TY - JOUR
T1 - The Synthesis of Tris(silyl)silanides Revisited. A Study of Reactivity and Stability
AU - Lainer, Thomas
AU - Fischer, Roland C.
AU - Haas, Michael
N1 - Publisher Copyright:
© 2022 The Authors. Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH.
PY - 2022/10/14
Y1 - 2022/10/14
N2 - In this contribution, we investigated the stability of (H3Si)3SiLi (2a) in the presence of tetramethylethylenediamine (TMEDA) and 1,2-bis(diphenylphosphino)ethane (DPPE). Moreover, the synthesis to obtain tris(silyl)silanides with alternated counter ions by the base mediated desilylation approach was described. Additionally, metal-metal exchange reactions of 2 a with MgBr2, ZnCl2, HgCl2 were examined. Subsequently, we reacted 2 a with 1.0 and 0.5 equivalents of ZnCl2[TMEDA] and could obtain the isolable zinc substituted silanides 5 a,b. Finally, we reacted 2 a with equimolar amounts of [(MesNacnac)MgI(OEt2)] and [(DippNacnac)MgI(OEt2)] and found the selective transmetalation to the corresponding magnesium substituted silanides 6 a,b in good yields. Interestingly, for compounds 5 a,b and 6 a,b the removal of the reaction solvents did not induce a degradation. For compound 6 a crystals suitable for X-ray analysis could be grown, which represents the first structural characterization of an isolable perhydrogenated hypersilanide.
AB - In this contribution, we investigated the stability of (H3Si)3SiLi (2a) in the presence of tetramethylethylenediamine (TMEDA) and 1,2-bis(diphenylphosphino)ethane (DPPE). Moreover, the synthesis to obtain tris(silyl)silanides with alternated counter ions by the base mediated desilylation approach was described. Additionally, metal-metal exchange reactions of 2 a with MgBr2, ZnCl2, HgCl2 were examined. Subsequently, we reacted 2 a with 1.0 and 0.5 equivalents of ZnCl2[TMEDA] and could obtain the isolable zinc substituted silanides 5 a,b. Finally, we reacted 2 a with equimolar amounts of [(MesNacnac)MgI(OEt2)] and [(DippNacnac)MgI(OEt2)] and found the selective transmetalation to the corresponding magnesium substituted silanides 6 a,b in good yields. Interestingly, for compounds 5 a,b and 6 a,b the removal of the reaction solvents did not induce a degradation. For compound 6 a crystals suitable for X-ray analysis could be grown, which represents the first structural characterization of an isolable perhydrogenated hypersilanide.
KW - hydrides
KW - metallation
KW - silanes
KW - silanides
KW - silicon
UR - http://www.scopus.com/inward/record.url?scp=85129237397&partnerID=8YFLogxK
U2 - 10.1002/zaac.202200137
DO - 10.1002/zaac.202200137
M3 - Article
AN - SCOPUS:85129237397
SN - 0044-2313
VL - 648
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
IS - 19
M1 - e202200137
ER -