Tellurium(II)‐Centered Dications from the Pseudohalide “Te(OTf)<sub>2</sub>”

Dutton, Jason L.; Tuononen, Heikki M.; Ragogna, Paul J.

doi:10.1002/anie.200901495

Cited by 50 publications

(46 citation statements)

References 38 publications

(28 reference statements)

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“…NHCs such as imidazolylidenes [57] or CAACs [58] [73] or telleriums (Te II ) [74] cations have also been considered as carbenestabilized complexes. Recently, a non-negligible -accepting character of aminocarbenes [75] has been claimed to account for the stabilization of main-group radical or radical ions centered at boron [76], silicon [77], or phosphorus [78].…”

Section:  1 -Sp 2 Carbon Ligands Of Main Group Lewis Acids Phosphenmentioning

confidence: 99%

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Lepetit

Maraval

Canac

et al. 2016

Coordination Chemistry Reviews

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Section:  1 -Sp 2 Carbon Ligands Of Main Group Lewis Acids Phosphenmentioning

confidence: 99%

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Lepetit

Maraval

Canac

et al. 2016

Coordination Chemistry Reviews

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“…[8] Additionally, various oxidation states encountered in germylenes Ge II , [9] silylenes Si II , [10] borenium B III , [11] or tellerium Te II [12] cations have also been reported to be efficiently stabilized by NHC ligands. By extension, even tetraaminoethenes could be interpreted as the ultimate products of primary donor-acceptor adducts between the filled sp 2 orbital of one diaminocarbene and the formally empty p orbital of the other.…”

Section: Introductionmentioning

confidence: 99%

Imidazoliophosphines are True N‐Heterocyclic Carbene (NHC)–Phosphenium Adducts

Abdellah

Lepetit

Canac

et al. 2010

Chemistry A European J

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Whereas the external nucleophilic reactivity of α-amidiniophosphines has been previously illustrated by their complexation to transition-metal centers, their internal electrophilic reactivity is herein investigated by using BIMIONAP (BIMIONAP=N-methylated BIMINAP cation, BIMINAP=formal contraction of the acronyms BIMIP=2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole and BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl). Reaction of tetraethylammonium chloride with free BIMIONAP is found to induce heterolytic cleavage of the N(2)C-P bond to give chlorodiphenylphosphine and a transient phosphine-N-heterocyclic carbene (NHC) species that is trapped in situ by protonation to the corresponding phosphine-benzimidazolium cation. When the chloride anion reacts with the cationic [Pd(η(2)-BIMIONAP)Cl(2)] complex, the same cleavage occurs and the phosphine-NHC moiety is trapped in the corresponding [PdCl(2)(η(2)-phosphine-NHC)] complex. When the chloride anion reacts with the dicationic [Pd(π-allyl)(η(2)-BIMIONAP)](+) complex, allyldiphenylphosphine is produced, and the [PdCl(η(2)-phosphine-NHC)(PPh(2)CH(2)CH=CH(2))](+) complex is obtained. Reaction of free BIMIONAP with the harder n-butyllithium nucleophile also induces heterolytic cleavage of the N(2)C-P bond, from which the phosphine-NHC moiety is trapped by hydrolysis of the benzimidazole ring or by P,C-sulfurization. Cleavage of a C-P bond with the weak Cl(-) nucleophile to release the reactive NHC moiety (according to the unusual scheme C-P+Cl(-)→C:+Cl-P) is a definite experimental indication of the dative nature of the N(2)C-P bond of amidiniophosphines, which are, therefore, better described as NHC→phosphenium adducts. This interpretation is supported by the calculation, at the DFT level, of a heterolytic dissociation mode of the N(2)C-P bond lower in energy than the homolytic one. A mesomeric description of the NHC→phosphenium entity is also proposed on the basis of electron localization function (ELF) and atoms in molecules (AIM) analyses. Finally ELF and AIM-based Fukui indices, molecular orbitals, and MESP analyses show that the initial attack of Cl(-) takes place at the carbenic atom of BIMIONAP.

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“…[7] All other relevant compoundsi ncluding [RTe(NHC)] + (4a 2.091(8) ; [8] 4c 2.117(5) ; [9] Scheme 2), [(NHC) 2 Te] 2 + (2.136(8), 2.138(5) ), [6] (NHC)Te X 2 (X = Cl, 2.103(3) ; [10] X = I, 2.106(5) [11a] ), and (NHC)[TeN(OÀBF 3 ) = C(H)(C 6 H 4 )] (2.179(9) ) [11b] possessm uch shorter CÀTe bond lengths. The CÀTe bond lengths of 1a·2 (2.343(4) )a nd 1a·3 (2.524(2)a nd 2.530(2) ;t wo independent conformers) are significantly longert han the sum of single-bond covalent radii for Te and C( 2.12 ).…”

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confidence: 99%

Nature of Bonding in Donor–Acceptor Interactions Exemplified by Complexes of N‐Heterocyclic Carbenes with 1,2,5‐Telluradiazoles

Pushkarevsky

Петров

Grigoriev

et al. 2017

Chemistry A European J

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Comprehensive structural, spectroscopic, and quantum chemical analyses of new donor-acceptor complexes between N-heterocyclic carbenes and 1,2,5-telluradiazoles and a comparison with previously known complexes involving tellurenyl cations showed that the dative C-Te bonds cannot be solitarily described with only one Lewis formula. Canonical Lewis formulas that denote covalency and arrows emphasizing ionicity complement each other in varying extents. Evaluation of the relative weights of these resonance forms requires proper bonding description with a well-balanced toolbox of analytical methods. If for conciseness only, one resonance form is used, it must be the most significant one according to the analytical evaluation. If unclear, all significant resonance forms should be displayed.

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Tellurium(II)‐Centered Dications from the Pseudohalide “Te(OTf)₂”

Cited by 50 publications

References 38 publications

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Imidazoliophosphines are True N‐Heterocyclic Carbene (NHC)–Phosphenium Adducts

Nature of Bonding in Donor–Acceptor Interactions Exemplified by Complexes of N‐Heterocyclic Carbenes with 1,2,5‐Telluradiazoles

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Tellurium(II)‐Centered Dications from the Pseudohalide “Te(OTf)2”

Cited by 50 publications

References 38 publications

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Imidazoliophosphines are True N‐Heterocyclic Carbene (NHC)–Phosphenium Adducts

Nature of Bonding in Donor–Acceptor Interactions Exemplified by Complexes of N‐Heterocyclic Carbenes with 1,2,5‐Telluradiazoles

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Tellurium(II)‐Centered Dications from the Pseudohalide “Te(OTf)₂”