The chemistry and the stereochemistry of poly(N-alkyliminoalanes)

Cesari, M.; Perego, G.; Piero, G. Del; Cucinella, S.; Cernia, E.

doi:10.1016/s0022-328x(00)89841-1

Cited by 66 publications

(27 citation statements)

References 12 publications

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“…The Al−C bond lengths (1.979(2) to 1.992(2) Å) are all within the expected range in comparison with the carbaalanes (Al−C 1.948(3)–2.212(2) Å),2 whereas the Al−N bond lengths (1.966(2) to 1.978(2) Å) are slightly longer than those in iminoalanes with the 12‐membered Al 6 N 6 core structure (e.g. Al−N 1.898(3)–1.955(3) Å in (HAlN i Pr) 6 ) 3e. The molecular symmetry is quite close to S 4 .…”

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confidence: 99%

A Polyhedral Aluminum Compound with an Al4C4N4 Framework

Zheng¹,

Stasch²,

Prust³

et al. 2001

Angew. Chem.

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Dedicated to Professor Philipp GütlichRecently the oligomeric and polyhedral compounds of aluminum containing Al À N and Al À C cores have attracted considerable interest following the preparation of a few threecoordinate iminoalanes [1] and the determination of the structures of carbaalanes. [2] Heteroatom-containing organoaluminum cage compounds [3] are potential precursors for various applications such as catalysts, reagents, and for chemical vapor deposition, [3a, 4, 5] as well as being of theoretical importance. [6] Although the formation of iminoalanes and carbaalanes is now almost understood, [1±3] compounds containing an Al n C n N n framework (n b 2) are still unknown. [7] We figured that such species should exhibit some interesting features. Herein we report the structure of the polyhedron 1 and the synthesis of the bridging compound with bulky pyrazolato ligands 2 (tBu 2 pz 3,5-di-tert-butylpyrazolato).

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confidence: 99%

A Polyhedral Aluminum Compound with an Al4C4N4 Framework

Zheng¹,

Stasch²,

Prust³

et al. 2001

Angew. Chem.

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“…The angles within the four-membered rings are very similar and are close to 90°, while the angles in the six-membered rings are smaller for N-Al-N (112.9°on average) than for Al-N-Al (126.7°), and are presumably influenced by the steric demand of the bulky CMe 3 group on Al. The hexagonal prism is a well-known structural motif for oligomeric organoaluminum imides, as is evident from reported structures such as [HAlNiPr] 6 , [22] [HAlNnPr] 6 , [23] [MeAlNPh] 6 , [24] [HAlN-(CH 2 ) 3 NMe 2 ] 6 [25] etc. Compound 4 is, however, unique in being the first example that features a structural motif with NH rather than NRЈ functionalities that may influence the reactivity of the compound, in particular with respect to further degradation.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2011

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The thermal decomposition of the hydrazine adducts R3Al←NH2–N(H)CMe3 (1a, R = CMe3; 1b, R = Me) was investigated. Compound 1a afforded the hydrazide [(Me3C)2Al–N(H)–N(H)–CMe3]2 (2) upon heating to 155 °C. Compound 2 is dimeric in the solid state with a four‐membered Al2N2 heterocycle in its molecular core. Heating of 2 to 190 °C gave the drum‐like imidoalane [Me3CAlNH]6 (4) in which the Al and N atoms occupy the vertices of a hexagonal prism. This reaction is believed to proceed via the dimeric amide [(Me3C)2Al–NH2]2 (3) that was isolated in small quantities from a mixture obtained at a slightly lower temperature. Adduct 1b, which is sterically less shielded than 1a, decomposes readily at room temperature to yield an unprecedented Al–N cage compound, [Me2Al–N(H)–N(H)CMe3]2[MeAl–N(CMe3)–NH] (5), with a norbornane‐like arrangement of three Al and four N atoms, and a hydrazinediido group in the bridging position. Heating of 5 gave, with the release of methane, the tetraaluminum compound [MeAlN(H)–NCMe3]4 (6) in which four hydrazinediide moieties are bridged by AlMe groups. Heating of 6 resulted in the gradual degradation of the N–N bonds and the formal release of 1 or 3 equiv. of nitrene, N–H, to give the unique cage compounds (MeAl)4[N(H)–NCMe3]3(NCMe3) (7) and (MeAl)4[N(H)–NCMe3](NCMe3)3 (8). The structures of compounds 6–8 may be derived from Al4N4 cubes in which a number of edges (four, three or one) are bridged by nitrogen atoms of hydrazinediido groups.

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“…15.305 (3) 15.216 (3) 13.447(2) c (Å ) 20.996 (4) 21.059 (4) 17.086 (3) a (8) 82.71 (3) 82.75 (3) 908 b (8) 75.80 (3) 75.89 (3) 91.094 (14) g (8) 75.50 (3) 75.38 (3) Table 2 Selected bond distances (Å ) and bond angles (8) [7] 1.917-1.932 1.923 (4-C 6 H 4 FNAlMe) 4 [24] 1.922-1.951 1.934 (PhNAlPh) 4 [25] 1.900-1.930 1.914 (n-PrNAlH) 6 [8] 1.884-1.972 1.913 (p-CF 3 C 6 H 4 CH 2 NAlH) 6 [22] 1.880-1.980 1.919 (PhCH 2 NAlH) 6 [22] 1.886-1.974 1.918 (PhNAlMe) 6 [26] 1. Compound 2 was prepared from 1 using Me 3 SnF as a fluorinating agent.…”

Section: Resultsmentioning

confidence: 99%

“…Al-N rings and clusters have been reviewed recently [5]. There are a few reports on aluminum imides (RNAlH) n (n ¼ 4, 6 or 8) [6][7][8] containing hydridic hydrogens bound to aluminum atoms. Compounds of composition (RNAlH) 7 with Al-H bonds are not known.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structural characterization of an unusual heptameric aluminum imide and the surface fluorination products of the Al7N7 and Al4C4N4 cores

Peng

Rong

Vidović

et al. 2004

Journal of Fluorine Chemistry

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The chemistry and the stereochemistry of poly(N-alkyliminoalanes)

Cited by 66 publications

References 12 publications

A Polyhedral Aluminum Compound with an Al4C4N4 Framework

A Polyhedral Aluminum Compound with an Al4C4N4 Framework

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

Synthesis and structural characterization of an unusual heptameric aluminum imide and the surface fluorination products of the Al7N7 and Al4C4N4 cores

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The chemistry and the stereochemistry of poly(N-alkyliminoalanes)

Cited by 66 publications

References 12 publications

A Polyhedral Aluminum Compound with an Al4C4N4 Framework

A Polyhedral Aluminum Compound with an Al4C4N4 Framework

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

Synthesis and structural characterization of an unusual heptameric aluminum imide and the surface fluorination products of the Al7N7 and Al4C4N4 cores

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