Divalent Ytterbium Iodide Supported by β‐Diketiminato Based Tridentate Ligand: Synthesis, Structure and Small Molecule Activation^†

Abstract

Summary of main observation and conclusion Divalent ytterbium iodide [LYb(μ‐I)(THF)]2 (1; L = [MeC(NDIPP)CHC(Me)NCH2CH2NMe2]−, DIPP = 2,6‐(iPr)2C6H3) was synthesized and its reactivity was studied. Complex 1 was synthesized by salt metathesis of YbI2(THF)2 with the potassium salt of ligand (KL) in high yield. In the reactions with trimethylsilyl azide, azobenzene, sulfur and diphenyl disulfide, complex 1 acts as a 2e reductant. In the reaction with CO2, the central carbon atom of β‐diketiminato backbone in 1 nucleophilically attacks the CO2 molecule to give a divalent ytterbium carboxylate.

Azobenzenyl Calcium Complex: Synthesis and Reactivity Studies of a Ca(I) Synthon

“…12 The molecular structure of 6 exhibits a centro-symmetric dimer (Figure 5). The N(2)−Si(1) bond distance (1.7261 (19) Å) is consistent with the previous N−Si literature values (1.725(2)−1.732(2) Å), while it is obviously shorter than the C−Si bond distances (1.81−1.84 Å). 13 The resonance form Ca−N(SiMe 3 )�N�C, where N( 2) is a neutral atom and C(1) has an anionic character, may be involved.…”

“…The molecular structure of 8 shows a centro-symmetric dimer (Figure 8). The Ca(1)−N(1) length (2.414(3) Å) is close to that of the previously characterized azido calcium complex 5 (Ca(1)−N(1) 2.3928 (19), Ca(1)−N(3) 2.4283(19) Å), but is slightly longer than that of 6 (Ca(1)− N(2) (2.3714(17) Å) and (DIPP-nacnac)Ca[N(SiMe 3 ) 2 ] (2.3174(19) Å). 15 The different Ca−O distances are observed in complex 8: the Ca(1)−O(6) bond length of 2.390(2) Å is close to the Ca(1)−O THF coordination bond lengths (range 2.373(2)−2.438(2) Å), but longer than the Ca(1 24 and L 2 Ca (L = a NNO-tridentate ketiminate ligand, 2.2460( 18) Å) 25 but shorter than that found in the complex [Ca(salen-(Bu t ))(HOEt) 2 (THF)] (the average Ca−O(aryloxide) bond length is 2.30 Å).…”

“…Nucleophilic reactions between β-diketiminate γ-carbon and the small molecule compounds including NO, SCNPh, OCCPh 2 , O 2 , CO 2 , CS 2 , nitriles, and diazoacetate have been well documented. 19 To the best of our knowledge, this is the first radical-induced reaction of CS 2 with β-diketiminate ligand.…”

Synthesis of Benzoxazine Functionalized Amine‐Bridged Bis(phenolato) Rare Earth Complexes and Their Application in Ring‐Opening Polymerization of rac‐Lactide

“…The bond lengths of Yb—N of complex 6 (2.463(4)—2.534(4) Å) are longer than that of the reported one (2.118(5)—2.421(5) Å). [ 38 ] Bond lengths of Yb—O range from 2.127(3) to 2.099(3) Å in complex 6 , which fall in similar ranges to reported values, [ 39 ] and are comparable to those of the La—O bond lengths when the difference in the ionic radii is considered. [ 40 ]…”

Structural Diversity and Multielectron Reduction Reactivity of Samarium(II) Iodido-β-diketiminate Complexes Dependent on Tetrahydrofuran Content

“…The exception is trinuclear donor-free cationic complexes [Gd 3 ( R Nacnac) 3 Cl 5 ] + (R = 2,6-dimethyl- or 2,6-diethylphenyl) obtained as the result of full desolvation of [Gd­( R Nacnac)­Cl 2 (thf) 2 ] by the action of Al i Bu 3 . Among divalent lanthanides, four binuclear β-diketiminato complexes of ytterbium − and one of samarium of the type [Ln II L­(thf) n (μ-I)] 2 (L = β-diketiminate; n = 0, 1) are known. All of them are dimeric with two Ln 2+ cations bridged by two μ-I – anions.…”