Syntheses and crystal structure of [Li4Zn(μ3,η2-ddbfo)2(μ,η2-ddbfo)3Cl(CH3CN)2]·2CH3CN, [Na4(μ,η2-ddbfo)4(CH3CN)4] and [Zn2(μ,η1-ddbfo)2Cl2(py)2] aggregates

Structural Variations within Group 1 (Li−Cs)+(2,2,6,6-Tetramethyl-1-piperidinyloxy)− Complexes Made via Metallic Reduction of the Nitroxyl Radical

“…Although both complexes 1 and 2 are tetranuclear, their structures differ markedly from one another. The central core of 2 (Figure ) consists of interpenetrating tetrahedra of Na and O TEMPO atoms resulting in the formation of a distorted cubanea motif which is commonly encountered in sodium alkoxide/aryloxide or siloxide chemistry. − Each Na atom coordinates to three anionic O TEMPO centers, and the metal’s coordination sphere is completed by complexation to a THF molecule. In contrast to 1 , there appears to be no significant M−N bonding in 2 , which may be attributed to the relatively more compact nature of the M 4 O 4 core in 2 and the fact that the metal to THF ratio in 2 is 1:1 (cf., 2:1 for 1 ).…”

Recent developments in the synthetic and structural chemistry of lithium zincates

“…3 However, more recently, this structure type has manifested itself in the non-trivial cluster (MeCN)Cl(m 3 ,Z 2 -ddbfo) 2 -(m,Z 2 -ddbfo) 3 ZnLi 4 10 (ddbfo ¼ 2,3-dihydro-2,2-dimethyl-7benzofuranoxide), which is based on an irregular array of edge-fused metallocycles in the solid state. 28 As part of a study into the interaction of 2-arsa-1,3-dionatolithium complexes with metal halides, mono-halide bridges between lithium and zinc have been noted in {As[C(O)Bu t ] 2 } 2 Zn[(m-Cl)LiÁdme] 2 11 (dme ¼ dimethoxyethane). 29 Monobridged motifs are also possible in the absence of a heteroatom, and in fact the Zn(m-C)Li unit is common in ion-bonded lithium zincate chemistry.…”

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“…79 The synthesis and crystal structure of [Li 4 Zn(m 3 ,h 2 -ddbfo) 2 (m,h 2ddbfo) 3 Cl(MeCN) 2 ] revealed tetrahedral metal centres linked by m-and m 3 -bridging aryloxides whereas [Na 4 (m 3 ,h 2 -ddbfo) 4 (MeCN) 4 ] forms centrosymmetric cubes. 80 Depending on the bulkiness of the substituents and the solvent, lithium salts of N,Obis(silyl)hydroxylamines crystallize as dimeric, trimeric or tetrameric lithium N,Nbis(silyl)hydroxylamides, e.g. [(Bu t SiMe 2 ) 2 NOLi(thf)] 2 , [(Bu t SiMe 2 ) 2 NOLi] 3 and [(Bu t SiMe 2 )(SiMe 3 )NOLi] 4 .…”