[CpAlN(2,6-i-Pr2C6H3)]2:  A Dimeric Iminoalane Obtained by Alkane Elimination

Fisher, James D.; Shapiro, Pamela J.; Yap, Glenn P. A.; Rheingold, Arnold L.

doi:10.1021/ic951201k

Cited by 53 publications

(42 citation statements)

References 42 publications

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“…These bond-lengths were comparable to the reported values, such as 1.824 in the four-membered ring of [(Mes*AlNPh) 2 ] (Mes* = 2,4,6-(tBu) 3 C 6 H 2 ), [24b] 1.970-2.013 in [Cp*AlA C H T U N G T R E N N U N G (m-NH(C 6 H 2 -4,6-Me 2 -2-CH 2 ))], [26] and 1.804 (average) in [CpAlN(2,6-iPr 2 C 6 H 3 )] 2 . [27] As in typical Al 2 N 2 rings, [24] the endocyclic N-Al-N angles (average 86.368) in compounds 2-5 were smaller than the Al-N-Al angles (average 92.038). The Al···Al separation across the Al 2 N 2 ring in compound 5 (2.744(2) ) was somewhat longer than that in compounds 1 (2.658(2) ), 2 (2.637(1) ), 3 (2.6273(11) ), and 4 (2.6238(11) ), but was a little shorter than the longest Al À Al bond (2.7512 ) reported to date.…”

Section: Discussionmentioning

confidence: 97%

“…The average AlN bond‐lengths for the four‐membered Al 2 N 2 rings was 1.832 Å, and the exocyclic AlN bonds (to the α‐diimine ligand L) were much longer (average 1.928 Å). These bond‐lengths were comparable to the reported values, such as 1.824 Å in the four‐membered ring of [(Mes*AlNPh) 2 ] (Mes*=2,4,6‐( t Bu) 3 C 6 H 2 ),24b 1.970–2.013 Å in [Cp*Al(μ‐NH(C 6 H 2 ‐4,6‐Me 2 ‐2‐CH 2 ))],26 and 1.804 Å (average) in [CpAlN(2,6‐ i Pr 2 C 6 H 3 )] 2 27. As in typical Al 2 N 2 rings,24 the endocyclic N‐Al‐N angles (average 86.36°) in compounds 2 – 5 were smaller than the Al‐N‐Al angles (average 92.03°).…”

Section: Discussionmentioning

confidence: 99%

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Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L²⁻Al^IIAl^IIL²⁻]

Zhao

Liu

Yang

et al. 2012

Chemistry A European J

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An α-diimine-stabilized Al-Al-bonded compound [L(2-)Al(II)-Al(II)L(2-)] (L = [{(2,6-iPr(2)C(6)H(3))NC(Me)}(2)]; 1) consists of dianionic α-diimine ligands and sub-valent Al(2+) ions and thus could potentially behave as a multielectron reductant. The reactions of compound 1 with azo-compounds afforded phenylimido-bridged products [L(-)Al(III)(μ(2)-NPh)(μ(2)-NAr)Al(III)L(-)] (2-4). During the reaction, the dianionic ligands and Al(2+) ions were oxidized into monoanions and Al(3+), respectively, whilst the [NAr](2-) imides were produced by the four-electron reductive cleavage of the N=N double bond. Upon further reduction by Na, the monoanionic ligands in compound 2 were reduced to the dianion to give [(L(2-))(2)Al(III)(2)(μ(2)-NPh)(2)Na(2)(thf)(4)] (5). Interestingly, when asymmetric azo-compounds were used, the asymmetric adducts were isolated as the only products (compounds 3 and 4). DFT calculations indicated that the reaction was quite feasible in the singlet electronic state, but the final product with the triplet-state monoanionic ligands could result from an exothermic singlet-to-triplet conversion during the reaction process.

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Section: Discussionmentioning

confidence: 97%

Section: Discussionmentioning

confidence: 99%

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L²⁻Al^IIAl^IIL²⁻]

Zhao

Liu

Yang

et al. 2012

Chemistry A European J

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“…The Al-N distances average 1.853(9) Å while the corresponding Ga-N distances average 1.889(4) Å. These distances are significantly longer that those found in the iminoaluminum dimer [CpAl(µ-Naryl)] 2 (1.796(2) and 1.811(3) Å) 8 Reaction of H[(1,2-C 5 H 3 (C(Ph)NH) 2 )] with either AlMe 3 or AlEt 3 affords the dimethyl and diethyl derivatives of 1, [(1,2-C 5 H 3 (C(Ph)NH) 2 )]AlR 2 , R ) Me (3), Et (4) (Scheme 1). The rust orange compounds 3 and 4 were isolated in 83% and 69% yields, respectively.…”

Section: Resultsmentioning

confidence: 73%

1,2-Cyclopentadienyl Diimine−Group 13 Complexes

Ong

Stephan

1999

Inorg. Chem.

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“…[21] Finally, 184.0/184.2 pm and 92.9/93.28 were measured for R = C 5 (CH 3 ) 5 and R' = SitBu 3 . [22] All these values are in pleasing agreement to the ones calculated for [HAlNH] 2 .…”

Section: Alnhmentioning

confidence: 99%

Possible Pathways of CVD Processes Leading to III–V Semiconductors via a Two‐Dimensional Growth

Himmel

2005

ChemPhysChem

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Quantum-chemical calculations were carried out to shed more light upon possible first intermediates formed during chemical vapour deposition (CVD) processes leading to III-V semiconductors. Information about possible structures of intermediates and about thermodynamic properties in dependence of the temperature were collected. Because some of the systems calculated herein contain a substantial number of atoms (up to 144), it is limited to intermediates on the way to solid AIN. According to our suggestion, the first intermediates are species with the overall formula AINH2, Al2N2H4, Al3N3H6, AI5N5H8, AI7N7H, and Al9N9H, AI12N12H12. In further calculations the growth of a second layer, on top of the first layer, which is modelled by the Al12N12H12 cluster, is simulated. The Al12N12H12 "surface" offers two places for the attachment of an Al3N3H6 ring. At temperatures of 1000 K, the deltaG value for this attachment is only slightly negative, which suggests that the molecules can move relatively freely on the surface. This might be of importance for a defect-free growth process. Up to four layers are built on top of the first Al12N12H12 layer leading to Al24N24H24 (two layers), Al36N36H36 (three layers) and Al48N48H48 (four layers). The structures are compared with that of solid AIN in its most stable Wurzit-type structure.

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[CpAlN(2,6-i-Pr₂C₆H₃)]₂: A Dimeric Iminoalane Obtained by Alkane Elimination

Cited by 53 publications

References 42 publications

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L²⁻Al^IIAl^IIL²⁻]

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L²⁻Al^IIAl^IIL²⁻]

1,2-Cyclopentadienyl Diimine−Group 13 Complexes

Possible Pathways of CVD Processes Leading to III–V Semiconductors via a Two‐Dimensional Growth

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[CpAlN(2,6-i-Pr2C6H3)]2: A Dimeric Iminoalane Obtained by Alkane Elimination

Cited by 53 publications

References 42 publications

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L2−AlIIAlIIL2−]

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L2−AlIIAlIIL2−]

1,2-Cyclopentadienyl Diimine−Group 13 Complexes

Possible Pathways of CVD Processes Leading to III–V Semiconductors via a Two‐Dimensional Growth

Contact Info

Product

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[CpAlN(2,6-i-Pr₂C₆H₃)]₂: A Dimeric Iminoalane Obtained by Alkane Elimination

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L²⁻Al^IIAl^IIL²⁻]

Mechanistic Insight into the NN Bond‐Cleavage of Azo‐Compounds that was Induced by an AlAl‐bonded Compound [L²⁻Al^IIAl^IIL²⁻]