Cyclopentanolates of Aluminum Hydride/Aluminum Chloride forming Aluminum‐Oxygen‐Hetero‐Cages and Mixed Coordination Oligomers

Ali, Awadelkadereem A.; Hüch, Volker; Aktas, Cenk; Veith, Michael

doi:10.1002/zaac.201600217

Cited by 5 publications

(5 citation statements)

References 21 publications

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“…The combination of alcohols (or thiols) with “AlH 3 ” sources or [AlH 4 ] − yields neutral or anionic O-donor substituted aluminum hydrides, respectively. Along these lines, a number of new aluminum hydrides supported by alkoxy, aryloxy, siloxy and thiolate substituents have been reported. − A notable exception exhibiting a unique molecular structure was reported by Roesky in 2004 . Rather than using an organic alcohol, the aluminum hydroxide [( Dipp Nacnac)Al(Me)OH] was combined with two equivalents of Me 3 N·AlH 3 , yielding the molecular aluminoxane [{( Dipp Nacnac)Al(Me)O} 2 (AlH 2 ) 2 ] ( 572 ) (eq 67 ); the corresponding dihydrido-gallium analogue 573 was also prepared. …”

Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

Molecular Main Group Metal Hydrides

et al. 2021

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This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12−16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

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Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

Molecular Main Group Metal Hydrides

et al. 2021

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“…Both, cation and anion show a disorder: in the cation the single chlorine bonded to aluminum is distributed over the six aluminum atoms incorporated in the molecular cages in exchange with hydrogen whereas in the anion the ammonium proton is distributed over the two nitrogen atoms. The hydride/chloride disorder in crystals is a phenomenon, which seems to occur quite frequently, as we have found it recently also for alkoxi‐alanes, which have simultaneously hydride and chloride ligands in the same molecule . In the case of the ring species there is structural evidence that [( t Bu–N)( t Bu–NH)(AlCl 2 ) 2 ] – is an anion as the neutral [( t Bu–NH) 2 (AlCl 2 ) 2 ] has been determined by X‐ray structure analysis independently .…”

Section: Resultsmentioning

confidence: 91%

Aluminum/Nitrogen Cycles and an Open Cage with Al–H and N–H Functions

Veith

Walgenbach

Hüch

et al. 2017

Zeitschrift anorg allge chemie

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The cyclic tert‐butyl‐amino alane dimer [tBu–N(H)AlH2]2 (1) was obtained from reaction between alane with tert‐butylamine and its boranate derivative [tBu–N(H)–Al(BH4)2)]2 (2) subsequently from 1 by hydride/chloride exchange using PbCl2 followed by reaction with LiBH4. Both compounds form four‐membered Al2N2 cycles with typical Al–N bond lengths of 1.940(5) Å (1) and 1.945(5) Å (2) as found from X‐ray diffraction analysis. The tert‐butyl substituents at the nitrogen atoms may be situated at the same side of the ring (cis) or at opposite sides (trans). For compound 1 both isomers are present in solution, showing particular temperature dependent NMR shifts. In the solid both compounds 1 and 2 adopt the trans arrangement. When 1 is reacted with PbCl2 in half of the molarity ratio used for 2, surprisingly the novel compound 3, a zwitterion, can be obtained: [(tBu–N)(Al–H)3(tBu–N(H))3Cl((H)N–tBu)3(Al–H)2(Al–Cl)(N–tBu)]+[(tBu–N)(tBu–N(H))(AlCl2)2]–. X‐ray structure analysis reveals that the anion is made of a tert‐butyl amino aluminum dichloride dimer (central Al2N2 ring) with one of the two nitrogen atoms being deprotonated. The cationic counterpart consists of three entities: (i) There is a first seco‐norcubane like Al3N4 basket with tert‐butyl groups at the nitrogen atoms, two hydride and one chloride ligand at the aluminum atoms and three hydrogen atoms on the open side of the basket, all pointing in the same direction; (ii) There is a second similar Al3N4 basket with the same substituent pattern except that all aluminum atoms have exclusively hydrogen ligands; (iii) Both baskets coordinate a central chloride through the six protons at the open nitrogen face of the baskets in such a way that the chloride lies in the center of a H6 trigonal anti‐prism [mean H–Cl–H = 56.1(9)°]. As each of the open cages has a positive charge the overall charge by combination with the chloride adds to +1. The structure of the cationic part of 3 is unprecedented in AlN polycycles.

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Section: Resultsmentioning

confidence: 99%

“…The gallium compound 1 , with respect to its composition, is very similar to (HAl) 5 (O‐C 5 H 9 ) 8 O, which has aluminum in the place of gallium and cyclopentanolate in the place of isopropylate groups . Structurally, they are different as the oxygen atom in (HAl) 5 (O–C 5 H 9 ) 8 O is five‐coordinate (the Al 5 subunit forms an almost ideal quadratic pyramid (including the central oxygen atom the τ 5 value is 0.01), whereas it is three‐coordinate in 1 . In a simplified picture (not considering the different ionic parts in the Al‐O, respectively Ga–O bonds) the atomic and ionic radii of aluminum (1.43, 0.39 Å) are shorter than those of gallium (1.53, 0.47 Å) , which could explain that the mean Al–O(R) distances in (HAl) 5 (O–C 5 H 9 ) 8 O with 1.85(8) Å are in general smaller than those in (HGa) 5 (O i Pr) 8 O ( 1 ) with 1.99(8) Å.…”

Section: Resultsmentioning

confidence: 99%

Gallium and Indium Alkoxides with Hydride, Cyclopentadienediide and Copper(I) tert‐Butoxide as further Components

Veith

Summa

Annel

et al. 2019

Zeitschrift anorg allge chemie

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Gallium hydride stabilized by the base quinonuclidine reacts with acetone under addition of the Ga‐H function to the carbon–oxygen double bond yielding (HGa)5(OiPr)8O (1) as isolable compound. (HGa)5(OiPr)8O may be formally split in to four entities of HGa(OiPr)2 and one entity HGaO. The inner atomic skeleton of 1 is a novel Ga5O9 heterocluster with gallium atoms occupying the corners of a distorted trigonal bi‐pyramid, an oxygen atom in the center and the remaining alcoholate oxygen atoms bridging eight of the nine edges of the bi‐pyramid (X‐ray diffraction analysis). Potassium indium alkoxide KIn(OtBu)4 has been used to synthesize several new compounds like In4(OtBu)8(C5H4)2 (2), (py)2CuIn(OtBu)4 (3), and [CuIn(OtBu)4]2 (4) by reaction with TiCl2cp2 (2) and CuCl (3, 4). All compounds were characterized by spectroscopic means and by X‐ray structure analyses revealing novel polycyclic structures.

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Cyclopentanolates of Aluminum Hydride/Aluminum Chloride forming Aluminum‐Oxygen‐Hetero‐Cages and Mixed Coordination Oligomers

Cited by 5 publications

References 21 publications

Molecular Main Group Metal Hydrides

Molecular Main Group Metal Hydrides

Aluminum/Nitrogen Cycles and an Open Cage with Al–H and N–H Functions

Gallium and Indium Alkoxides with Hydride, Cyclopentadienediide and Copper(I) tert‐Butoxide as further Components

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