Silicon-transition metal bonds halogens

When the silicon-transition-metal bond is reasonably strong, hydrogen attached to the metal may be replaced (mode 4b in Fig. 2) by halogens (entries 26,27, and 30) or deuterium (entry 29). In the case of the ruthenium example, halogenation can be followed by reductive elimination of RsSiH (226). 

Electrophiles such as halogens may cleave the transition metal-silicon (or germanium) bonds. We have already seen that in the case of the hydrido complexes they induce deinsertion reactions with retention of configuration at silicon (cf. Sect. 3.1). 

The increased reactivity of triflate groups bonded to silicon relative to halogen substituents can also be utilized for the synthesis of multifunctional cyclopolysilane transition metal derivatives, as has recently been shown for 1,3-disubstituted cyclohexasilanes104 (equation 35). 

There are countless examples of the interactions of various atoms and molecules with the clean Si(100) surface. In addition these adsorbate-surface interactions can differ with deposition conditions, such as the rate of deposition or temperature of the sample. For example, even the simplest adsorbate, hydrogen, can etch the surface at room temperature and also form a variety of ordered structures at elevated sample temperatures [57]. A number of adsorbates can form ordered structures commensurate with the surface (e.g. Ag [58], Ga [59], Bi [60]), most transition metals react with the surface to form silicides (e.g. Ni [61], Co [62], Er [63]), halogens can etch the surface at room temperature (e.g. F2 [64], CI2 [65], Br2 [66]), some molecules dissociate on the surface (e.g. PH3 [67], B2H6 [68], NH3 [37]) and other molecules can bond to the silicon in different adsorption configurations but remain intact (e.g. Benzene [69], Cu-phthalocyanine [70], C60 [71]). A detailed review of a number of adsorbate-Si(lOO) interactions can be found in [23,72] and a more specific review relating to organic adsorbates can be found in [22]. As an example of an adsorbate-silicon system we shall here consider the adsorption of a molecule that our group has extensive experience with phosphine. 

Transition-metal catalyzed metathesis of carbon-halogen bonds with Si-Si bonds provides useful access to organosilicon compounds. Most of the reaction may involve initial oxidative addition of the carbon-halogen bond onto the transition-metal followed by activation of the Si-Si bond to give (organosilyl)(orga-no)palladium(II) complex, which undergoes reductive elimination of the carbon-silicon bond. 

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