0000000001302143
AUTHOR
Felicitas Lips
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand, Ch-M-Ch, bond angles that are often well below 90°. Furthermore, and contrary to normal steric expectations, the interligand angles were found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, in…
Tetracyclic silaheterocycle formed through a pericyclic reaction cascade including a two-fold intramolecular C–C bond activation
Reductive debromination of the tribromoamidosilane 2 gave the tetracyclic silaheterocycle 3 through a unique reaction cascade involving unprecedented two-fold intramolecular cycloaddition by transient silylenes. Experimental and computational analyses of the reaction mechanism allowed the identification of the key intermediates that lead to the silaheterocycle 3 or, alternatively, to the cyclotrisilene 19. peerReviewed
Reversible complexation of ethylene by a silylene under ambient conditions.
Treatment of toluene solutions of the silylenes Si(SArMe6)2 (ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2, 1) or Si(SArPri4)2 (ArPri4 = C6H3-2,6(C6H3-2,6-Pri2)2, 2) with excess ethylene gas affords the siliranes (ArMe6S)2tiebar above startSiCH2tiebar above endCH2 (3) or (ArPri4S)2tiebar above startSiCH2tiebar above endCH2 (4). Silirane 4 evolves ethylene spontaneously at room temperature in toluene solution. A Van’t Hoff analysis by variable-temperature 1H NMR spectroscopy showed that ΔGassn = −24.9(2.5) kJ mol–1 for 4. A computational study of the reaction mechanism using a model silylene Si(SPh)2 (Ph = C6H5) was in harmony with the Van’t Hoff analysis, yielding ΔGassn = −24 kJ mol–1 and an activatio…
Reactions of Alkenes and Alkynes with an Acyclic Silylene and Heavier Tetrylenes under Ambient Conditions
Cycloaddition reactions of the acyclic silylene Si(SAriPr4)2 (AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) with a variety of alkenes and alkynes were investigated. Its reactions with the alkynes phenylacetylene and diphenylacetylene and the diene 2,3-dimethyl-1,3-butadiene yielded silacycles (AriPr4S)2tiebar above startSi(CH═tiebar above endCPh) (1), (AriPr4S)2tiebar above startSi(PhC═tiebar above endCPh) (2), and (AriPr4S)2tiebar above startSiCH2CMeCMetiebar above endCH2 (3) at ambient temperature. The compounds were characterized by X-ray crystallography, 1H, 13C, and 29Si NMR spectroscopy, and IR spectroscopy. No reaction was observed with more substituted alkenes such as propene, (Z)-2-butene, te…
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features—the most notable of which is their strong tendency to display acute interligand, Ch–M–Ch, bond angles that are often well below 90°. Furthermore, and contrary to normal steric expectations, the interligand angles were found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, in…
CCDC 955314: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955316: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955306: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955308: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 1427361: Experimental Crystal Structure Determination
Related Article: Felicitas Lips, James C. Fettinger, Akseli Mansikkamäki, Heikki M. Tuononen, and Philip P. Power|2014|J.Am.Chem.Soc.|136|634|doi:10.1021/ja411951y
CCDC 2118011: Experimental Crystal Structure Determination
Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A
CCDC 955309: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955315: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955300: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 2118012: Experimental Crystal Structure Determination
Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A
CCDC 1035161: Experimental Crystal Structure Determination
Related Article: Felicitas Lips, Akseli Mansikkamäki, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2014|Organometallics|33|6253|doi:10.1021/om500947x
CCDC 1035162: Experimental Crystal Structure Determination
Related Article: Felicitas Lips, Akseli Mansikkamäki, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2014|Organometallics|33|6253|doi:10.1021/om500947x
CCDC 955298: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955313: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955302: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 1035163: Experimental Crystal Structure Determination
Related Article: Felicitas Lips, Akseli Mansikkamäki, James C. Fettinger, Heikki M. Tuononen, Philip P. Power|2014|Organometallics|33|6253|doi:10.1021/om500947x
CCDC 2118009: Experimental Crystal Structure Determination
Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A
CCDC 955312: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955307: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955303: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 1427362: Experimental Crystal Structure Determination
Related Article: Felicitas Lips, James C. Fettinger, Akseli Mansikkamäki, Heikki M. Tuononen, and Philip P. Power|2014|J.Am.Chem.Soc.|136|634|doi:10.1021/ja411951y
CCDC 955310: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955299: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 2118008: Experimental Crystal Structure Determination
Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A
CCDC 2118010: Experimental Crystal Structure Determination
Related Article: Joschua Helmer, Olli J. Pakkanen, Chris Gendy, Alexander Hepp, Heikki M. Tuononen, Felicitas Lips|2022|Chem.Commun.|58|3549|doi:10.1039/D2CC00298A
CCDC 955301: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955311: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955305: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a
CCDC 955304: Experimental Crystal Structure Determination
Related Article: Brian D. Rekken , Thomas M. Brown , James C. Fettinger , Felicitas Lips , Heikki M. Tuononen , Rolfe H. Herber , and Philip P. Power|2013|J.Am.Chem.Soc.|135|10134|doi:10.1021/ja403802a