Ambiphilic boryl groups in a neutral Ni(<scp>ii</scp>) complex: a new activation mode of H<sub>2</sub>

Ríos, Pablo; Borge, Javier; Córdova, Francisco Fernández de; Sciortino, Giuseppe; Lledós, Agustı́; Rodríguez, Amor

doi:10.1039/d0sc06014c

Cited by 15 publications

(22 citation statements)

References 93 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Ethylene binding to give complex 5•(C 2 H 4 ) 2 is thermodynamically unfavorable (18.5 kcal mol −1 higher than 5•C 2 H 4 ), as depicted in Figure 5. This is in line with our previous studies on H 2 activation by neutral, square planar Ni(II) complexes, 50,69 for which the filled d z 2 orbital on nickel gave rise to weak σ-H 2 complexes. 70 Indeed, 5•(C 2 H 4 ) 2 exhibits very little C�C bond elongation upon binding (1.36 vs 1.33 Å in free ethylene).…”

Section: Effects Of Alkylating Reagent and Lewis Acidsupporting

confidence: 92%

Ethylene Dimerization and Oligomerization Using Bis(phosphino)boryl Supported Ni Complexes

et al. 2022

Self Cite

View full text Add to dashboard Cite

We report the dimerization and oligomerization of ethylene using bis(phosphino)boryl supported Ni(II) complexes as catalyst precursors. By using alkylaluminum(III) compounds or other Lewis acid additives, Ni(II) complexes of the type ( R PBP)NiBr (R = tBu or Ph) show activity for the production of butenes and higher olefins. Optimized turnover frequencies of 640 mol ethylene •mol Ni −1 •s −1 for the formation of butenes with 41(1)% selectivity for 1butene using ( Ph PBP)NiBr, and 68 mol ethylene •mol Ni −1 •s −1 for butenes production with 87.2(3)% selectivity for 1-butene using ( tBu PBP)NiBr, have been demonstrated. With methylaluminoxane as a co-catalyst and ( tBu PBP)NiBr as the precatalyst, ethylene oligomerization to form C 4 through C 20 products was achieved, while the use of ( Ph PBP)NiBr as the pre-catalyst retained selectivity for C 4 products. Our studies suggest that the ethylene dimerization is not initiated by Ni hydride or alkyl intermediates. Rather, our studies point to a mechanism that involves a cooperative B/Ni activation of ethylene to form a key 6-membered borametallacycle intermediate. Thus, a cooperative activation of ethylene by the Ni−B unit of the ( R PBP)Ni catalysts is proposed as a key element of the Ni catalysis.

show abstract

Section: Effects Of Alkylating Reagent and Lewis Acidsupporting

confidence: 92%

Ethylene Dimerization and Oligomerization Using Bis(phosphino)boryl Supported Ni Complexes

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…[64][65][66] As shown in Figure 6, the E (2) value presents an upward trend from V to Ni. The E (2) value of Fe-RC is 61.17 [35,37,39,43] LBO has a direct correlation with the bond dissociation energy. [67] The LBOs of B-H b for M-PCs decrease from V to Ni (Figure 6).…”

Section: Full Papermentioning

confidence: 96%

“…[34][35][36][37][38][39][40][41][42][43] A considerable number of LA-TM catalysts, such as tri(azaindolyl)borane-Rh, MesB(o-PPh 2 C 6 H 4 ) 2 -Ni (DPB-Ni), tris(phosphino)borane-Fe (TPB-Fe), bis-phosphinoboryl-Co (PBP-Co), PBP-Ni, (boryl)iminomethane-Pt (BIM-Pt), heterobimetallic LA-TM complexes, and so on, show high catalytic activity in H 2 activation. [34][35][36][37][38]40,41,43] To better understand the mechanism of H 2 activation and hydrogenation catalyzed by LA-TM catalysts, relevant theoretical studies have been performed as well. [44][45][46][47][48][49][50][51][52] The HÀ H bond cleavage is regarded as the key step for LA-TM catalyzed H 2 activation.…”

Section: Introductionmentioning

confidence: 99%

Metal Effect Meets Volcano Plots: A DFT Study on Tris(phosphino)borane‐Transition Metal Complexes Catalyzed H₂ Activation

2021

Chemistry An Asian Journal

View full text Add to dashboard Cite

Bifunctional transition metal complexes are of particular interest in metal-ligand cooperative activation of small molecules. As a novel type of bifunctional catalyst, Lewis acid transition metal (LA-TM) complexes have attracted increasing interest in hydrogen activation and storage. To advance the catalyst design, herein the metal effect of LA-TM complexes on the hydrogen activation has been systematically studied with a series of tris(phosphino)borane (TPB) complexes with V, Cr, Mn, Fe, Co, and Ni as metal centers. The metal effect not only influences the mechanism of hydrogen activation, but also notably casts a volcano plot for the activity. TPB complexes of V, Cr, Mn, Fe, and Co tend to activate H 2 through a stepwise mechanism, while TPB-Ni prefers a synergetic mechanism for H 2 activation. More importantly, the metal effect significantly influences the activity of H 2 activation and the formation of the LA-H-TM bridging hydride. The trend of changes in the LA-H-TM structures, the second-order perturbation stabilization energies, and the Laplacian bond orders, along with different metals (from V to Ni), are all interestingly constitute volcano plots for the performance of TPB-TM complexes catalyzed H 2 activation. TPB-Mn and TPB-Fe are found to be the optimal catalysts among the discussed TPB-TM complexes. The volcano plots disclosed for the metal effects should be informative and instructive for homogeneous and heterogeneous LA-TM catalysts development.

show abstract

“…Complex 1 features Al centers that bear a σ-accepting role to Ni, generating a more electron-rich Al center compared to LAlH and a relatively electron-deficient Ni(0) center; however, further studies are needed to differentiate between a Ni(II) hydride with an alane/aluminyl assignment versus alanes and Ni(0) designation. Bridging hydrides between transition metals and borane/boryl centers are established; − however, complex 1 is a rare experimental finding observing three-center bonding of a hydride between Ni and Al. ,, …”

mentioning

confidence: 99%

Amplifying Reactivity of Metal Hydrides: A Heterotrimetallic NiAl₂(μ²-H)₂ Catalyst for the Dearomatization of N-Heterocycles

et al. 2023

View full text Add to dashboard Cite

Identifying methods to modulate the reactivity of metal hydrides is lacking yet highly desirable given the role they play in a plethora of catalytic applications. Herein we report novel methodology to amplify the reactivity of metal hydrides through the design of well-defined heterometallic bridged hydride species. Catalytic hydroboration of quinolines was dramatically altered by the addition of a secondary metal to bridge the Al–hydride species LAlH. Specifically, the addition of Ni(COD)2 led to the formation of novel heterotrimetallic species 1 which features Ni participating in 3-center bonding with sterically accessible Al–H species and exhibits catalytic hydroboration of sterically encumbered quinolines and approximately a 400 times enhancement in catalytic reactivity in comparison to LAlH.

show abstract

Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H₂

Abstract: A bis(boryl)nickel complex promotes the facile and reversible activation of H2 through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process.

Cited by 15 publications

References 93 publications

Ethylene Dimerization and Oligomerization Using Bis(phosphino)boryl Supported Ni Complexes

Ethylene Dimerization and Oligomerization Using Bis(phosphino)boryl Supported Ni Complexes

Metal Effect Meets Volcano Plots: A DFT Study on Tris(phosphino)borane‐Transition Metal Complexes Catalyzed H₂ Activation

Amplifying Reactivity of Metal Hydrides: A Heterotrimetallic NiAl₂(μ²-H)₂ Catalyst for the Dearomatization of N-Heterocycles

Contact Info

Product

Resources

About

Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H2

Abstract: A bis(boryl)nickel complex promotes the facile and reversible activation of H2 through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process.

Cited by 15 publications

References 93 publications

Ethylene Dimerization and Oligomerization Using Bis(phosphino)boryl Supported Ni Complexes

Ethylene Dimerization and Oligomerization Using Bis(phosphino)boryl Supported Ni Complexes

Metal Effect Meets Volcano Plots: A DFT Study on Tris(phosphino)borane‐Transition Metal Complexes Catalyzed H2 Activation

Amplifying Reactivity of Metal Hydrides: A Heterotrimetallic NiAl2(μ2-H)2 Catalyst for the Dearomatization of N-Heterocycles

Contact Info

Product

Resources

About

Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H₂

Metal Effect Meets Volcano Plots: A DFT Study on Tris(phosphino)borane‐Transition Metal Complexes Catalyzed H₂ Activation

Amplifying Reactivity of Metal Hydrides: A Heterotrimetallic NiAl₂(μ²-H)₂ Catalyst for the Dearomatization of N-Heterocycles