A Ga4N8 cage structure formed by reaction of trimethylgallium with phenylhydrazine

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn4N8, Zn4N6O and Zn4N4O2 Cage Structures

“…The topology is in principle related to that of [{(MeGa)(NHNPh)} 4 ], which contains a Ga 4 N 8 cage and a dianionic ligand compensating the charge of a formally doubly charged cationic unit MeGa 2 + . [19] There is also a structural relationship to the zinc oximate [{(MeZn)-(ONCMe 2 )} 4 ] with its Zn 4 N 4 O 4 core, [20] but this has oxygen as the primary bonding atoms.…”

Novel Aluminum‐Containing Ring Systems: An Octanuclear Structural Analogue of a Calix[4]pyrrole

“…The structures were solved by direct methods, and all the nonhydrogen atoms were refined anisotropically with full-matrix least squares based on [1±4] For example, a deformation of the porphyrin skeleton in heme and photosynthetic proteins is believed to arise from environmental effects. [3,5,6] Synthetic dodecaphenylporphyrins which contain a phenyl ring at each b-pyrrole and meso position of the porphyrin macrocycle are known to adopt a nonplanar conformation. [3, 7±9] Nonplanarity of the porphyrin ring due to steric repulsion between ring substituents in dodecasubstituted porphyrins affects their optical properties.…”

“…For example, difunctional molecules such as 1,2-diaminobenzene (1,2-(NH 2 ) 2 C 6 H 4 ), salicylic acid (1-(CO 2 H)-2-(OH)C 6 H 4 ), and 1,2-diphosphanylbenzenes (1,2-(PR 2 ) 2 C 6 H 4 ; R H, Me) have been shown to react with Me 3 M (M Al, Ga) to give ring and cage structures for both aluminum and gallium; [3] other ring and cage structures have been accessed from reactions involving the use of primary or secondary amines [4] and phenylhydrazine. [5] In separate studies, gallium-mediated coupling reactions involving acetonitrile have recently been described. For example, the trimethylgallium-induced trimerization of acetonitrile, in the presence of a catalytic amount of caesium salt, was supported by the isolation and crystal structure determination of the heterocycle [Me 2 Ga{HNC(Me)} 2 C(CN)]; [6] further reaction with Me 3 Ga/MeCN gave [(Me 2 Ga) 4 (MeGa) 2 {HNC(Me)C(CN)CH(NCMe) 2 } 2 ].…”

From tert‐Butylhydrazine Adducts of AlR3 (R = Me, CMe3) to Oligonuclear AlN Cage Compounds – Evidence for a Hydrazine Twist Across an Al3 Triangle

“…In the absence of steric influences the five-membered heterocycles were calculated to be thermodynamically favorable. [13] Experiments on the controlled thermolysis of hydrazides have given access to large EN cages such as [R-E-N(H)-NRЈ] 4 (R = Me, E = Al, RЈ = Ph; [7] R = Et, E = Ga, RЈ = Ph; [7] R = Me, E = Ga, RЈ = CMe 3 ; [8] R = iPr, E = Ga, RЈ = Ph; [8] R = Me, E = Ga, RЈ = CMe 3 or Ph [3,14] ), (Me 3 CGaNH) 8 [8] and very recently the unprecedented gallium compound (GaMe) 4 -(GaMe 2 ) 4 [N(H)-NMe] 4 (N 2 ) [15] that features as a unique structural motif a completely deprotonated tetraanionic N 2 4-group stabilized by six gallium atoms. These compounds and larger cages may, under thermolysis conditions, occur as intermediate compounds between the initially formed adducts and the corresponding element nitrides.…”