Disilenes, reactions with carbon

In contrast to alkenes, disilene derivatives react very smoothly with various haloalkanes as shown in Eqs. (81) and (82). Tetramesityldisilene 1 reacts with tert-butyl chloride to give hydrogen chloride adduct 172 together with 2-methylpropene (173), while treatment of 1 with benzyl chloride affords l-benzyl-2-chlorodisilane 174.126 The reactions of tetrasilyldisilene 22 with haloalkanes proceed in a similar way to give l-halo-2-(haloalkyl)disilanes 175, whereas the reaction with carbon tetrahal-ides affords the corresponding 1,2-dihalodisilanes 176.127... 

From the reactions of carbon monoxide in frozen matrices with Me2Si155 and several arylsilylenes Mes(R)Si (R = Mes, 2,6-diisopropylphenoxy, f-Bu)156, adducts were formed (see Section V.A.2). Theoretical calculations led to consideration of both a linear silaketene and a pyramidal n-donor base complex structure for the Me2Si(CO) adduct249. The observation that warming the carbon monoxide adducts of the arylsilylenes led to the formation of disilenes was interpreted as indicating the formation of a nonplanar complex that could dissociate as do other silylene-n-donor base complexes156. 

The reactions of cyclic disilenes with haloalkanes proceed in a similar way. Cyclotrisilene 48 reacts with carbon tetrachloride without cleavage of endocyclic Si-Si bonds to give trans-1,2-dichlorocyclotrisilane 179 stereo specifically [Eq. (84)].24 The a h -stereochemistry is in good accord with the radical mechanism of the reactions as stated above. Similarly, cyclic disilenes 49 and 50 react with carbon tetrachloride and 1,2-dibromoethane giving the corresponding trau.v-1,2-dihalodi-silanes 180 [Eq. (85)].129 Methyl iodide adds to cyclic disilene 50 in an a tz-addition manner to give 181.104... 

Silanones, the silicon analogs of ketones, are produced via rDA reactions. One attempt to prepare a suitable DA precursor for retrograde decomposition to a silanone met with unexpected results. The desired DA reaction between 2,2-dimethyl-l-oxa-2-silacyclohexa-3,S-diene (251) and perfluoro-2-but-yne was complete in one day at room temperature. The observed product was o-bis(trifluoromethyl)ben-zene, as the initial adduct apparently underwent retrodiene decomposition to yield the intermediate dimethylsilanone (252) (equation 111). The occurrence of this retro ene process at room temperature was not consistent with the analogous extrusions of silenes and disilenes that require elevated temperatures. However, the reaction sequence was substantiated by comparison with its carbon analog in which tetramethylpyran and dimethyl acetylenedicarboxylate react at room temperature to afford only acetone and the corresponding phthalate. Stable adducts that extrude silanones are also known. Reactions of 2-sili yrans and nudeic anhydride provide stable adducts, such as (253), that decompose upon thermolysis... 

---