-Ln , and [Ln(Tp) 2 (X)] in the literature. , The Ln–N7 bond distances in 3-Ln [Ln = Dy, 2.376(8) Å; Yb, 2.373(3) Å] are consistent with the Ln–N bond distances in related literature complexes. ,, …”

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“…5b , 6 The Ln–N7 bond distances in 3-Ln [Ln = Dy, 2.376(8) Å; Yb, 2.373(3) Å] are consistent with the Ln–N bond distances in related literature complexes. 15 , 16 , 18 …”

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Synthesis and Reactivity of Bis-tris(pyrazolyl)borate Lanthanide/Aluminum Heterobimetallic Trihydride Complexes

Chowdhury,

Murphy,

Kennedy

et al. 2024

Inorg. Chem.

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Molecular heterobimetallic hydride complexes of lanthanide (Ln) and main-group (MG) metals exhibit chemical properties unique from their monometallic counterparts and are highly reactive species, making their synthesis and isolation challenging. Herein, molecular Ln/Al heterobimetallic trihydrides [Ln(Tp) 2 (μ-H) 2 Al(H)(N″)] [2-Ln; Ln = Y, Sm, Dy, Yb; Tp = hydrotris(1-pyrazolyl)borate; N″ = N(SiMe 3 ) 2 ] have been synthesized by facile insertion of aminoalane [Me 3 N•AlH 3 ] into the Ln− N amide bonds of [Ln(Tp) 2 (N″)] (1-Ln). Thus, this is a simple synthetic strategy to access a range of Ln/Al hydrides. Reactivity studies demonstrate that 2-Ln is a heterobimetallic hydride, with evidence for the cooperative nature of 2-Ln shown by the catalytic amine−borane dehydrocoupling under ambient conditions in contrast to its monomeric counterparts. * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c00824.Data that support the findings of this study and additional references 22 (PDF)Accession Codes CCDC 2313687−2313695 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

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Synthesis and reactivity of rare-earth-N,N’-(diphenyl)formamidinate and rare-earth-N,N’-bis(2,4-dimethylphenyl)formamidinate complexes

Cited by 7 publications

References 57 publications

Synthesis, structure, and corrosion inhibiting properties of RE^III 3-thiophenecarboxylate complexes

Synthesis, structure, and corrosion inhibiting properties of RE^III 3-thiophenecarboxylate complexes

Reactivity of [Sm(DippForm)₂(thf)₂] with Substrates Containing Azo Linkages

Synthesis and Reactivity of Bis-tris(pyrazolyl)borate Lanthanide/Aluminum Heterobimetallic Trihydride Complexes

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Synthesis and reactivity of rare-earth-N,N’-(diphenyl)formamidinate and rare-earth-N,N’-bis(2,4-dimethylphenyl)formamidinate complexes

Cited by 7 publications

References 57 publications

Synthesis, structure, and corrosion inhibiting properties of REIII 3-thiophenecarboxylate complexes

Synthesis, structure, and corrosion inhibiting properties of REIII 3-thiophenecarboxylate complexes

Reactivity of [Sm(DippForm)2(thf)2] with Substrates Containing Azo Linkages

Synthesis and Reactivity of Bis-tris(pyrazolyl)borate Lanthanide/Aluminum Heterobimetallic Trihydride Complexes

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Synthesis, structure, and corrosion inhibiting properties of RE^III 3-thiophenecarboxylate complexes

Synthesis, structure, and corrosion inhibiting properties of RE^III 3-thiophenecarboxylate complexes

Reactivity of [Sm(DippForm)₂(thf)₂] with Substrates Containing Azo Linkages