TY - JOUR
T1 - Vinylmetalloids. I. Coupling reactions of group IV metalloidal halides with magnesium in tetrahydrofuran
AU - Soderquist, John A.
AU - Hassner, Alfred
PY - 1978/8/15
Y1 - 1978/8/15
N2 - The reaction of vinyl bromide with a mixture of magnesium and either dichlorodimethylsilane or dichlorodiethylgermane in tetrahydrofuran was found to give the corresponding coupled products: 1,1,2,2-tetramethyl-1,2-divinyldisilane (II) and 1,1,2,2-tetraethyl-l,2-divinyldigermane (XI), respectively, in ca. 30% yield. Other vinyl bromides also were investigated. The reaction of dichlorodimethylsilane with vinyl bromide/magnesium appears to proceed via chloro(dimethyl)vinylsilane (III) which was found to react directly with magnesium in THF to give II in 53% yield. It is shown that the reaction of a vinylsilyl halide with magnesium, if carried out in the presence of chlorotrimethylsilane or chlorotriethylgermane, leads to pentamethylvinyldisilane (VI) or triethyl(vinyldimethylsilyl)germane (V) in yields of 67 and 43%, respectively. However, the reaction of III and chlorotrimethylgermane with magnesium in THF gives a 40/60 mixture of trimethyl(vinyldimethylsilyl)germane (VII) and hexamethyldigermane (VIII). Under similar conditions, chlorotrimethylgermane was found to give VIII directly with magnesium in THF in 48% yield while chlorotriethylgermane is inert to Mg. These results are discussed in terms of the formation of metalloidalmagnesium bonds.
AB - The reaction of vinyl bromide with a mixture of magnesium and either dichlorodimethylsilane or dichlorodiethylgermane in tetrahydrofuran was found to give the corresponding coupled products: 1,1,2,2-tetramethyl-1,2-divinyldisilane (II) and 1,1,2,2-tetraethyl-l,2-divinyldigermane (XI), respectively, in ca. 30% yield. Other vinyl bromides also were investigated. The reaction of dichlorodimethylsilane with vinyl bromide/magnesium appears to proceed via chloro(dimethyl)vinylsilane (III) which was found to react directly with magnesium in THF to give II in 53% yield. It is shown that the reaction of a vinylsilyl halide with magnesium, if carried out in the presence of chlorotrimethylsilane or chlorotriethylgermane, leads to pentamethylvinyldisilane (VI) or triethyl(vinyldimethylsilyl)germane (V) in yields of 67 and 43%, respectively. However, the reaction of III and chlorotrimethylgermane with magnesium in THF gives a 40/60 mixture of trimethyl(vinyldimethylsilyl)germane (VII) and hexamethyldigermane (VIII). Under similar conditions, chlorotrimethylgermane was found to give VIII directly with magnesium in THF in 48% yield while chlorotriethylgermane is inert to Mg. These results are discussed in terms of the formation of metalloidalmagnesium bonds.
UR - http://www.scopus.com/inward/record.url?scp=0012939539&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)84880-9
DO - 10.1016/S0022-328X(00)84880-9
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AN - SCOPUS:0012939539
SN - 0022-328X
VL - 156
SP - 227
EP - 233
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -