@article{PhilippRadius2022,
  author    = {Philipp, Michael S. M. and Radius, Udo},
  title     = {A Versatile Route To Cyclic (Alkyl)(Amino)Carbene-Stabilized Stibinidenes},
  series = {Zeitschrift f{\"u}r Anorganische und Allgemeine Chemie},
  volume    = {648},
  journal   = {Zeitschrift f{\"u}r Anorganische und Allgemeine Chemie},
  number    = {17},
  issn      = {0044-2313},
  doi       = {10.1002/zaac.202200085},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-318272},
  year      = {2022},
  abstract  = {A convenient route for the synthesis of the cAAC\(^{Me}\) (cAAC=cyclic (alkyl)(amino)carbene, cAAC\(^{Me}\)=1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene) and cAAC\(^{Cy}\) (cAAC\(^{Cy}\)=2-azaspiro[4.5]dec-2-(2,6-diisopropylphenyl)-3,3-dimethyl-1-ylidene) stabilized stibinidenes cAAC\(^{Me}\)⋅SbMes (2a) (Mes=2,4,6-trimethylphenyl) and cAAC\(^{Cy}\)⋅SbMes (2b) is reported. A mechanism for the formation of [cAAC\(^{R}\)Cl][SbCl\(_{3}\)Mes] 1 and cAAC\(^{R}\)⋅SbMes 2 from the reaction of cAAC with the antimony(III) precursor SbCl\(_{2}\)Mes, which proceeds via the isolable intermediate [cAAC\(^{R}\)SbClMes][SbCl\(_{3}\)Mes] (3), is proposed.},
  language  = {en}
}
@article{HuangHuShietal.2022,
  author    = {Huang, Mingming and Hu, Jiefeng and Shi, Shasha and Friedrich, Alexandra and Krebs, Johannes and Westcott, Stephen A. and Radius, Udo and Marder, Todd B.},
  title     = {Selective, Transition Metal-free 1,2-Diboration of Alkyl Halides, Tosylates, and Alcohols},
  series = {Chemistry-A European Journal},
  volume    = {28},
  journal   = {Chemistry-A European Journal},
  number    = {24},
  doi       = {10.1002/chem.202200480},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-318262},
  year      = {2022},
  abstract  = {Defunctionalization of readily available feedstocks to provide alkenes for the synthesis of multifunctional molecules represents an extremely useful process in organic synthesis. Herein, we describe a transition metal-free, simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols. Control experiments demonstrated that the key to this high reactivity and selectivity is the addition of a combination of potassium iodide and N,N-dimethylacetamide (DMA). The practicality and industrial potential of this transformation are demonstrated by its operational simplicity, wide functional group tolerance, and the late-stage modification of complex molecules. From a drug discovery perspective, this synthetic method offers control of the position of diversification and diastereoselectivity in complex ring scaffolds, which would be especially useful in a lead optimization program.},
  language  = {en}
}
@article{PhilippBertermannRadius2022,
  author    = {Philipp, Michael S. M. and Bertermann, R{\"u}diger and Radius, Udo},
  title     = {N-Heterocyclic Carbene and Cyclic (Alkyl)(amino)carbene Adducts of Germanium(IV) and Tin(IV) Chlorides and Organyl Chlorides},
  series = {European Journal of Inorganic Chemistry},
  volume    = {2022},
  journal   = {European Journal of Inorganic Chemistry},
  number    = {32},
  doi       = {10.1002/ejic.202200429},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-293865},
  year      = {2022},
  abstract  = {A study on the reactivity of N-heterocyclic carbenes (NHCs) and the cyclic (alkyl)(amino)carbene cAAC\(^{Me}\) with selected germanium(IV) and tin(IV) chlorides and organyl chlorides is presented. The reactions of the NHCs Me\(_{2}\)Im\(^{Me}\), iPr\(_{2}\)Im\(^{Me}\) and Dipp2Im with the methyl chlorides ECl\(_{2}\)Me\(_{2}\) afforded the adducts NHC ⋅ ECl\(_{2}\)Me\(_{2}\) (E=Ge (1), Sn (2)), NHC=Me\(_{2}\)Im\(^{Me}\) (a), iPr\(_{2}\)Im\(^{Me}\) (b), Dipp\(_{2}\)Im (c)). The reaction of Me2Im\(^{Me}\) with GeCl\(_{4}\) led to isolation of Me\(_{2}\)Im\(^{Me}\) ⋅ GeCl\(_{4}\) (3), the reaction of iPr\(_{2}\)Im\(^{Me}\) with SnCl\(_{4}\) in THF afforded the THF adduct iPr\(_{2}\)Im\(^{Me}\) ⋅ SnCl\(_{4}\) ⋅ THF (4). Dipp\(_{2}\)Im ⋅ GeCl\(_{2}\)Me\(_{2}\) (1 c) isomerized into the backbone coordinated imidazolium salt [aDipp\(_{2}\)Im ⋅ GeClMe\(_{2}\)][Cl] (5) upon thermal treatment. The reactions of cAAC\(^{Me}\) with (i) ECl\(_{2}\)R\(_{2}\) (E=Ge, Sn) gave the adducts cAAC\(^{Me}\) ⋅ ECl\(_{2}\)R\(_{2}\) (R=Me: E=Ge (6); Sn (7); Ph: E=Ge (8)), with (ii) GeClMe\(_{3}\) and GeCl\(_{4}\) the salts [cAAC\(^{Me}\) ⋅ GeMe\(_{3}\)][Cl] (9) and [cAACMeCl][GeCl\(_{3}\)] (10), and (iii) with SnCl\(_{4}\) the salt [cAACMeCl][SnCl\(_{3}\)] (11) and the adduct cAAC\(^{Me}\) ⋅ SnCl\(_{4}\) (12). Reduction of 2 a with KC\(_{8}\) afforded the NHC-stabilized stannylene Me\(_{2}\)Im\(^{Me}\) ⋅ SnMe\(_{2}\) 13, reduction of 7 with either KC8 or 1,4-bis-(trimethylsilyl)-1,4-dihydropyrazin in the presence of SnCl\(_{2}\)Me\(_{2}\) yielded cAAC\(^{Me}\) ⋅ SnMe\(_{2}\) ⋅ SnMe\(_{2}\)Cl\(_{2}\) (14).},
  language  = {en}
}
@article{TenderaLuffKrummenacheretal.2022,
  author    = {Tendera, Lukas and Luff, Martin S. and Krummenacher, Ivo and Radius, Udo},
  title     = {Cationic Nickel d\(^{9}\)-Metalloradicals [Ni(NHC)\(_{2}\)]\(^{+}\)},
  series = {European Journal of Inorganic Chemistry},
  volume    = {2022},
  journal   = {European Journal of Inorganic Chemistry},
  number    = {31},
  doi       = {10.1002/ejic.202200416},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-293702},
  year      = {2022},
  abstract  = {A series of five new homoleptic, linear nickel d\(^{9}\)-complexes of the type [Ni\(^{I}\)(NHC)\(_{2}\)]\(^{+}\) is reported. Starting from the literature known Ni(0) complexes [Ni(Mes\(_{2}\)Im)\(_{2}\)] 1, [Ni(Mes\(_{2}\)Im\(^{H2}\))2] 2, [Ni(Dipp\(_{2}\)Im)\(_{2}\)] 3, [Ni(Dipp\(_{2}\)Im\(^{H2}\))\(_{2}\)] 4 and [Ni(cAAC\(^{Me}\))\(_{2}\)] 5 (Mes\(_{2}\)Im=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene, Mes\(_{2}\)Im\(^{H2}\)=1,3-bis(2,4,6-trimethylphenyl)-imidazolidin-2-ylidene, Dipp\(_{2}\)Im=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene, Dipp\(_{2}\)Im\(^{H2}\)=1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene, cAAC\(^{Me}\)=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-yliden), their oxidized Ni(I) analogues [Ni\(^{I}\)(Mes\(_{2}\)Im)\(_{2}\)][BPh\(_{4}\)] 1\(^{+}\), [Ni\(^{I}\)(Mes\(_{2}\)Im\(^{H2}\))\(_{2}\)][BPh\(_{4}\)] 2\(^{+}\), [Ni\(^{I}\)(Dipp\(_{2}\)Im)\(_{2}\)][BPh\(_{4}\)] 3\(^{+}\), [Ni\(^{I}\)(Dipp\(_{2}\)Im\(^{H2}\))\(_{2}\)][BPh\(_{4}\)] 4\(^{+}\) and [Ni\(^{I}\)(cAAC\(^{Me}\))\(_{2}\)][BPh\(_{4}\)] 5\(^{+}\) were synthesized by one-electron oxidation with ferrocenium tetraphenyl-borate. The complexes 1\(^{+}\)-5\(^{+}\) were fully characterized including X-ray structure analysis. The complex cations reveal linear geometries in the solid state and NMR spectra with extremely broad, paramagnetically shifted resonances. DFT calculations predicted an orbitally degenerate ground state leading to large magnetic anisotropy, which was verified by EPR measurements in solution and on solid samples. The magnetic anisotropy of the complexes is highly dependent from the steric protection of the metal atom, which results in a noticeable decrease of the g-tensor anisotropy for the N-Mes substituted complexes 1\(^{+}\) and 2\(^{+}\) in solution due to the formation of T-shaped THF adducts.},
  language  = {en}
}
@article{PhilippBertermannRadius2023,
  author    = {Philipp, Michael S. M. and Bertermann, R{\"u}diger and Radius, Udo},
  title     = {Activation of Ge-H and Sn-H Bonds with N-Heterocyclic Carbenes and a Cyclic (Alkyl)(amino)carbene},
  series = {Chemistry - A European Journal},
  volume    = {29},
  journal   = {Chemistry - A European Journal},
  number    = {3},
  doi       = {10.1002/chem.202202493},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-311929},
  year      = {2023},
  abstract  = {A study of the reactivity of several N-heterocyclic carbenes (NHCs) and the cyclic (alkyl)(amino)carbene 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene (cAAC\(^{Me}\)) with the group 14 hydrides GeH2Mes2 and SnH2Me2 (Me=CH\(_{3}\), Mes=1,3,5-(CH\(_{3}\))\(_{3}\)C\(_{6}\)H\(_{2}\)) is presented. The reaction of GeH\(_{2}\)Mes\(_{2}\) with cAAC\(^{Me}\) led to the insertion of cAAC\(^{Me}\) into one Ge-H bond to give cAAC\(^{Me}\)H-GeHMes\(_{2}\) (1). If 1,3,4,5-tetramethyl-imidazolin-2-ylidene (Me\(_{2}\)Im\(^{Me}\)) was used as the carbene, NHC-mediated dehydrogenative coupling occurred, which led to the NHC-stabilized germylene Me\(_{2}\)Im\(^{Me}\)⋅GeMes\(_{2}\) (2). The reaction of SnH\(_{2}\)Me\(_{2}\) with cAAC\(^{Me}\) also afforded the insertion product cAAC\(^{Me}\)H-SnHMe\(_{2}\) (3), and reaction of two equivalents Me\(_{2}\)Im\(^{Me}\) with SnH\(_{2}\)Me\(_{2}\) gave the NHC-stabilized stannylene Me\(_{2}\)Im\(^{Me}\)⋅SnMe\(_{2}\) (4). If the sterically more demanding NHCs Me\(_{2}\)Im\(^{Me}\), 1,3-di-isopropyl-4,5-dimethyl-imidazolin-2-ylidene (iPr\(_{2}\)Im\(^{Me}\)) and 1,3-bis-(2,6-di-isopropylphenyl)-imidazolin-2-ylidene (Dipp\(_{2}\)Im) were employed, selective formation of cyclic oligomers (SnMe\(_{2}\))\(_{n}\) (5; n=5-8) in high yield was observed. These cyclic oligomers were also obtained from the controlled decomposition of cAAC\(^{Me}\)H-SnHMe\(_{2}\) (3).},
  language  = {en}
}
@article{JosSzwetkowskiSlebodnicketal.2022,
  author    = {Jos, Swetha and Szwetkowski, Connor and Slebodnick, Carla and Ricker, Robert and Chan, Ka Lok and Chan, Wing Chun and Radius, Udo and Lin, Zhenyang and Marder, Todd B. and Santos, Webster L.},
  title     = {Transition Metal-Free Regio- and Stereo-Selective trans Hydroboration of 1,3-Diynes: A Phosphine-Catalyzed Access to (E)-1-Boryl-1,3-Enynes},
  series = {Chemistry - A European Journal},
  volume    = {28},
  journal   = {Chemistry - A European Journal},
  number    = {63},
  doi       = {10.1002/chem.202202349},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-293784},
  year      = {2022},
  abstract  = {We report a transition metal-free, regio- and stereo-selective, phosphine-catalyzed method for the trans hydroboration of 1,3-diynes with pinacolborane that affords (E)-1-boryl-1,3-enynes. The reaction proceeds with excellent selectivity for boron addition to the external carbon of the 1,3-diyne framework as unambiguously established by NMR and X-ray crystallographic studies. The reaction displays a broad substrate scope including unsymmetrical diynes to generate products in high yield (up to 95 \%). Experimental and theoretical studies suggest that phosphine attack on the alkyne is a key process in the catalytic cycle.},
  language  = {en}
}
@article{FoehrenbacherKrahfussZapfetal.2021,
  author    = {F{\"o}hrenbacher, Steffen A. and Krahfuss, Mirjam J. and Zapf, Ludwig and Friedrich, Alexandra and Ignat'ev, Nikolai V. and Finze, Maik and Radius, Udo},
  title     = {Tris(pentafluoroethyl)difluorophosphorane: a versatile fluoride acceptor for transition metal chemistry},
  series = {Chemistry Europe},
  volume    = {27},
  journal   = {Chemistry Europe},
  number    = {10},
  doi       = {10.1002/chem.202004885},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256665},
  pages     = {3504-3516},
  year      = {2021},
  abstract  = {Fluoride abstraction from different types of transition metal fluoride complexes [L\(_n\)MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C\(_2\)F\(_5\))\(_3\)PF\(_2\) to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C\(_2\)F\(_5\))\(_3\)PF\(_3\)]\(^-\)) is reported. (C\(_2\)F\(_5\))\(_3\)PF\(_2\) reacted with trans-[Ni(iPr\(_2\)Im)\(_2\)(Ar\(^F\))F] (iPr2Im=1,3-diisopropylimidazolin-2-ylidene; Ar\(^F\)=C\(_6\)F\(_5\), 1 a; 4-CF\(_3\)-C\(_6\)F\(_4\), 1 b; 4-C\(_6\)F\(_5\)-C\(_6\)F\(_4\), 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr\(_2\)Im)\(_2\)(solv)(Ar\(^F\))]FAP (2 a-c[solv]; solv=Et\(_2\)O, CH\(_2\)Cl\(_2\), THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh\(_3\), solvent coordination was suppressed and the complexes trans-[Ni(iPr\(_2\)Im)\(_2\)(PPh\(_3\))(C\(_6\)F\(_5\))]FAP (trans-2 a[PPh\(_3\)]) and cis-[Ni(iPr\(_2\)Im)\(_2\)(Dipp\(_2\)Im)(C\(_6\)F\(_5\))]FAP (cis-2 a[Dipp\(_2\)Im]) (Dipp\(_2\)Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp\(_2\)Im)CuF] (3) in CH\(_2\)Cl\(_2\) or 1,2-difluorobenzene led to the isolation of [{(Dipp\(_2\)Im)Cu}\(_2\)]\(^2\)\(^+\)2 FAP\(^-\) (4). Subsequent reaction of 4 with PPh\(_3\) and different carbenes resulted in the complexes [(Dipp\(_2\)Im)Cu(LB)]FAP (5 a-e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp\(_2\)Im)Cu(C\(_6\)Me\(_6\))]FAP (5 f), which serves as a source of [(Dipp\(_2\)Im)Cu)]\(^+\). Fluoride abstraction of [Cp\(_2\)TiF\(_2\)] (7) resulted in the formation of dinuclear [FCp\(_2\)Ti(μ-F)TiCp\(_2\)F]FAP (8) (Cp=η\(^5\)-C\(_5\)H\(_5\)) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.},
  language  = {en}
}
@article{ZapfPetersBertermannetal.2022,
  author    = {Zapf, Ludwig and Peters, Sven and Bertermann, R{\"u}diger and Radius, Udo and Finze, Maik},
  title     = {Tricyanoborane-Functionalized Anionic N-Heterocyclic Carbenes: Adjustment of Charge and Stereo-Electronic Properties},
  series = {Chemistry - A European Journal},
  volume    = {28},
  journal   = {Chemistry - A European Journal},
  number    = {39},
  doi       = {10.1002/chem.202200275},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-287200},
  year      = {2022},
  abstract  = {The 1-methyl-3-(tricyanoborane)imidazolin-2-ylidenate anion (2) was obtained in high yield by deprotonation of the B(CN)3-methylimidazole adduct 1. Regarding charge and stereo-electronic properties, anion 2 closes the gap between well-known neutral NHCs and the ditopic dianionic NHC, the 1,3-bis(tricyanoborane)imidazolin-2-ylidenate dianion (IIb). The influence of the number of N-bonded tricyanoborane moieties on the σ-donating and π-accepting properties of NHCs was assessed by quantum chemical calculations and verified by experimental data on 2, IIb, and 1,3-dimethylimidazolin-2-ylidene (IMe, IIa). Therefore NHC 2, which acts as a ditopic ligand via the carbene center and the cyano groups, was reacted with alkyl iodides, selenium, and [Ni(CO)\(_{4}\)] yielding alkylated imidazoles 3 and 4, the anionic selenium adduct 5, and the anionic nickel tricarbonyl complex 8, respectively. The results of this study prove that charge, number of coordination sites, buried volume (\%V\(_{bur}\)) and σ-donor and π-acceptor abilities of NHCs can be effectively fine-tuned via the number of tricyanoborane substituents.},
  language  = {en}
}
@article{LuisHorrerPhilippetal.2021,
  author    = {Luis, Werner and Horrer, G{\"u}nther and Philipp, Michael and Lubitz, Katharina and Kuntze-Fechner, Maximilian W. and Radius, Udo},
  title     = {A General Synthetic Route to NHC-Phosphinidenes: NHC-mediated Dehydrogenation of Primary Phosphines},
  series = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie},
  volume    = {647},
  journal   = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie},
  number    = {8},
  doi       = {10.1002/zaac.202000405},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-258016},
  pages     = {881-895},
  year      = {2021},
  abstract  = {The dehydrocoupling of primary phosphines with N-heterocyclic carbenes (NHCs) to yield NHC-phosphinidenes is reported. The reaction of two equivalents of the NHCs Me\(_2\)Im (1,3-dimethylimidazolin-2-ylidene), Me\(_4\)Im (1,3,4,5-tetramethylimidazolin-2-ylidene), iPr\(_2\)Im (1,3-di-iso-propylimidazolin-2-ylidene) and Mes\(_2\)Im (2,4,6-trimethylphenylimidazolin-2-ylidene) with PhPH\(_2\) and MesPH\(_2\) led to the NHC stabilized phosphinidenes (NHC)PAr: (iPr\(_2\)Im)PPh (1), (Mes\(_2\)Im)PPh (2), (Me\(_4\)Im)PPh (3), (Mes\(_2\)Im)PMes (4), (Me\(_2\)Im)PMes (5), (Me\(_4\)Im)PMes (6) and (iPr\(_2\)Im)PMes (7). The reaction of tBuPH\(_2\) with two equivalents of the NHCs afforded the corresponding NHC stabilized parent phosphinidenes (NHC)PH: (iPr\(_2\)Im)PH (8), (Mes\(_2\)Im)PH (9) and (Me\(_4\)Im)PH (10). Reaction of 1 with oxygen and sulfur led to isolation of iPr\(_2\)Im-P(O)\(_2\)Ph (11) and iPr\(_2\)Im-P(S)\(_2\)Ph (12), whereas the reaction with elemental selenium and tellurium gave (NHC)PPh cleavage with formation of (iPr\(_2\)Im)Se (13), iPr\(_2\)ImTe (14) and different cyclo-oligophosphines. Furthermore, the complexes [{(iPr\(_2\)Im)PPh}W(CO)\(_5\)] (15), [Co(CO)\(_2\)(NO){(iPr\(_2\)Im)PPh}] (16) and [(η\(^5\)-C\(_5\)Me\(_2\))Co(η\(^2\)-C\(_2\)H\(_4\)){(iPr\(_2\)Im)PPh}] (17) have been prepared starting from 1 and a suitable transition metal complex precursor. The complexes 16 and 17 decompose in solution upon heating to ca. 80 °C to yield the NHC complexes [Co(iPr\(_2\)Im)(CO)\(_2\)(NO)] and [(η\(^5\)-C\(_5\)Me\(_5\))Co(iPr\(_2\)Im)(η\(^2\)-C\(_2\)H\(_4\))] with formation of cyclo-oligophosphines. The reaction of 1 with [Ni(COD)\(_2\)] afforded the diphosphene complex [Ni(iPr\(_2\)Im)\(_2\)(trans-PhP=PPh)] 18.},
  language  = {en}
}
@article{PhilippKrahfussRadackietal.2021,
  author    = {Philipp, Michael S. M. and Krahfuss, Mirjam J. and Radacki, Krzysztof and Radius, Udo},
  title     = {N-Heterocyclic Carbene and Cyclic (Alkyl)(amino)carbene Adducts of Antimony(III)},
  series = {European Journal of Inorganic Chemistry},
  volume    = {2021},
  journal   = {European Journal of Inorganic Chemistry},
  number    = {38},
  doi       = {10.1002/ejic.202100632},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257408},
  pages     = {4007-4019},
  year      = {2021},
  abstract  = {A systematic study on Lewis-acid/base adducts of N-heterocyclic carbenes (NHCs) and the cyclic (alkyl)(amino)carbene cAAC\(^{Me}\) (1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene) with antimony(III) chlorides of the general formula SbCl\(_{2}\)R (R=Cl, Ph, Mes) is presented. The reaction of the NHCs Me\(_{2}\)Im\(^{Me}\) (1,3,4,5-tetra-methyl-imidazolin-2-ylidene), iPr\(_{2}\)Im\(^{Me}\) (1,3-di-isopropyl-4,5-dimethyl-imidazolin-2-ylidene), Mes\(_{2}\)Im, Dipp\(_{2}\)Im (R\(_{2}\)Im=1,3-di-organyl-imidazolin-2-ylidene; Mes=2,4,6-trimethylphenyl, Dipp=2,6-di-isopropylphenyl) and cAAC\(^{Me}\) with antimony(III) compounds SbCl\(_{2}\)R (R=Cl (1), Ph (2) and Mes (3)) yields the adducts NHC ⋅ SbCl\(_{2}\)R (R=Cl (4), Ph (5) and Mes (6); NHC=Me\(_{2}\)Im\(^{Me}\) (a), iPr\(_{2}\)Im\(^{Me}\) (b), Dipp\(_{2}\)Im (c) and Mes\(_{2}\)Im (d)) and cAAC\(^{Me}\) ⋅ SbCl\(_{2}\)R (R=Cl (4 e) and Ph (5 e)). Thermal treatment of (Dipp\(_{2}\)Im) ⋅ SbCl\(_{2}\)Ar (Ar=Ph (5 c) and Mes (6 c)) in benzene leads to isomerization to the backbone coordinated \(^{a}\)NHC-adduct \(^{a}\)Dipp\(_{2}\)Im ⋅ SbCl\(_{2}\)Ar (Ar=Mes (7) and Ph (8)) (\(^{"a"}\) denotes "abnormal" coordination mode of the NHC) in high yields. One of the chloride substituents at antimony of 7 can be abstracted by GaCl3 or Ag[BF\(_{4}\)] to obtain the imidazolium salts [\(^{a}\)Dipp\(_{2}\)Im ⋅ SbClMes][BF\(_{4}\)] (9) and [\(^{a}\)Dipp\(_{2}\)Im ⋅ SbClMes][GaCl\(_{4}\)] (10).},
  language  = {en}
}