Dimeric complexes of lithium and sodium forming a tetrametallacyclobuta[1,2:1,4:2,3:3,4]tetracyclopentane structure

Abstract

The reaction of 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrole (DIP 2 -pyr)H with nBuLi and NaH resulted in the dimeric lithium and sodium compounds [(DIP 2 -pyr)M] 2 (M = Li, Na). In the solid-state both compounds exhibit diamond-shaped M 2 N 2 cores, in which the metal atoms are tetra-coordinated. The structures consist of four five membered rings forming a tetrametallacyclobuta[1,2:1,4:2,3:3,4]tetracyclopentane structure for each compound.

Alkali Blues: Blue‐Emissive Alkali Metal Pyrrolates

“…The centrosymmetric arrangement of the dimeric core [Li( t Bu L)] 2 is similar to the few reported structures of alkali metal‐pyrrolate complexes (Scheme ) and to the solid‐state structure of the parent ligand H t Bu L, which crystallizes as a centrosymmetric hydrogen‐bridged dimer (H t Bu L) 2 (Scheme ) . These centrosymmetric dimers, [Li( t Bu L)] 2 and (H t Bu L) 2 , differ from the C 2 ‐symmetric copper(I) dimer [Cu( t Bu L)] 2 (Scheme ) .…”

“…[53] The NaÀNa nd NaÀCd istances in [2] n agree well with those reported for similar [(NaL) 2 ] n oligomers (Scheme 1). [31,33,34,52] The aryl torsion angles of 2 in the solids tate are closer to ap lanar orientation with C5-N2-C6-C7 = 9.0(7)8 and C20-N4-C21-C22 = 13.6(11)8 compared with the lithium 2-iminopyrrolates. The Na1ÀNa2 distances are 3.471(4) and 3.525(4) .…”

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

“…[(DIP 2 -pyr)Li 2 ]) resulting from the de-protonation (via n-BuLi) of 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrole (DIP 2 -pyrH) [126]. Analogous reactions of this precursor with NaH yield the Na dimer [(DIP 2 -pyr)Na 2 ]) which possesses a related but not isostructural motif to that of the Li complex [126].…”

New Development in Rare Earth Metal Complexes Containing Anionic Bis(imino)pyrrolyl and Bis(phosphanyl)amide Ligands

“…The solid state structures of complexes 6 and 7 were established by single crystal Xray diffraction and showed a dimeric structure, in which two (DIP 2 pyr) -ligands are 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 6 bridged by two metal atoms, forming a diamond-shaped M 2 N 2 core [11]. This structural motif is very rare in lithium chemistry and unknown for sodium compounds [5,[12][13][14].…”