Synthesis and characterization of rare examples of stable potassium and arylcalcium triethylboranate complexes

Krieck, Sven; Görls, Helmar; Westerhausen, Matthias

doi:10.1016/j.inoche.2010.08.018

Cited by 19 publications

(6 citation statements)

References 52 publications

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“…To further support the transient formation of [Cu( 2 H )(H)] in the above reactions, we sought to deliberately trap this species with a Lewis acid, e.g. BEt 3 , in order to bring kinetic stability as previously reported for the stabilization of a Ca–H bond . Hydrogenation (1 atm) of a THF solution of 4 in the presence of 1 equiv of BEt 3 cleanly afforded, after 24 h at room temperature, the new complex 6 .…”

Section: Resultsmentioning

confidence: 99%

“…BEt 3 , in order to bring kinetic stability as previously reported for the stabilization of a Ca−H bond. 46 Hydrogenation (1 atm) of a THF solution of 4 in the presence of 1 equiv of BEt 3 cleanly afforded, after 24 h at room temperature, the new complex 6. The conversion never exceeded a 20% yield, but no side reaction was observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Copper–Ligand Cooperativity in H₂ Activation Enables the Synthesis of Copper Hydride Complexes

et al. 2021

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Copper(I) complexes of a new participative triphosphane ligand (2 H ) have been prepared and structurally characterized, in particular [Cu(2 H )I] and [Cu(2)]2. Hydrogenation of the latter species afforded the trimetallic hydride species [Cu3(2)2(µ-H)] or in the presence of BEt3, [Cu(2 H )(HBEt3)]. Their formation evidences transient formation of [Cu(2 H )H] formed by hydrogenolysis of the Cu-N bond of [Cu(2)]2. [Cu(2 H )(HBEt3)] behaves like a hydride complex and inserts CO2 to yield the formate product [Cu(2 H )(O2CH)]. QTAIM analysis of the Cu-H-BEt3 interaction indicates a hydride complex stabilized by the Lewis acid BEt3.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Copper–Ligand Cooperativity in H₂ Activation Enables the Synthesis of Copper Hydride Complexes

et al. 2021

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“…BEt3, in order to bring kinetic stability as previously reported for the stabilization of a Ca-H bond. 46 Hydrogenation (1 atm.) of a THF solution of 4 in the presence of one equivalent of BEt3 cleanly afforded, after 24h at room temperature, the new complex 6.…”

Section: Scheme 4 Formation Of 5 Through Activation Of H2 On 4 and Putative Generation Of A Copper Hydride Intermediatementioning

confidence: 99%

Copper–Ligand Cooperativity in H2 Activation Enables the Synthesis of Copper Hydride Complexes

Aloisi¹,

Crochet²,

Nicolas³

et al. 2021

Preprint

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Copper(I) complexes of a new participative triphosphane ligand (2H) have been prepared and structurally characterized, in particular [Cu(2H)I] and [Cu(2)]2. Hydrogenation of the latter species afforded the trimetallic hydride species [Cu3(2)2(µ-H)] or in the presence of BEt3, [Cu(2H)(HBEt3)]. Their formation evidences transient formation of [Cu(2H)H] formed by hydrogenolysis of the Cu‒ N bond of [Cu(2)]2. [Cu(2H)(HBEt3)] behaves like a hydride complex and inserts CO2 to yield the formate product [Cu(2H)(O2CH)].

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“…Two common examples are [Ar Mes 2 ] and [Ar Dipp 2 ] (Figure ) Indeed, structurally characterized [κ 1 -Ar Ar 2 ]M compounds are known for a substantial number of metals, including transition metals (Sc, Y, , Ti, Ta, Cr, Mo, Mn, , Fe, ,− , Co, ,− , Cu, Ag, , Au), main group metals (Li, Na, Be, Mg, , Ca, Zn, Cd, , Hg, , Al, Ga, , In, Tl, Ge, Sn, Pb, As, , Sb, Bi, , ), and lanthanides (Sm, , Eu, Er, Tm, , Yb, ,, Lu). However, despite this interest in the use of terphenyl ligands, there are still many elements that have received little attention (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structural Characterization, and Cyclometalation Chemistry of Tantalum Terphenyl Compounds

Sattler

Parkin

2015

Organometallics

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The κ 1 -m-terphenyl complex of tantalum, [Ar Tol 2 ]Ta-(NMe 2 ) 3 Cl ([Ar Tol 2 ] = 2,6-di-p-tolylphenyl), has been synthesized by the reaction of [Ta(NMe 2 ) 3 Cl 2 ] 2 with two equivalents of [Ar Tol 2 ]Li.[Ar Tol 2 ]Ta(NMe 2 ) 3 Cl provides access to a variety of monoalkyl compounds, [Ar Tol 2 ]Ta(NMe 2 ) 3 R (R = Me, Et, Pr n , Bu n , and Np; Np = CH 2 Bu t ), via the reactions with the corresponding RLi. In addition, the reaction of [Ta(NMe 2 ) 3 Cl 2 ] 2 with excess [Ar Tol 2 ]Li affords the bis(terphenyl) complex, [Ar Tol 2 ] 2 Ta(NMe 2 ) 3 , while the reaction of [Ar Tol 2 ]Ta(NMe 2 ) 3 Cl with LiBH 4 gives the borohydride complex, [Ar Tol 2 ]Ta(NMe 2 ) 3 (κ 2 -BH 4 ). The dichloride compound, [Ar Tol 2 ]Ta(NMe 2 ) 2 Cl 2 , which is obtained via the reaction of [Ar Tol 2 ]Ta(NMe 2 ) 3 Cl with Me 3 SiCl, provides access to a series of dialkyl derivatives, [Ar Tol 2 ]Ta(NMe 2 ) 2 R 2 (R = Me, Et, Pr n , Bu n , and Np), via the reactions with the corresponding RLi. The κ 1 -mterphenyl ligands in these complexes are susceptible to metalation. Thus, [Ar Tol 2 ]Ta(NMe 2 ) 3 R eliminates RH to afford [κ 2 -Ar Tol,Tol′ ]Ta(NMe 2 ) 3 (Tol′ = C 6 H 3 Me), while [Ar Tol 2 ]Ta(NMe 2 ) 2 Np 2 eliminates NpH to form [κ 2 -Ar Tol,Tol′ ]Ta(NMe 2 ) 2 Np. ■ INTRODUCTIONAncillary ligands play a critical role in organometallic chemistry by allowing tunable properties of a metal center. 1 One such class that has received considerable attention is that of the mterphenyl ligand ([Ar Ar 2 ]) (Figure 1), which provides significant steric protection by virtue of the outer aryl rings. Two common examples are [Ar Mes 2 ] and [Ar Dipp 2 ] (Figure 1). 2 Indeed, structurally characterized [κ 1 -Ar Ar 2 ]M compounds are known for a substantial number of metals, including transition metals despite this interest in the use of terphenyl ligands, there are still many elements that have received little attention (Figure 2). In this regard, our recent use of the 2,6-di-p-tolylphenyl ligand ([Ar Tol 2 ]) to synthesize [Ar Tol 2 ]TaMe 3 Cl and [Ar Tol 2 ]TaMe 2 Cl 2 represents, to the best of our knowledge, the first application of terphenyl ligands to tantalum chemistry. 6 While many of the applications of m-terphenyl ligands have focused on the use of steric protection to allow for the isolation of uncommon and low coordination complexes, 2 our interest pertains to the potential of using such ligands to construct multidentate variants via cyclometalation. As an illustration, we recently employed this approach to obtain the first examples of transition metal compounds that feature a [CCC] X 3 -donor pincer ligand, 36 namely [κ 3 -Ar Tol′ 2 ]Ta(PMe 3 ) 2 MeCl, [κ 3 -Figure 1. Examples of [κ 1 -m-terphenyl] ligands.Figure 2. Elements for which κ 1 -m-terphenyl compounds have been structurally characterized by X-ray diffraction (blue), and those for which there are no structurally characterized examples listed in the Cambridge Structural Database (red).Article pubs.acs.org/Organometallics

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Synthesis and characterization of rare examples of stable potassium and arylcalcium triethylboranate complexes

Cited by 19 publications

References 52 publications

Copper–Ligand Cooperativity in H₂ Activation Enables the Synthesis of Copper Hydride Complexes

Copper–Ligand Cooperativity in H₂ Activation Enables the Synthesis of Copper Hydride Complexes

Copper–Ligand Cooperativity in H2 Activation Enables the Synthesis of Copper Hydride Complexes

Synthesis, Structural Characterization, and Cyclometalation Chemistry of Tantalum Terphenyl Compounds

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