Organosilyls

Early work on the chemistry of organosilyl anions/anionoids has been thoroughly reviewed (/). The most frequently employed preparative routes involve either cleavage of a disilane, when HMPA (CAUTION—CANCER SUSPECT AGENT) is normally required as solvent, or reaction of bulky silyl chlorides with lithium metal. 

The trimeric platinum(O) complex [Pt3(CNBu )6] undergoes a double oxidative addition reaction with 2,2-bis(disilanyl)dithiane to give tetrakis(organosilyl)bis(/-butylisocyanide)platinum(IV) complexes.53 The Si—Ge bonds in bis(silylgermyl)dithiane are also cleaved by [Pt3(CNBu )6] giving analogous platinum(IV) complexes with Pt—Si and Pt—Ge bonds.53... 

See entry ORGANOSILYL PERCHLORATES See Other NON-METAL PERCHLORATES... 

Reactivity of Very Electron-Rich Organosilyl Amines... 

Isomerization sets in at higher temperatures than 273 K as apparent from NMR line broadening. The reason for a preference for the particular (cis O, N1) isomer is not obvious neither the O/N alternative for organosilyl migration nor the position of the cis/trans equilibrium with respect to the N-C(=X) bonds is easily predictable. 

Tetrahydropyridinium methy lides, for example, 209, have been prepared in situ from the organotin- or organosilyl-substituted imines. These react with iV-phcnylmalcimidcs to produce the completely saturated pyrroloindolizines <1997TL5441, 2004JOC1919> (Equation 25). 

The Sn6P6 cages 19c and 19d are accessible by two different Bronsted acid-base reaction pathways Reaction of lc and Id, respectively, with two different stannanediyl derivatives furnished in 80-89% yield red-black crystals of the aggregates (Eq. 12) (39). The tin(II) phosphandiides are somewhat related to the previously described oligomeric bis (phosphaneyl) stannanediyls of the type PkSn, which easily form intermolecular aggregates (50, 51) or remain monomeric, if the phosphorus atoms bear very crowded organosilyl substituents (52). 

ORGANOSILYL PERCHLORATES PERCHLORATE-DOPED CONDUCTING POLYMERS PERCHLORATE SALTS OF NITROGENOUS BASES and the individually indexed entries ... 

ALKYLHALOSILANES, ALKYLSILANES HALOSILANES, ORGANOSILYL PERCHLORATES SILANES, SILICONE GREASE, SILICONE LIQUID, SILICONE OIL SILYLHYDRAZINES, TRIALKYLSILYLOXY ORGANOLEAD DERIVATIVES... 

However, the 0-(fluorosilyl)-Af,Af-bis(organosilyl)hydroxylamine 204 undergoes an irreversible rearrangement yielding the isomeric Af-(fluorosilyl)-Af,0-bis(organosilyl) hydroxylamine 205 . The rearrangement proceeds via a dyotropic transition state to yield the hydroxylamine 205. An intermolecular thermal rearrangement with the insertion... 

These unusual shifts may be an indication of a significant d orbital participation, especially in phosphiran which probably has a nearly planar geometry and may possess some aromatic character as in the parent cyclopropanes [the P-H coupling in 3 of 155 Hz is between that found in PH2s (138 Hz) and PH3 (182 Hz)]. The same conclusions would to some extent apply to organogermyl-, organostannyl- and organosilyl-phosphines recently discussed by Schumann/1969,14)... 

Bis(organosilyl) peroxides are prepared by nucleophilic substitution reactions of hydrogen peroxide with chlorosilanes in the presence of base . Thus, bis(triorganosilyl) peroxide has been prepared from the reaction of 98% hydrogen peroxide and chlorosilane with ammonia as an HCl acceptor (equation 3). Bis(triphenylsilyl) peroxide 2 can also be prepared by the reaction of hydrogen peroxide and triphenyl silylamine (equation 4). 

Organosilyl substituted 7)5-cyclopentadienyl complexes may be prepared by two main procedures (a) reactions of silylated cyclopenta-dienes or their alkali metal derivatives, with an appropriate transition metal compound (carbonyl or halide) with formation of ir-bonds (b) metalation of a preformed 7j5-cyclopentadienyl complex, followed by treatment with an organohalosilane. 

Cyclopentadienylnickel carbonyl dimer is also known to react with acetylenes to form bridged complexes. With bis(trimethylsilyl)acetylene and with l,4-bis(trimethylsilyl)butadiyne it reacts to give organosilyl acetylene complexes 63) [Eqs. (47) and (48)]. The silylated butadiyne... 

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