Pentacoordinated Siliconates

In 1999, Demnark disclosed that silacyclobutane derivatives (34) were very effective coupling partners for the transfer of alkenyl and aryl groups. The original theory was that the release of strain energy upon treatment with fluoride to make the silicon pentacoordinate is what made these species so active. However, later studies showed that under the conditions of the cross-coupling reactions, silacyclobutanes formed silanols (35) and disoloxanes (36), which themselves proved... 

The expansion of coordination at silicon. Pentacoordinated species seem to be quite intimately involved in many processes taking place at silicon. Expansion of coordination is the fundamental step not only in the nucleophilic induced racemization reviewed some years ago (13), but also in nucleophilic substitution activated by nucleophiles. A part of this review is devoted to the stereochemical and mechanistic aspects of nucleophilic activation. Furthermore, in connection with a possible isomerization of trigonal bipyramidal silicon by Berry pseudorotation, the dynamic stereochemistry of pentacoordinated silicon compounds is discussed. 

In the past few years, numerous experimental results have illustrated the fundamental importance of penta- and hexacoordinate silicon species in reactions at silicon. The implication of pentacoordinate intermediates in substitution reactions at silicon is now well accepted (10, 11) the nucleophilically induced racemization (13,268) and hydrolysis (or alcoholysis) of halosilanes (268, 269), both controlled by entropy factors, take place through expansion of coordination at silicon. Pentacoordinate species with two or three carbon atoms attached to silicon have been isolated (129, 155) and finally, five-coordinate anions with five carbon atoms around silicon have been identified in the gas phase (107). This shows how much the expansion of coordination at silicon is an energetically favorable process. 

The results of the NMR studies of silatranes gave one of the first unambiguous pieces of evidence for the existence of the transannular Si-s—N bonding in silatrane solutions . Moreover, extensive NMR investigations of silatranes revealed a number of reliable spectral indications for the silicon pentacoordination and earlier unknown spectral and structural regularities which appeared to be typical for most organic derivatives of the TBP silicon . ... 

According to the 29Si NMR spectral data (vide infra), the silicon center of 36 is assumed to be pentacoordinated due to its intramolecular interaction with both terminal amino groups attached to the substituents. This kind of two-fold coordination of the nucleophilic side arm of the 2-(dimethylaminomethyl)phenyl substituent to... 

Today it is widely accepted that fivefold coordinated silicon plays a key role in the reaction mechanisms of the nucleophilic substitution having a trigonal bipyramidal transition state species which ressemble these transition states can be isolated in some special cases. The structural features fit well to kinetic data and possibly explain the significantly higher reactivity (proved by experimental data) of Si-pentacoordinated compounds compared to their tetracoordinated analoga. 

The reactivity of penta- and hexacoordinated silicon compounds has been described to be very different from the reactivity of the corresponding tetracoordinated derivatives [ 1], An increase in reactivity towards nucleophiles has been observed in the case of neutral and anionic pentacoordinated silicon compounds as exemplified by the following Schemes [2],... 

The mechanism of these reactions can be described as a nucleophilic attack on a pentacoordinate silicon compound. Supporting this assumption, neutral or anionic hexacoordinated structures have been isolated and their X-ray structures obtained [5]. 

In the case of anionic systems, following the ideas of Diinitz [6], crystal structure (C) is a good model of an intermediate in which a nucleophile attacks a silicon atom included in a pentacoordinated anionic structure. Such an intermediate occurs during the nucleophilic displacement illustrated in Scheme 3. 

Alternatively, unreactive mixtures of organosilicon hydrides and carbonyl compounds react by hydride transfer from the silicon center to the carbon center when certain nucleophilic species with a high affinity for silicon are added to the mixture.76 94 This outcome likely results from the formation of valence-expanded, pentacoordinate hydrosilanide anion reaction intermediates that have stronger hydride-donating capabilities than their tetravalent precursors (Eq. 6).22,95 101... 

As can be seen from the data presented, the high energies of complex formation decrease sharply the endothermicity of the retro-Wittig type decomposition and, moreover, fundamentally change the reaction mechanism. As has been shown for betaines (")X-E14Me2-CH2-E15( + )Me3 (X = S, Se E14 = Si, Ge E14 = P, As), the reaction occurs as bimolecular nucleophilic substitution at the E14 atom. For silicon betaines, the transition states TS-b-pyr with pentacoordinate silicon and nearby them no deep local minima corresponding to the C-b complexes can be localized in the reaction coordinate. 

Quite recently, it was established that the formation of the pentacoordinated germanium and tin compounds EF4(CH2CH=CH2) from EF3(CH2CH=CH2) (E = Ge, Sn) by the addition of F is exothermic148. The nucleophilicity of the allylic y-carbon is much enhanced when the pentacoordinated EF4(CH2CH=CH2) is formed. These results are qualitatively similar to those found for the reaction of the corresponding silicon compound. The pentacoordinated Ge and Sn complexes have a significant Lewis acidity which allows them to form stable hexacoordinated intermediates in the course of the reaction. 

Pentacoordinate silicon complexes can also be prepared via the reaction of diaryldichlorosilanes with carbenes 4 (R = Et, Pr R = Me). Interestingly, a 2-(trimethylsilyl)imidazolium salt (56) was formed when Me3SiI was treated with 4 (39). Unfortunately, no information regarding the crystal structures of these species is available. 

The literature on these structures is sparse, and generally the articles report preparations of several of them in similar ways. These compounds are constituted by oxygen, sulfur, or nitrogen adducts at the silicon atom, thus providing pentacoordinated silicon compounds or structural analogs (Scheme 33). 

The report suggests that the actual reagent may be a pentacoordinate allyl-siliconate, such as CH,CH=CHCH2Si F4Cs+, which reacts with an aldehyde via a six-membered cyclic transition state. 

Reductions. Silicon hydrides such as 1, which can achieve intramolecular pentacoordination, show enhanced reducing properties. Thus they can reduce aldehydes or ketones to alcohols,1 and reduce carboxylic acids to aldehydes via thermal decomposition of a silyl carboxylate (equation I).2 Reaction of acid chlo-... 

Photoswitching has allowed Kawashima et al. to control the configuration of the N-N double bond and the coordination number of potassium 18-crown-6 2-(phenylazo)phenyltetrafluorosilicates 836 and 837, which are accessible by the reaction of 2-(phenylazo)phenyltrifluorosilane 838 with KF/18-crown-6 (Scheme 116).830 In the (Z)-form, the silicon atom of 837 is pentacoordinated, whereas in the (E)-form, one nitrogen atom of the azo group of 836 intramoleculary coordinates to the silicon atom, thus extending its coordination sphere to six ligands. Almost... 

PhCCSiF3 are in equilibrium with the pentacoordinated 1 1 complex 843. Only at low temperatures, a second equivalent of pyridine slowly coordinates to the silicon to selectively form one of three conceivable isomers, namely, the hexacoordinated 1 2 complex 844 having the two pyridine molecules in /raor-position (Scheme 118).832... 

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