Homoleptic quasilinear metal(<scp>i</scp>/<scp>ii</scp>) silylamides of Cr–Co with phenyl and allyl functions – impact of the oxidation state on secondary ligand interactions

Weller, Ruth; Ruppach, Lutz; Shlyaykher, Alena; Tambornino, Frank; Werncke, C. Gunnar

doi:10.1039/d1dt01543e

Cited by 9 publications

(10 citation statements)

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“…Building on recent examples of low-coordinate imido cobalt silylamides in higher spin-states 23,24 we report herein the trigonal iron imido complexes [Fe(NMes)L 2 ] 0,− (L = –N(Dipp)SiMe 3 ; Dipp = 2,6-diisopropyl-phenyl; Mes = 2,4,6-trimethylphenyl) in the formal oxidation states +III and +IV, which can be interconverted by oxidation/reduction. Detailed spectroscopic and computational analyses reveal the ambiguous electronic structure of both complexes.…”

Section: Introductionmentioning

confidence: 99%

Between imide, imidyl and nitrene – an imido iron complex in two oxidation states

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Between imide, imidyl and nitrene – an imido iron complex in two oxidation states

et al. 2022

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“…The aryl substituent of the silylamide ligand is oriented toward the chromium center (Cr1–N1–C Aryl 102.43(16)°). This implicates secondary Cr···C ipso interactions as in related divalent low-coordinate chromium aryl/silylamides. ,, To allow for these interactions, the two principal ligand planes are nearly orthogonal to each other (79.1(3)°). In 1b the silylamide is less distorted (Cr1–N1–C ipso 110.25(19)°; Figure , right).…”

Section: Resultsmentioning

confidence: 99%

“…This is remarkable as the linear chromium(I) complex [TerCr(PMe 3 )] (Ter = 2,6-Tripp 2 -3,5- i Pr 2 -C 6 H, Tripp = 2,4,6- i Pr 2 -C 6 H 2 ) was the very first example within this class of molecules (Figure A) . Apart from the heteroleptic [TerCr(PMe 3 )], a singular cationic (Figure B) and few anionic silylamide-based homoleptic complexes were reported since then (Figure C/D). − Fundamental insights into their reactivity remained thus scarce. The anionic chromium silylamide [Cr(N{Dipp}S i Pr 3 ) 2 ] − reported by Tilley et al (Figure C) could be methylated to form a rare three-coordinate alkyl chromium(III) complex.…”

Section: Introductionmentioning

confidence: 96%

Synthesis, Properties, and Reactivity of a Linear NHC-Based Chromium(I) Silylamide

et al. 2023

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We describe the synthesis of the linear N-heterocyclic carbene (NHC)-based chromium(I) silylamide [(IMes)Cr(N{Dipp}-Si i Pr 3 )] (IMes = 1,3-dimesityl-imidazol-2-ylidene, Dipp = 2,6-di-isopropylphenyl) via protolytic ligand displacement of the homoleptic chromium(I) silylamide [KCr(N{Dipp}Si i Pr 3 )] with the imidazolium salt IMes•HCl. This could also be extended to the bulkier NHC IDipp (IDipp = 1,3-bis(2,6-di-iso-propylphenyl)imidazol-2-ylidene). Analysis of the magnetic properties of [(IMes)Cr(N{Dipp}Si i Pr 3 )] reveals an isotropic high-spin S = 5/2 state. First reaction studies with this linear chromium(I) complex yields with CO the four-coordinate chromium dicarbonyl complex [(IMes)Cr(CO) 2 (N{Dipp}Si i Pr 3 )], with benzyl bromide oxidation to the trigonal chromium(II) bromide [(IMes)-Cr(Br)(N{Dipp}Si i Pr 3 )], and with DippN 3 the first three-coordinate chromium(III) imide ([(IMes)Cr(NDipp)(N{Dipp}Si i Pr 3 )]).

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“…While not attempted, these compounds could be purified via high temperature vacuum distillation as HL1 has been. 33 However, attempting to purify HL1 by this procedure resulted in thermal decomposition, most likely due to prolonged heating above 120 °C. Additionally, these compounds are not stable on silica, preventing purification via chromatography.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Characterization of Uranium Complexes Supported by Substituted Aryldimethylsilylanilide Ligands

Reinhart,

Studvick,

Tondreau

et al. 2024

Organometallics

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We report the synthesis and characterization of substituted aryldimethylsilyldiisopropylanilide ligands and their respective bisamido complexes of U(III), (3,5-R 2 -PhMe 2 SiNDipp) 2 UI(dioxane) x (1, R = H, x= 0; 2, R = Me, x = 0; 3, R = t Bu, x = 1). We found that the steric bulk of the 3,5-R 2 -Ph ring affects the hapticity of the U−arene interaction. In the solid-state, 1 is a U− (η 6 -arene) complex, while 2 is a bis(U−(η 1 -arene)) complex. Theoretically calculated bond orders at PBE0 and PBE0-D3 levels of theory support these hapticity assignments. The 3,5-t Bu 2 -Ph rings of 3 are too bulky to interact with U and solid-state metrical parameters initially suggested a U−(η 1 -arene) interaction with one of the Dipp rings. However, bond order calculations show that this interaction is even weaker than in the previously reported ((PhMe 2 Si) 2 N) 3 U complex, leading to the conclusion that 3 is best described as a U−(η 0 -arene) complex. Molecular orbital analyses in conjunction with electron localization methods reveal that the U−(η 6 -arene) bonding in 1 is primarily electrostatic in nature. Some charge transfer takes place from the arene π orbitals to the U 6d/5f hybrid orbitals in addition to subtle δ-back-bonding. In 2 and 3, both π and δ interactions are substantially weaker, in agreement with the differences in the U−arene coordination modes. Surprisingly, attempts to generate less sterically bulky (3,5-R 2 -PhMe 2 SiNPh) 2 UI complexes results in disproportionation to homoleptic tetraamido (3,5-R 2 -PhMe 2 SiNPh) 4 U(IV) (4, R = H; 5, R = Me) complexes.

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Homoleptic quasilinear metal(i/ii) silylamides of Cr–Co with phenyl and allyl functions – impact of the oxidation state on secondary ligand interactions

Abstract: Herein we describe the synthesis and characterization of a variety of new quasilinear metal(I/II) silylamides of the type [M(N(Dipp)SiR3)2]0,− (M = Cr − Co) with different silyl substituents (SiR3 =...

Cited by 9 publications

References 116 publications

Between imide, imidyl and nitrene – an imido iron complex in two oxidation states

Between imide, imidyl and nitrene – an imido iron complex in two oxidation states

Synthesis, Properties, and Reactivity of a Linear NHC-Based Chromium(I) Silylamide

Synthesis and Characterization of Uranium Complexes Supported by Substituted Aryldimethylsilylanilide Ligands

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