Molecular structure of [(tBu)2Al(μ-OPh)]2

Aitken, Candice L.; Barron, Andrew R.

doi:10.1007/bf01677784

Cited by 10 publications

(7 citation statements)

References 8 publications

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“…In fact in compound 2 the amine's lone pair is directed away from the aluminium centers. The bond lengths and angles within the Al 2 O 2 core are within the range expected 14, 18 and are similar to those in [(Bu t ) 2 Al(µ-OPr n )] 2 3. Compound 3 is isolated from the reaction of Al(Bu t ) 3 with HOPr n (see Experimental section) and its molecular structure is shown in Fig.…”

Section: (Busupporting

confidence: 76%

Alcohol and secondary amine complexes of tri-tert-butylaluminium: enhanced stability through intramolecular hydrogen bonding

McMahon¹,

Bott²,

Barron³

1997

J. Chem. Soc., Dalton Trans.

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Reaction of Al(Bu t ) 3 with between 1 and 2 equivalents of HOCH 2 CH 2 CH 2 NMe 2 allows for the isolation of the Lewis acid-base complex, (Bu t ) 3 Al[O(H)CH 2 CH 2 CH 2 NMe 2 ] 1, which undergoes alkane elimination above 45 ЊC to yield [(Bu t ) 2 Al(µ-OCH 2 CH 2 CH 2 NMe 2 )] 2 2. Compound 2 is also formed directly when 2 equivalents of Al(Bu t ) 3 react with 1 equivalent of HOCH 2 CH 2 CH 2 NMe 2 . The molecular structure of 1 shows an Al᎐O bond distance comparable to that found in the bridging alkoxide compounds 2 and [(Bu t ) 2 Al(µ-OPr n )] 2 3, suggesting that the Al᎐O ؒ ؒ ؒ H unit may be considered analogous to a bridging alkoxide unit, Al(µ-OR)Al, as a consequence of a significant contribution from the zwitterionic alkoxide Ϫ /ammonium ϩ form made possible by a strong intraligand hydrogen bond. The kinetics of the conversion of 1 into 2 have been studied. A large activation energy and positive deuterium isotope effect are consistent with breaking of the hydrogen bond during the transition state. The reaction of (Bu t ) 3 Al(NMe 3 ) 4 with ethanol yields [(Bu t ) 2 Al(µ-OEt)] 2 5. The reaction of Al(Bu t ) 3 with HN(Me)(CH 2 ) n NMe 2 (n = 3 or 2) yields the stable Lewis acid-base adducts (Bu t ) 3 Al[NH(Me)CH 2 CH 2 CH 2 NMe 2 ]

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Section: (Busupporting

confidence: 76%

Alcohol and secondary amine complexes of tri-tert-butylaluminium: enhanced stability through intramolecular hydrogen bonding

McMahon¹,

Bott²,

Barron³

1997

J. Chem. Soc., Dalton Trans.

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“…22 The 5-fold coordination of the Al( t Bu) moiety is a result of the chelation by the nonbridging oxygens of both glycolate ligands, one of which remains proto- Et 2 Al(OEt) 2) is essentially the same as found for dimeric alkoxides, [( t Bu) 2 Al(µ-OR)] 2 . 23 All of the Al-C and Al-O bond lengths are within their respected ranges, 24 and there are no significant intermolecular interactions. The alcohol hydrogen was located in the X-ray difference map as being bonded to O(4) and refined, see Figure 2.…”

Section: Resultsmentioning

confidence: 92%

“…The geometries about Al (1) and Al(2) are essentially the same as found for dimeric alkoxides, [( t Bu) 2 Al(µ-OR)] 2 . 23 All the Al-C and Al-O bond lengths are within their respected ranges, 23 and there are no significant intermolecular interactions.…”

Section: Resultsmentioning

confidence: 99%

Reaction of Al(^tBu)₃ with Ethylene Glycol: Intermediates to Aluminum Alkoxide (Alucone) Preceramic Polymers

et al. 1999

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The reaction of Al(tBu)3 with ethylene glycol (HOCH2CH2OH) in hexane yields “alucone” polymers, [Al(tBu)2 x (OCH2CH2O)1.5 - x ] n (0.3 ≤ 2x ≤ 0.8), with the concurrent formation of [Al2(tBu)3(OCH2CH2O)(OCH2CH2OH)] (1). If the reaction is carried out in Et2O solution, then [Al3(tBu)5(OCH2CH2O)2] (2) may be isolated. The molecular structure of compound 1 consists of a dimer formed by the alkoxide termini of two ligands bridging the Al(tBu) and Al(tBu)2 units. The Al(tBu) moiety is chelated by the nonbridging oxygens of the glycolate ligands, one of which remains protonated. Compound 2 consists of two Al(tBu)2 units and two glycolate ligands forming a cryptand-like 10-membered heterocycle; the Al(tBu) unit is positioned capping the four oxygen atoms. As with the previously reported ethoxy-substituted alucone polymers, [Al(OR)2 x (OCH2CH2O)1.5 - x ] n , thermolysis of [Al(tBu)2 x (OCH2CH2O)1.5 - x ] n , results in the formation of η-alumina (η-Al2O3) as determined by XRD. This is in contrast to the formation of γ-Al2O3 from the thermolysis of alumoxanes, [Al(O)(OR) x (OH)1 - x ] n , and may be rationalized by the structural relationship of compounds 1 and 2, and hence the alucones, to Bayerite rather than the boehmite core observed for alumoxanes.

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“…the tert-butyl groups and the O-C carbons are essentially identical to the equivalent peaks found for the aluminium aryloxide dimer, [( t Bu) 2 Al(µ-OPh)] 2 . 3 Al MAS NMR was used to investigate the aluminium coordination environment in compound 1 and shows a single broad resonance (δ = 6 ppm, W 1/2 = 4030 Hz), (Fig. 2).…”

Section: Resultsmentioning

confidence: 99%

1,4-Dioxobenzene compounds of aluminium

Poppel

Bott

Barron

2002

J. Chem. Soc., Dalton Trans.

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Molecular structure of [(tBu)2Al(μ-OPh)]2

Cited by 10 publications

References 8 publications

Alcohol and secondary amine complexes of tri-tert-butylaluminium: enhanced stability through intramolecular hydrogen bonding

Alcohol and secondary amine complexes of tri-tert-butylaluminium: enhanced stability through intramolecular hydrogen bonding

Reaction of Al(^tBu)₃ with Ethylene Glycol: Intermediates to Aluminum Alkoxide (Alucone) Preceramic Polymers

1,4-Dioxobenzene compounds of aluminium

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Molecular structure of [(tBu)2Al(μ-OPh)]2

Cited by 10 publications

References 8 publications

Alcohol and secondary amine complexes of tri-tert-butylaluminium: enhanced stability through intramolecular hydrogen bonding

Alcohol and secondary amine complexes of tri-tert-butylaluminium: enhanced stability through intramolecular hydrogen bonding

Reaction of Al(tBu)3 with Ethylene Glycol: Intermediates to Aluminum Alkoxide (Alucone) Preceramic Polymers

1,4-Dioxobenzene compounds of aluminium

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Reaction of Al(^tBu)₃ with Ethylene Glycol: Intermediates to Aluminum Alkoxide (Alucone) Preceramic Polymers