Surprising reactivity of the unsymmetrically substituted amidinate anion [MeC(NEt)(NtBu)]−

Schmielau, Andrea; Hrib, Cristian G.; Lorenz, Volker; Hilfert, Liane; Zörner, Florian; Busse, Sabine; Edelmann, Frank T.

doi:10.1016/j.jorganchem.2015.05.061

Cited by 3 publications

(8 citation statements)

References 42 publications

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“…The significance of the latter is reflected by the elongation of the other Li–N bonds going from 3‐oP (203.2(5)–215.4(5) pm) to 3‐oF (210(1)–219(1) pm). The modification 3‐oF is isotypic with the previously reported crystal structure of the analog praseodymium complex Li(THF)[Pr(L) 4 ] …”

Section: Resultssupporting

confidence: 64%

“…Chemical formula C 28 7pm, which is within the range of La-N distances observed for other octa-coordinate lanthanum complexes with nitrogen ligands (Figure 1). [31] Depending on the crystallization conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li.…”

Section: -Op 3-ofsupporting

confidence: 78%

“…Clean formation of 1 was observed when the reaction was carried out in Et 2 O/THF mixtures while the same preparations on pure diethyl ether or DME (= 1,2‐dimethoxyethane) resulted in formation of unexpected hepta‐ and octanuclear lithium amidinate clusters. Treatment of anhydrous praseodymium(III) chloride with in situ‐prepared 1 in Et 2 O/THF afforded green Li(THF)[Pr(L) 4 ] as the first tetrakis(amidinato)lanthanide(III) complex in 55 % isolated yield . We now report an extension of this chemistry to other rare‐earth metals and the structural differences of the resulting amidinate complexes depending on the ionic radii of the central metals.…”

Section: Introductionmentioning

confidence: 88%

“…. [28] The central holmium atom [32] and in the guanidinate (3)-239.6(3) pm]. [30] The range of Ho-N distances usually observed in hexa-coordinate complexes is 230-260 pm.…”

Section: -Op 3-ofmentioning

confidence: 99%

“…Treatment of anhydrous praseodymium(III) chloride with in situ-prepared 1 in Et 2 O/ THF afforded green Li(THF)[Pr(L) 4 ] as the first tetrakis(amidinato)lanthanide(III) complex in 55 % isolated yield. [28] We now report an extension of this chemistry to other rare-earth metals and the structural differences of the resulting amidinate complexes depending on the ionic radii of the central metals.…”

Section: Introductionmentioning

confidence: 99%

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New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

Harmgarth

Liebing

Hilfert

et al. 2019

Zeitschrift anorg allge chemie

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New homoleptic complexes of selected rare-earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(NtBu)] -[= (L) -] were synthesized and fully characterized. Treatment of in situ-prepared Li(L) (1) with anhydrous lanthanide(III) chlorides, LnCl 3 (Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La 3+ formed the octa-coordinate DME solvate La(L) 3 (DME) (2). Using Ce 3+ , the octa-coordinate "ate" complex Li(THF)[Ce(L) 4 ] (3) was formed. Depending on the crystallization 1101 conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li. In the case of the smaller Sc 3+ and Ho 3+ ions, six-coordinate homoleptic Sc(L) 3 (4) and Ho(L) 3 (5) were isolated. The title compounds were fully characterized by spectroscopic and analytical methods as well as single-crystal X-ray diffraction. With Ln = La and Ce, several by-products incorporating lithium, chlorine and/or oxygen were also isolated and structurally characterized.

show abstract

Section: Resultssupporting

confidence: 64%

Section: -Op 3-ofsupporting

confidence: 78%

Section: Introductionmentioning

confidence: 88%

“…. [28] The central holmium atom [32] and in the guanidinate (3)-239.6(3) pm]. [30] The range of Ho-N distances usually observed in hexa-coordinate complexes is 230-260 pm.…”

Section: -Op 3-ofmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

Harmgarth

Liebing

Hilfert

et al. 2019

Zeitschrift anorg allge chemie

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Structure of non-symmetric lithium amidinate complexes prepared by addition of lithium amides to various nitriles

Novotný

Růžičková

Růžička

2017

Journal of Organometallic Chemistry

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Zirconium Permethylpentalene Amidinate Complexes: Characterization, Bonding, and Olefin Polymerization Catalysis

et al. 2022

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The synthesis and characterization of new zirconium permethylpentalene (form)amidinate complexes are described: Pn*Zr{N(Dipp)2CH}Cl (1), Pn* = η8-C8Me6 and Dipp = 2,6- i Pr-C6H3; [Pn*Zr{N(p-tol)2CH}Cl]2 (2), p-tol = 4-Me-C6H4; [Pn*Zr{N( i Pr)2CMe}Cl]2 (3); Pn*Zr{N( i Pr)2CPh}Cl (4); Pn*Zr{N(4-Me-C6H4)2CH}2 (5); [Pn*Zr{N( i Pr)2CCH2}]2 (6); and Pn*Zr{N( i Pr)2CPh}(O-2,6,-Me-C6H3) (7). The monohalide derivatives 1–4 demonstrate considerable structural diversity as the nature of the (form)amidinate-supporting ligand is changed. While complexes with acidic backbone protons proved susceptible to deprotonation using mild bases, those without underwent straightforward salt metathesis reactions with alkali metal salts, leading to complexes [Pn*Zr{N( i Pr)2CCH2}]2 (6) and Pn*Zr{N( i Pr)2CPh}(O-2,6-Me-C6H3) (7). Preliminary slurry-phase ethylene polymerization studies are also reported using complexes 2, 4, 5, and 7 to gain a direct comparison to the highly active, yet electronically saturated, Pn*Zr(CpR)Cl catalyst family.

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Surprising reactivity of the unsymmetrically substituted amidinate anion [MeC(NEt)(NtBu)]−

Cited by 3 publications

References 42 publications

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

Structure of non-symmetric lithium amidinate complexes prepared by addition of lithium amides to various nitriles

Zirconium Permethylpentalene Amidinate Complexes: Characterization, Bonding, and Olefin Polymerization Catalysis

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Surprising reactivity of the unsymmetrically substituted amidinate anion [MeC(NEt)(NtBu)]−

Cited by 3 publications

References 42 publications

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]–

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]–

Structure of non-symmetric lithium amidinate complexes prepared by addition of lithium amides to various nitriles

Zirconium Permethylpentalene Amidinate Complexes: Characterization, Bonding, and Olefin Polymerization Catalysis

Contact Info

Product

Resources

About

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–