N‐Heterocyclic Carbene Stabilized Digermanium(0)

Sidiropoulos, Anastas; Jones, Cameron; Stasch, Andreas; Klein, Susanne; Frenking, Gernot

doi:10.1002/ange.200905495

Cited by 111 publications

(58 citation statements)

References 49 publications

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“…Compounds 1-5 are representative examples of syntheses achieved prior to the material that forms the focus of this review. Successful isolations have been carried out for C 1 , [4] Si 2 , [2] Ge 2 , [5] P 2 , [6] and As 2 [7] stabilised by NHC (Ar 2 NHC; Ar = 2,6-diispropylphenyl in most cases) ligands, and P 1 /P 2 by the cyclic alkyl amino carbene ligand (CAAC, for example, 5). [8] Stabilisation of larger P n fragments and clusters by either NHC or CAAC ligands has also been accomplished.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Field of Main‐Group Mono‐ and Diatomic “Allotropes” Stabilised by Neutral Ligands

Wilson¹,

Dutton²

2013

Chemistry A European J

103

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The study of ligand stabilised mono- and diatomic zero oxidation state complexes is a young and fascinating topic. This area merges the fields of low-oxidation-state main-group chemistry, homoatomic multiple bonding and fundamental coordination chemistry. As with a great deal of recent coordination chemistry within the d-block, carbene ligands are clearly the star of the show, highlighting their importance within the p-block as well. This Minireview focuses on the significant developments of the past two years.

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Section: Introductionmentioning

confidence: 99%

Recent Advances in the Field of Main‐Group Mono‐ and Diatomic “Allotropes” Stabilised by Neutral Ligands

Wilson¹,

Dutton²

2013

Chemistry A European J

103

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“…However, NHCs may also be regarded as "stabilizing ligands" of highly reactive nonmetallic electrodeficient species with low coordinence. Stabilization of p-block elements in the zero-oxidation state by NHCs was recently reported for the :Si=Si:, [4] :Ge=Ge:, [5] :PÀP:, [6] P n , [7] and C 1 fragments.…”

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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“…For the Group 14 species, trans-bent NHC-E=E-NHC motifs are observed. [2,3] In the latter case EÀE single bonds are observed, with two lone pairs of electrons about each Group 15 center. [4,5] Either a trans-bent or gauche configuration was observed in the crystal structures depending on the steric demands of the NHC used.…”

mentioning

confidence: 95%

“…The synthesis and theoretical assessment of Lewis basestabilized E 0 "allotropes" of p-block elements continues to provide exciting developments, with new molecules having recently been synthesized for elements in Groups 14 and 15, including "C 1 ", [1] "Si 2 ", [2] "Ge 2 ", [3] "P 2 ", [4] and "As 2 ". [5] In the majority of cases the stabilizing base is an N-heterocyclic carbene (NHC) ligand.…”

mentioning

confidence: 99%