@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{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{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{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}
}