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Controlled Conversion of the Transient 2‐Mesityl‐1,1‐bis(trimethylsilyl)silene into a Tetrahydro‐2,3‐disilanaphthalene, a 1,2‐Disilacyclobutane, or a 1,3‐Disilacyclobutane
Author(s) -
Krempner Clemens,
Reinke Helmut,
Oehme Hartmut
Publication year - 1995
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19951281105
Subject(s) - chemistry , trimethylsilyl , silylation , medicinal chemistry , silene , electrophile , bromide , polymer chemistry , organic chemistry , catalysis , biology , genetics
Mesityl[tris(trimethylsilyl)silyl]methanol ( 1 ) reacts with strong bases with elimination of trimethylsilanolate according to a Peterson‐type mechanism, the outcome of the reaction being dependent on solvent, temperature, and nature of the organometallic base applied. Thus, 1 was converted by treatment with MeLi in ether at –78°C to ( E )‐1,2,3,8a‐tetra ‐hydro‐1‐mesityl‐5,7,8a‐trimethyl‐2,2,3,3‐tetrakis (trimethylsi‐lyl)‐2,3‐disilanaphthalene ( 3 ), formally a [2 + 4] cyclodimer of the transient silene (Me 3 Si) 2 Si=CHMes ( 2 ). The reaction of 1 with PhMgBr in THF after some days resulted in the formation of ( Z )‐3,4‐dimesityl‐1,1,2,2‐tetrakis(trimethylsilyl) ‐1,2‐disilacyclobutane ( 6 ) as the main product besides small quantities of 3 , the polysilane (Me 3 SiSi(SiMe 3 ) 2 CH 2 Mes ( 10 ), and the alkoxysilane (Me 3 Si) 3 SiCH(Mes)OSi(Si‐Me 3 ) 2 CH 2 Mes ( 7 ). Compound 6 , the formal [2 + 2] cycloadduct of 2 , can also be obtained by thermal treatment of 3 and is considered to be the thermodynamically more stable silene dimer whereas 3 is the kinetically preferred product. At high LiBr concentrations in the reaction mixture 1 was converted by PhMgBr in THF to ( E )‐2,4‐dimesityl‐1,1,3,3‐tetrakis(tri‐ methylsilyl)‐1,3‐disilacyclobutane ( 13 ) besides 6 and [bis(tri‐methylsilyl)silyl]mesityl(trimethylsiloxy)methane ( 11 ). The unforeseen formation of 13 is discussed as proceeding via the silene‐lithium bromide adduct (Me 3 Si) 2 Si(Br)CH(Li)Mes ( 12 ). In the absence of LiBr 1 was converted by MeLi in THF at –78°C to 11 and the trisilane (Me 3 Si) 2 Si(Me)CH 2 Mes ( 4b ). Probable pathways of the formation of all new compounds are discussed. For 6 and 13 the results of the X‐ray structural analyses are given.