Disilene structure

Can one find systems, in which the bridged non conventional isomer is more stable than the conventional disilene structure Examination of the two dimerization paths in Scheme 3 suggests that a higher donor ability of the lone-pair on the substituent should favor the bridged structure. 

Bis(diisopropylamino)silylene has been generated by photolysis of the precursor (76), and trapped chemically by reaction with triethylvinylsilane and 2,3-dimethylbuta-l,3-diene.Contrary to theoretical prediction, its dimer seems to have a disilene structure and not a bridged structure. 

Very recently, synthesis and structure of molybdenum and tungsten complexes of the relatively unhindered disilene Si2Me4 were reported. The x-ray structure of 84 shows a metallacyclosilane structure with W — Si = 2.606(2) A and Si —Si = 2.260(3) A. The W — Si bond length is within the range of various estimates of the Si and W covalent radii and the Si —Si distance falls midway between the expected values for a single (2.35 A) and a double bond (2.14 A) (Fig. 13). 

Using CO-saturated hydrocarbon matrices, Pearsall and West" photolyzed sily-lene precursors at 77 K and monitored CO coordination to the silylenes by UV-vis spectroscopy (Scheme 13). Bis(trimethylsilyl)silanes 44a-c or SifiMcji were irradiated at 254 nm to create silylenes 45a-d, which reacted with CO, causing new peaks to ca. 290 and 350 nm, which were attributed to complex 46a-d, a resonance structure of silaketene 47a-d. Silylene adducts form fairly weak bonds, as seen by warming of the matrices. In the case of silylene adducts where one R = Mes, the CO dissociates and the corresponding disilene 48a-c peaks in the UV-vis spectra observed upon warming (R2 = Me most likely produced silane rings Si, Me6. etc.). 

In the photolysis of trisilanes RR Si(SiMe3)2 (R = R = Mes R = Mes, R = Tip R = R = Tip), the rate of disilene formation was predicted to increase in this order because the Si—Si—Si bond angles decrease in the same order, as revealed by X-ray structural analyses, thus facilitating the formation of Me3SiSiMe3. Although the predicted trend in the rates of photolysis was found, the differences were small.12... 

X-ray crystal structures have been determined for eleven disilenes, some of whose structural parameters are summarized in Table III. Some important structural characteristics follow. (1) The Si=Si bond distances... 

The classic disilene 1 is unusual in that it exists in at least three crystalline modifications orange and yellow unsolvated forms and a yellow toluene solvate (Fig. 2). The orange polymorph has a helical conformation in which all of the mesityl substituents are twisted in the same direction thus molecules of 1 in this form are chiral.51 The toluene solvate has an unusual conformation in which two mesityl rings cis to each other are nearly coplanar with the Si=Si bond, while the other two cis mesityl groups are nearly orthogonal.41 The structure of the yellow unsolvated form is not yet known. Because of the flat potential surface for the Si=Si... 

From X-ray crystal structures of the products, the reactions of these stereoisomeric disilenes with episulfides, and with sulfur, were shown to proceed with retention of configuration at silicon. These findings suggest that the reaction proceeds in a concerted fashion, through intermediates or transition states involving tetracoordination for the sulfur atom being transferred (Scheme 13). Similar intermediates are believed to occur in other sulfur-transfer reactions.86... 

Quite unusual reactions take place between disilenes and the active forms of the group 15 elements, P4 and As4. In nearly all reactions of disilenes, the Si—Si w-bond is broken in the first step, leaving the products isolated from the reaction of disilenes 1,11, and 12 with P4 were found to have the [1.1. OJbicyclobutane structure 698-c.98,99 In these butterflyshaped compounds the silicon atoms are completely separated, although a P—P [Pg.266]

The highly hindered disilene 2 did not react with white phosphorus, even under forcing conditions. With disilene 3, which is more hindered than 1 but less so than 2, the reaction with P4 was more complicated. It proceeded slowly, producing small amounts of both stereoisomers of the bicyclobutane compounds 70 and 70. The major product, however, was a more complex compound containing four phosphorus and four silicon atoms, also obtained as a mixture of two stereoisomers. Two-dimensional 31P NMR spectroscopy established the probable structures to be 71.98... 

At this time, although details remain to be elucidated, it seems that most of the main kinds of reactions of disilenes, have been discovered. These have led to numerous new classes of cyclic compounds, some with unprecedented and beautiful structures. In addition, the chemical bonding in disilenes has received serious study and is at least partially understood. 

Finally, the chemical properties of the new structures available from disilene addition reactions have hardly been touched. In future developments, theoretical and experimental studies are likely to proceed together and complement one another, as they have from the beginning days of this research. 

The photochemical cleavage of Si-Si bonds of cyclotetrasilanes has been reported to generate several reactive intermediates. For example, Nagai and co-workers reported that silylene and cyclotrisilane are generated during the photolysis of a cyclotetrasilane with a folded structure.73 Shizuka, Nagai, West, and co-workers reported that the photolysis of planar cyclotetrasilanes gives two molecules of disilene.74... 

The first 7]2-disilene complexes of palladium were described in 2003 structural data for L2Pd 7]2-(Me2ButSi)2Si=Si(SiMe2But)2 (L2 = (PMe3)2 or dmpe) indicate that a metallocyclic description with strong... 

---