Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species

Nagata, Kôichi; Murosaki, Takahiro; Agou, Tomohiro; Sasamori, Takahiro; Matsuo, Tsukasa; Tokitoh, Norihiro

doi:10.1002/ange.201606684

Cited by 36 publications

(4 citation statements)

References 57 publications

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“…In the solid state three hydrides were found to be μ‐bridging, whereas Cl and the additional hydrides occupy end‐on positions on Al, with the Cp*‐substituents being η 5 ‐coordinated on Al1 and Al2, and showing a rather unsymmetric coordination on Al3 in line with a η 3 ‐coordination mode. The Al−( μ ‐H)−Al distances range from 1.65–1.75 Å, which agrees with the Al−H distances in the dimeric (ArAlH 2 ) 2 (1.60–1.72 Å, Ar=2,6‐(CH(SiMe 3 ) 2 ) 2 ‐4‐ t Bu‐C 6 H 2 ) [44] . Again, after removal of the supernatant solution from 7 , the desired Cp* 2 AlH was isolated in good yields by crystallization.…”

Section: Resultssupporting

confidence: 76%

On the Reactivity of Mes*P(PMe₃) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

et al. 2023

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Phosphaalumenes are the heavier isoelectronic analogs of alkynes and have eluded facile synthesis until recently. We have reported that the combination of a phosphinidene transfer agent, ArTerP(PMe3) (ArTer=2,6‐Ar2‐C6H3), with (Cp*Al)4 (Cp*=C5(CH3)5) afforded the phosphaalumenes ArTerPAlCp* as isolable, violet, thermally stable compounds. In here we describe attempts to utilize Mes*P(PMe3) (Mes*=2,4,6‐tBu3‐C6H2) as a phosphinidene source in combination with different Al(I) precursors, namely DipNacnacAl (DipNacnac=HC[C(Me)NDip]2, Dip=2,6‐iPr2‐C6H3), (Cp*Al)4 and Cp3tAl (Cp3t=1,2,4‐tBu3‐C5H2). In all cases the formation of phosphaalumenes was not observed, however, their intermediate formation is indicated by formation of the dimer [Cp*Al(μ‐PMes*)]2 (2) and C−H‐bond activation products along the putative P=Al bond, giving unusual 1,2‐P,Al‐tetrahydronaphtalene derivatives 1 and 4, clearly underlining the role the sterically demanding group on phosphorus plays in these transformations. The reactivity studies are supported by theoretical studies, demonstrating a thermodynamic preference for the C−H activation products. Additionally, we show that there are potential pitfalls in the synthesis of Cp*2AlH, the precursor to make (Cp*Al)4 and give recommendations how to circumvent these.

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Section: Resultssupporting

confidence: 76%

On the Reactivity of Mes*P(PMe₃) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

et al. 2023

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“…Braunschweig et al reported an unusual cleavage of the CC triple bond of 2-butyne upon photolysis of the phosphinestabilized diborene 475 in diethyl ether at room temperature to give the monophosphine-stabilized homoaromatic 1,3-dihydro-1,3-diborete 476 (Scheme 145). 361 Interestingly, analogous reaction of 1,2-bis(trimethylsilyl)acetylene with the benzeneligated dialumene 13 resulted in cycloaddition to give the 1,2dialuminacyclobut-3-ene 477 44 whereas the related digallene Ar Dipp GaGaAr Dipp (16) underwent double cycloaddition of phenylacetylene to furnish 1,4-digallacyclohexa-2,5-diene 478. 362 In both cases complete cleavage of the CC bond does not occur.…”

Section: Cleavage Of Cx and Px Double Bondsmentioning

confidence: 99%

Oxidative Addition and Reductive Elimination at Main-Group Element Centers

2018

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Oxidative addition and reductive elimination are key steps in a wide variety of catalytic reactions mediated by transition-metal complexes. Historically, this reactivity has been considered to be the exclusive domain of d-block elements. However, this paradigm has changed in recent years with the demonstration of transition-metal-like reactivity by main-group compounds. This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements. We also discuss the significant discovery of reversible activation of single bonds and distinct examples of reductive elimination at main-group element centers. The review consists of three major parts, starting with oxidative addition of single bonds, proceeding to cleavage of multiple bonds, and culminated by the discussion of reversible bond activation and reductive elimination. Within each subsection, the discussion is arranged according to the type of bond being cleaved or formed and considers elements from the left to the right of each period and down each group of the periodic table. The majority of results discussed in this Review come from the past decade; however, earlier reports are also included to ensure completeness.

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“…Similar reactivity was seen for the dialuminenebenzene cycloaddition products reported by Tokitoh and co-workers. 63 Upon retro-cycloaddition, free dialuminene is liberated in solution and was further found to react with H 2 to give the corresponding aluminum dihydride product. Inoue and co-workers also demonstrated that H 2 adds to the classical double bond in the dialuminene Trip(NHC)AlAl(NHC)Trip to give the dialane Trip(NHC)HAl-AlH(NHC)Trip.…”

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confidence: 99%

The Monomeric Alanediyl :AlAr^iPr8 (Ar^iPr8 = C₆H-2,6-(C₆H₂-2,4,6-Prⁱ₃)₂-3,5-Prⁱ₂): An Organoaluminum(I) Compound with a One-Coordinate Aluminum Atom

et al. 2020

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Reduction of the aluminum iodide AlI 2 Ar iPr8 (1;2 ) with 5% w/w Na/NaCl in hexanes gave a dark red solution from which the monomeric alanediyl :AlAr iPr8 (2) was isolated in ca. 28% yield as yellow-orange crystals. Compounds 1 and 2 were characterized by X-ray crystallography, electronic and NMR spectroscopy, and theoretical calculations. The Al atom in 2 is one-coordinate, and the compound displays two absorptions in its electronic spectrum at 354 and 455 nm. It reacts with H 2 under ambient conditions to give the aluminum hydride {AlH(μ-H)Ar iPr8 } 2 , probably via a weakly bound dimer of 2 as an intermediate.

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Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species

Abstract: Scheme 1. Reactionso fdialumanes 1a, 1b,a nd 4 with H 2 .

Cited by 36 publications

References 57 publications

On the Reactivity of Mes*P(PMe₃) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

On the Reactivity of Mes*P(PMe₃) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

Oxidative Addition and Reductive Elimination at Main-Group Element Centers

The Monomeric Alanediyl :AlAr^iPr8 (Ar^iPr8 = C₆H-2,6-(C₆H₂-2,4,6-Prⁱ₃)₂-3,5-Prⁱ₂): An Organoaluminum(I) Compound with a One-Coordinate Aluminum Atom

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Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species

Abstract: Scheme 1. Reactionso fdialumanes 1a, 1b,a nd 4 with H 2 .

Cited by 36 publications

References 57 publications

On the Reactivity of Mes*P(PMe3) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

On the Reactivity of Mes*P(PMe3) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

Oxidative Addition and Reductive Elimination at Main-Group Element Centers

The Monomeric Alanediyl :AlAriPr8 (AriPr8 = C6H-2,6-(C6H2-2,4,6-Pri3)2-3,5-Pri2): An Organoaluminum(I) Compound with a One-Coordinate Aluminum Atom

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On the Reactivity of Mes*P(PMe₃) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

On the Reactivity of Mes*P(PMe₃) towards Aluminum(I) Compounds – Evidence for the Intermediate Formation of Phosphaalumenes

The Monomeric Alanediyl :AlAr^iPr8 (Ar^iPr8 = C₆H-2,6-(C₆H₂-2,4,6-Prⁱ₃)₂-3,5-Prⁱ₂): An Organoaluminum(I) Compound with a One-Coordinate Aluminum Atom