Three-co-ordination in lanthanide chemistry: tris[bis(trimethylsilyl)amido]lanthanide(III) compounds

Abstract

The new compounds M[N(SiMe,),], (M = La, Pr, Sm, Eu, Gd, Lu) have been isolated and shown to be the first examples of 3-co-ordinated lanthanides.

Europium bis(dimethylsilyl)amides including mixed-valent Eu3[N(SiHMe2)2]6[μ-N(SiHMe2)2]2

“…5 Moreover, bis(dimethylsilyl)amide complexes have been frequently applied in surface organometallic chemistry (SOMC) due to the occurrence of mild surface-promoted amine elimination reactions and the presence of the Si-H moiety as a useful spectroscopic probe. 5 Moreover, bis(dimethylsilyl)amide complexes have been frequently applied in surface organometallic chemistry (SOMC) due to the occurrence of mild surface-promoted amine elimination reactions and the presence of the Si-H moiety as a useful spectroscopic probe.…”

“…6,7 We also described the synthesis of divalent Sm{[μ-N(SiHMe 2 ) 2 ] 2 Sm-[N(SiHMe 2 ) 2 ](THF)} 2 8 and, more recently, tetravalent Ce-[N(SiHMe 2 ) 2 ] 4 9 to be exploited as precursors in protonolysis reactions. 5 Trans(silyl)amination reactions exploit the different pK a values of (silyl)amines. Based on the fact that donor-and ate-complex-free trivalent "Ln[N(SiHMe 2 ) 2 ] 3 " are not accessible by simple salt metathesis reactions, alternative protocols had to be explored.…”

“…Molecular structure of Eu II {[μ-N(SiHMe 2 ) 2 ]Eu III [N(SiHMe 2 ) 2 ] 3 } 2(5). Heavy atoms are represented by atomic displacement ellipsoids at the 50% level; hydrogen atoms, except those attached to silicon, are omitted for clarity.…”

Electronic Structure of Organometallic Complexes of f Elements. Are Molecular Orbital Calculations a Useful Tool for Spectroscopists?

“…The most well-known representatives of σ complexes are the ψ-trigonal pyramidal Ln[HC(SiΜ4e3)2]3 compounds 45]. Both spectroscopists and theorists consider the isostructural and isoelectronic Ln[Ν(SiMe3)2]3 complexes [46] as ideal model compounds for these methanides [47]. The amides crystallize as needles, and the trigonal principal axes of the two molecules per unit cell are aligned along the needle axis of the single crystal [48].…”

Elevated‐Temperature Metathesis Syntheses of Structurally Novel Alkali‐Metal Tetrakis(3,5‐di‐tert‐butylpyrazolato)lanthanoidate(III) Complexes: Toluene‐Coordinated Discrete Bimetallic Complexes and Supramolecular Chains

“…Use of bulky ligands has enabled the formation of homoleptic divalent and trivalent mononuclear rare-earth organometallic compounds, [1±4] organoamides, [2, 4±7] and organooxometallics, [2, 7±9] [Ln(L) n ] (L= alkyl or aryl, NR 2 , or OR; n = 2 or 3), for example, [Ln{N(SiMe 3 ) 2 } 3 ], [10] [Ln(OC 6 H 2 -2,6-tBu 2 -4-Me) 3 ] [11] and [Ln{C(SiMe 3 ) 3 } 2 ], [12] even though the large size of Ln 3 + favors heteroleptic complexes [Ln(L) n (L') m ] (L' = neutral donor, usually a polar solvent).…”