Reaction of [Tris(trimethylsilyl)methyl]tribromogermane with Magnesium:  Generation of a Bromogermylene

Abstract

The reaction of [tris(trimethylsilyl)methyl]tribromogermane with magnesium in the presence of olefins and acetylenes has been investigated. 1,4-Digermabicyclo[2.2.0]hexanes and bromogermacyclopent-3-ene are obtained in the reactions of [tris(trimethylsilyl)methyl]bromogermylene with olefins and 1,3-butadiene, respectively. In the presence of diphenylacetylene a 1,2dihydro-1,2-digermacyclobutene was formed, which can be explained in terms of an electron-transfer reaction of the bromogermylene intermediate.

A Stable Halosilylene at Room Temperature in THF Solution

“…The precursor, tribromo[tris(trimethylsilyl)methyl]silane ( 5 ), containing the bulky tris(trimethylsilyl)methyl group to stabilize halosilylene, 6 , kinetically , was prepared in high yield …”

The Ate Complexes [M{C(SiMe3)3}(μ-SBu)2Li(THF)2] (M = Ge or Sn). The First Structural Characterization of Organometallic Ate Complexes of Group 14 Metals in Oxidation State II

“…The geometry of the Tsi group is as expected for the group attached to Ge or Sn . The Ge II −Tsi bond in 1 (2.096(5) Å) is similar in length to those in the Ge II compounds Ge(Tsi)CH(SiMe 3 ) 2 (2.067(4) Å) 33 or Ge(Tsi)(η 5 -C 5 H 5 ) (2.135(17) Å) 34 and significantly longer than Ge IV −Tsi bonds (1.94(1) −1.99(1) Å). ,− Likewise the Sn II −Tsi bond in 2 (2.295(3) Å) is similar in length to the Sn−C bonds in the Sn II compounds [Sn{C(SiMe 2 Ph) 3 }Cl] 2 (2.296(10) Å) and [Sn{C(SiMe 3 ) 2 (SiMe 2 OMe)}Cl] 2 14 (2.294(5) Å) and significantly longer than the Sn−C bonds in tris(triorganosilyl)methyl−Sn IV derivatives (2.120(11) to 2.191(11) Å). − …”

“…cantly longer than Ge IV -Tsi bonds (1.94(1) -1.99(1) Å).20,[35][36][37] Likewise the Sn II -Tsi bond in 2 (2.295(3) Å) is similar in length to the Sn-C bonds in the Sn II compounds [Sn{C(SiMe 2 Ph) 3 }Cl] 2 (2.296(10) Å) and [Sn{C(SiMe 3 ) 2 -(SiMe 2 OMe)}Cl] 2 14 (2.294(5) Å) and significantly longer than the Sn-C bonds in tris(triorganosilyl)methyl-Sn IV derivatives (2.120(11) to 2.191(11) Å).…”

From a Transient 3-Germa-1-phosphabutadiene to a 1,2-Bis(phosphaalkenyl)-1,2-digermacyclobutane

“…This molecule has longer Ge−C and C−C bonds than 2 (respectively 2.097(7) and 1.63(1) Å) but a much shorter Ge−Ge bond (2.422(2) Å). Other 1,2-digermacyclobutanes , and 1,4-digermabicyclo[2.2.0]hexanes , (thus, including two 1,2-digermacyclobutane rings) have been prepared from germylenes and alkenes. Such heterocycles also display long intracyclic Ge−Ge, Ge−C, and C−C bonds; however, these are not as long as those bonds in 2 .…”