Silicon-metal complexes

The diruthenium and diosmium species M2(SiMe3)2(CO)g are obtainable in high yield and are reduced by sodium amalgam to [M(SiMe3XCO)4] , whose reactions with various halides provide a route to silicon-metal complexes - . Addition of silicon halides to [M(CO)4] " is successful only in the synthesis of Fe(SiH3)2(CO)4 (see 5.8.3.3.1.) and is not a route generally available for M(SiR3)2(CO)4. 

Keywords silicon-metal complexes, halocarbons, polymerization... 

Part 28 of the series Metallo-Silanols and Metallo-Siloxanes . In addition, Part 56 of the series Synthesis and Reactivity of Silicon Metal Complexes . For Part 27/25, see Ref. [1]. 

The coordination sphere of transition-metal complexes can furthermore be utilized for the fixation of silicon ligands in their lowest oxidation states. Even examples of compounds containing a formally zerovalent silicon (E) are now known [41]. 

Investigations of silicon-metal systems are of fundamental interest, since stable coordination compounds with low valent silicon are still rare [64], and furthermore, silicon transition-metal complexes have a high potential for technical applications. For instance, coordination compounds of Ti, Zr, and Hf are effective catalysts for the polymerization of silanes to oligomeric chain-silanes. The mechanism of this polymerization reaction has not yet been fully elucidated, but silylene complexes as intermediates have been the subject of discussion. Polysilanes find wide use in important applications, e.g., as preceramics [65-67] or as photoresists [68-83],... 

The growing interest in volatile silyl-metal complexes for chemical vapor deposition reactions should also be mentioned. This technique is extremely useful for the preparation of silicide films in microelectronic devices. Further examples of applications of silicon-metal compounds are given in the appropriate sections. 

The oxidative addition of silanes (with silicon-hydrogen bonds) to coordinatively unsaturated metal complexes is one of the most elegant methods for the formation of metal-silicon bonds. Under this heading normally reactions are considered which yield stable silyl metal hydrides. However, in some cases the oxidative addition is accompanied by a subsequent reductive elimination of, e.g., hydrogen, and only the products of the elimination step can be isolated. Such reactions are considered in this section as well. 

Compared to the sum of covalent radii, metal-silicon single bonds are significantly shortened. This phenomenon is explained by a partial multiple bonding between the metal and silicon [62]. A comparison of several metal complexes throughout the periodic table shows that the largest effects occur with the heaviest metals. However, conclusions drawn concerning the thermodynamic stability of the respective M —Si bonds should be considered with some reservation [146], since in most cases the compared metals show neither the same coordination geometries nor the same oxidation states. 

Dihydro-lH-l,5,2-azasilaboroles derive from the 2,5-dihydro-lH-l,2-aza-boroles ( 6.5.3.3) by substitution of the carbon neighboring N by a silicon atom. They may act as four-electron donors using electron density from the C=C double bond and the N atom. The B atom behaves as an acceptor center. Two pathways are known for complex synthesis reaction with a generated transition-metal complex fragment and reaction with metal atoms by the metal-vapor synthesis method. 

E. Silicon-Transition Metal Complexes Having Special Structural... 

There is a large and growing field of transition metal chemistry in which silicon-containing ligands are involved. The object of this review is to provide a guide to the literature on those aspects of the subject described by the title and to deal in detail with topics not treated specifically elsewhere. Section II is concerned with complexes having Si-transition metal (M) bonds, Section III with the role of transition metal complexes in hydrosilylation, and Section IV with complexes having Si—C—M bonds. 

Silicon-Transition Metal Complexes with Special Structural Features... 

Two closely related reactions, (a) and (b), illustrated by Eq. (12) (Rj = HPhj, Etj, Phj, CI3, CljPh) and (13), of silicon hydrides with transition metal complexes generate compounds with Si—M bonds with elimination of hydrogen (a) cleavage of metal-metal bonds and (b) reaction with transition metal hydrides. Reactions discussed in this section are relevant to... 

Selected Distances and Angles eor Silicon-Transition Metal Complexes... 

In addition to activation of sihcon bonds by fluoride ions as discussed in Section 2.4, silicon-silicon, silicon-carbon, silicon-hydrogen, and silicon-nitrogen bonds are activated by transition metal salts and transition metal complexes. Thus, hydrolysis of silicon-carbon bonds such as in phenyltrimethylsilane 81 can be induced by... 

The methods available for synthesis have advanced dramatically in the past half-century. Improvements have been made in selectivity of conditions, versatility of transformations, stereochemical control, and the efficiency of synthetic processes. The range of available reagents has expanded. Many reactions involve compounds of boron, silicon, sulfur, selenium, phosphorus, and tin. Catalysis, particularly by transition metal complexes, has also become a key part of organic synthesis. The mechanisms of catalytic reactions are characterized by catalytic cycles and require an understanding not only of the ultimate bond-forming and bond-breaking steps, but also of the mechanism for regeneration of the active catalytic species and the effect of products, by-products, and other reaction components in the catalytic cycle. 

Roewer G, Herzog U, Trommer K, Muller E, Friihauf S (2002) Silicon Carbide - A Survey of Synthetic Approaches, Properties and Applications 101 59-136 Rosa A, Ricciardi G, Gritsenko O, Baerends EJ (2004) Excitation Energies of Metal Complexes with Time-dependent Density Functional Theory 112 49-116 Rosokha SV, Kochi JK (2007) X-ray Structures and Electronic Spectra of the n-Halogen Complexes between Halogen Donors and Acceptors with jc-Receptors. 126 137-160 Rudolf P, see Golden MS (2004) 109 201-229... 

Transition metals have been used to trap and stabilize many different types of reactive intermediates, such as carbenes. Reactive silicon intermediates have only recently yielded to this approach. In the case of alkenes, for instance, transition metal complexes are generally made by exposing the alkene to a transition metal bearing suitable leaving groups (e.g., carbonyl). Unlike carbon-based intermediates, however, silicon-based analogs have been very difficult to prepare until recently. Unless... 

Studies of the base-hydrolysis mechanism for hydrolysis of technetium complexes have further been expanded to an octahedral tris(acetylacetonato)techne-tium(III) [30], Although a large number of studies dealing with base hydrolysis of octahedral metal(III) complexes have been published [31], the mechanism of the tris(acetylacetonato)metal complex is still unclear. The second-order base hydrolysis of the cationic complex tris(acetylacetonato)silicon(IV) takes place by nucleophilic attack of hydroxide ion at carbonyl groups, followed by acetylacetone liberation, and finally silicon dioxide production [32], The kinetic runs were followed spectrophotometrically by the disappearance of the absorbance at 505 nm for Tc(acac)3. The rate law has the following equation ... 

Transition-metal chemistry is currently one of the most rapidly developing research areas. The record of investigation for compounds with metal silicon bonds is closely comparable to that for silicones it was in 1941 when Hein discovered the first metal silicon complex, followed by Wilkinson in 1956. A milestone in the development of this chemistry was Speier s discovery of the catalytic activity of nobel metal complexes in hydrosilylation reactions in 1977. Hydrosilylation is widely used in modem organic syntheses as well as in the preparation of organo functionalized silicones. Detailed investigations of the reaction mechanisms of various catalysts continue to be subject of intense research efforts. 

Other organosilicon polymer precursors for ceramics have either been prepared or improved by means of transition metal complex-catalyzed chemistry. For instance, the Nicalon silicon carbide-based ceramic fibers are fabricated from a polycarbosilane that is produced by thermal rearrangement of poly(dimethylsilylene) [18]. The CH3(H)SiCH2 group is the major constituent of this polycarbosilane. 

This brief review has shown that the transition metals and their compounds can play a very useful role in ceramics-directed silicon chemistry. Transition metal complexes find important applications as catalysts as well as stoichiometric reactants, and the metals themselves have found more direct application in the synthesis of silicon-containing ceramics and ceramic composites. 

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