Silylene complexes bonding

Does a Silylene-Complex exist This rhetorical question is the title of a theoretical paper published in 1983 [84], As a result of an ab-initio calculation, the authors came to the conclusion that a moderately positive answer can be given. However, silylene complexes are thermodynamically less stable than carbene complexes (the MSi bond energy for the hypothetical complex (OC)5Cr = Si(OH)H is 29.6 kcal/mol, the bond energy of the MC bond in (OC)5Cr = C(OH)H is 44.4 kcal/mol) [85], and therefore silylene complexes should be difficult to isolate. 

Basically the same methods known from the synthesis of classical metal-silyl complexes can also be applied to the preparation of low valent Si compounds. The procedures given here are summarized with the focus on silylene complexes These are a) reactions of appropriate metal anions with halosilanes, which are the most important methods for the formation of M-Si bonds. Alternatively, silyl... 

An interesting variant of metal-silicon bond formation is the combination of metal halides with silyl anions. Since silyl dianions are not available, only one metal-silicon bond can be formed directly. The silylene complexes are then accessible by subsequent reaction steps [113], An example of this approach is given by the reaction of cis-bistriethylphosphaneplatinumdichloride 25 with diphenylsilylli-thium, which yields, however, only dimeric platinadisilacyclosilanes 26a-c [114]. 

Starting from (OC)5MnSiR2H (R = Me, Ph, Cl), the p-silylene complex 70 is accessible via the oxidative addition of the Si —H bond to Pt(C2H4.)(PPh3)2 and Pt(PPh3)4, respectively. Structure 70 can be functionalized by displacement of the phosphine ligands alcoholysis and hydrolysis of the compound 70 leads to silicon-free complexes [175]. 

Triphenylphosphonium ylide reacts with the silylene complex 93 which has a highly electrophilic silicon center, to give the corresponding cationic adduct 94 [115]. The lengthening of the PC bond indicates a loss of the double bond character of the ylide and corresponds to the formation of a tetrahedral silicon center with four covalent bonds (Scheme 28). 

Various alkylgermanes add across the Si-C double bond in the silylene complex 116 to yield germyl(silyl)tungsten complexes (Equation (201), Table 25).248... 

Insertion into O-H, N-H, and C—Halogen Bonds. Alcohols are bases toward silylenes. Complexes (51) of alcohols with Mes2Si and other hindered silylenes are observed spectroscopically when a 3-MP matrix containing... 

Recently, the first base-stabilized iridium silylene complexes, IrH2 Si(OTf)Ph2) (TFBXPR3) (TFB = tetrafluorobenzobarrelene), were prepared and characterized following the reaction sequence of Scheme 27. As expected, in the complex with PR3 = P(Pr-z)3, the Ir—Si distance of 2.337(2) A is significantly shorter than those determined previously for the six-coordinate silyliridium(III) complexes (Table 11). The silylene character was also supported by the relatively long Si—O bond of 1.790(5) A compared with the normal range of 1.63-1.66 A186. 

In some cases, insertion of coordinately unsaturated metals into Si—H bonds has been used for the synthesis of silylene complexes, as in the reaction of equation 101. 

Bridged silylene complexes are the subject of a recent comprehensive review by Ogino and Tobita338. These complexes can be classified into three types A, B and C (Scheme 9). In type A complexes there is no metal-metal bonding, the silicon is essentially tetravalent, and the bonding is similar to that in mononuclear metal-silyl complexes. In type C complexes, the bonding is best described as /j2-coordination of the Si—H bond to the metal, or alternatively as a metal-hydrogen-silicon 3-center 2-electron bond. 

The structure and bonding of metal silylene complexes varied from those of their carbon analogs. While Fischer-type metal carbene complexes without solvent adducts have been extensively characterized,48 most metal silylenoid complexes contain a bound solvent molecule or counterion on the silicon atom. The bond energy for donor silicon complex 22 was determined to be between 15 and 20kcal/mol 49,50... 

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