Reduction of organic azides by indyl-anions. Isolation and reactivity studies of indium–nitrogen multiple bonds

Anker, Mathew D.; Lein, Matthias; Coles, Martyn P.

doi:10.1039/c8sc04078h

Cited by 48 publications

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“…A potential strategy for the synthesis of discrete molecular imide species involves the reaction of an organo azide with an Al I complex via elimination of N 2 . This strategy has previously been employed by Power, Roesky, and co‐workers (e.g., for IV and V , Figure ), and a related approach has been reported by Coles and co‐workers for the synthesis of an indium imide complex ( VI ) . Similar chemistry has also been employed both by ourselves and by Anker and Coles for the synthesis of molecular aluminium oxide species via the reaction of anionic Al I precursors with N 2 O ( I and II ) …”

Section: Figurementioning

confidence: 83%

“…This strategy has previously been employed by Power, Roesky, and co-workers (e.g., for IV and V, Figure 1), [11] and a related approach has been reported by Coles and co-workers for the synthesis of an indium imide complex (VI). [12] Similar chemistry has also been employed both by ourselves and by Anker and Coles for the synthesis of molecular aluminium oxide species via the reaction of anionic Al I precursors with N 2 O (I and II). [8d, 13] With the idea of extending this approach to anionic aluminium imide species, we therefore probed the reactivity of the potassium aluminyl complex 1 towards trimethylsilylazide, Me 3 SiN 3 .…”

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confidence: 99%

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Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

et al. 2020

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Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K2[(NON)Al(NDipp)]2 (NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethyl‐xanthene; Dipp=2,6‐diisopropylphenyl) structural characterization by X‐ray crystallography reveals a short Al−N distance, which is thought primarily to be due to the low coordinate nature of the nitrogen centre. The Al−N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate leads to C−C coupling and C≡O bond cleavage. Thermodynamically, this is driven, at least in part, by Al−O bond formation. Mechanistically, a combination of quantum chemical and experimental observations suggests that the reaction proceeds via exchange of the NR and O substituents through intermediates featuring an aluminium‐bound isocyanate fragment.

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Section: Figurementioning

confidence: 83%

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Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

et al. 2020

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“…The other component of the crystal, [Mg(BDI Mes )] 2 ( μ ‐NON Ph ), involves two “Mg(BDI Mes )” units bridged by a (NON Ph )‐ligand. The NON Ph ‐ligand is bound differently to each Mg centre, with a κ 2 ‐ N,O ‐coordination mode to Mg5 (previously only seen in a potassium salt of the NON Dipp ‐ligand) and mono‐dentate N‐coordination to Mg6. Despite these differences, the Mg‐N NON distances (1.990(3) and 1.970(3) Å) are essentially identical.…”

Section: Resultsmentioning

confidence: 99%

Distibanes and Distibenes from Reduction of Sb(NON^R)Cl by using Mg^IReagents

Schwamm

Coles

2019

Chemistry A European J

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The bis(amidodimethyl)disiloxane antimony chlorides Sb(NON R )Cl (NON R = [O(SiMe 2 NR) 2 ] 2À ;R = tBu, Ph, 2,6-Me 2 C 6 H 3 = Dmp, 2,6-iPr 2 C 6 H 3 = Dipp, 2,6-(CHPh 2 ) 2 -4-tBuC 6 H 2 = tBu-Bhp) are reduced to Sb II and Sb I species by using Mg I reagents,[ Mg(BDI R' )] 2 (BDI = [HC{C(Me)NR'} 2 ] À ;R ' = 2,4,6-Me 3 C 6 H 2 = Mes, Dipp). Stoichiometric reactions with Sb(NON R )Cl (R = tBu, Ph) form dimericS b II stibanes [Sb(NON R )] 2 ,s hown crystallographically to contain SbÀSb single bonds. The analogousd istibane with R = Dmp substituents has an exceptionally long SbÀSb interaction and exhibits spectroscopic and reactivityp roperties consistent with radicalc haracteri ns olution.W hen R = Dipp, reductions with Mg I reagents directly give distibenes [Sb(m-NON Dipp )Mg(BDI R' )(THF) n ] 2 (R' = Mes, n = 1; R' = Dipp, n = 0). Crystallographic analysiss hows a trans-substitutiono ft he Sb=Sb double bond,w ith bridging NON Dipp -ligands between the Sb I and Mg II centres.Anattempttoaccess the NON Ph -analogueu sing the same protocol afforded the polystibide cluster Sb 8 [m 4 ,h 2:2:2:2 -Mg(BDI Mes )] 4 ,w hich co-crystallized with the ligand transfer product, [Mg(BDI Mes )] 2 (m-NON Ph ). [a] Dr.R.J.S chwamm, Prof. Dr.M.P .C oles SchoolofC hemical and Physical Sciences,NMR reaction of 1a-c with excess [Mg(BDI Mes )] 2 or [Mg(BDI Dipp )] 2 AJ .Y oung's NMR tube was charged with [Mg(BDI Mes )] 2 or [Mg(BDI Dipp )] 2 (0.2 mmol) and Sb(NON R )Cl (0.05 mmol, R = tBu (1a) Ph (1b)o r ( 1c)) in C 6 D 6 (0.5 mL) and heated to 70 8Ca nd monitored using 1 HNMR spectroscopy at regular intervals over 78 h. A few colourless co-crystals of 6b and 7 were deposited from the re-action mixture of 1b and [Mg(BDI Mes )] 2 and analysed by single crystal X-ray diffraction.

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“…We have mitigated the influence of potassium contacts in aluminum–selenium and indium–nitrogen multiple bonds through cation sequestration. A similar attempt was made in this study by allowing the slow diffusion of a solution of [2.2.2]cryptand into a solution 2 at −30 °C, affording large colorless crystals 3 .…”

Section: Figurementioning

confidence: 99%

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

Anker

Coles

2019

Angew Chem Int Ed

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The deoxygenative conversion of carbon dioxide to carbon monoxide is promoted by the aluminyl anion [Al-(NON Ar )] À (NON Ar = [O(SiMe 2 NAr) 2 ] 2À ,A r= 2,6-iPr 2 C 6 H 3 ). The reaction proceeds via the isolable monoalumoxane anion [Al(NON Ar )(O)] À ,c ontaining at erminal aluminum-oxygen bond. This species reacts with as econd equivalent of carbon dioxide to affordthe carbonate [Al(NON Ar )(CO 3 )] À ,and with nitrous oxide to generate the hyponitrite anion, [Al-(NON Ar )(k 2 O,O'-N 2 O 2 )] À .

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Reduction of organic azides by indyl-anions. Isolation and reactivity studies of indium–nitrogen multiple bonds

Abstract: Stepwise reaction of an indyl-anion with organic azides initially forms the indium imide, which undergoes (2 + 3)-cycloaddition to generate the indium tetrazenide.

Cited by 48 publications

References 53 publications

Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

Distibanes and Distibenes from Reduction of Sb(NON^R)Cl by using Mg^IReagents

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

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Reduction of organic azides by indyl-anions. Isolation and reactivity studies of indium–nitrogen multiple bonds

Abstract: Stepwise reaction of an indyl-anion with organic azides initially forms the indium imide, which undergoes (2 + 3)-cycloaddition to generate the indium tetrazenide.

Cited by 48 publications

References 53 publications

Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

Distibanes and Distibenes from Reduction of Sb(NONR)Cl by using MgIReagents

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

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Distibanes and Distibenes from Reduction of Sb(NON^R)Cl by using Mg^IReagents