Transition-metal derivatives synthesis

Transition metal anions have widely been used in the synthesis of the first row transition metal derivatives of group IV metals however only in one case does the reaction take place with chlorosilanes... 

Transition Metal Derivatives in Organic Synthesis Annual Survey Covering the Year 1976 L. S. Hegedus, J. Organomet. Chem., 1977, 143, 309-383. 

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). 

Pyrroles, H.M.L. Davies. Synthesis of Porphyrins with Exocy-clic Rings from Cycloalkenopyrroles, T.D. Lash. Palladium-Catalyzed Coupling Reactions of Indoles, A.R. Martin and Q. Zheng. Cycloaddition Reactions of Indole Derivatives, U. Pindur. Transition-Metal Mediated Synthesis of Carbazole Derivatives, H. J. Knoiker. Synthesis of [b]-Annelated Indoles by Thermal Electrocyclic Reactions, S. Hibino and E. Sugi-no. Total Synthesis of (-) and ent (-) Duocarmycin SA, D.L. Boger. Index. I... 

In this convenient preparative route, an alkali metal salt is formed as a byproduct of the synthesis of the desired silicon-transition-metal derivative. The... 

The carbon-iodine bond in perfluoroalkyl iodides is usually susceptible to homolytic fission this was exploited in early work on the synthesis of mercurials and in later work relating to group IVB and transition-metal derivatives (Figure 10.2). 

Another possible explanation for enhanced stabilities of perfluoro-alkyltransition metal compounds concerns possible multiple bonding between the metal and the fluorocarbon group 230). Whatever the reason, a large number of fluorocarbon derivatives of the transition metals have now been described, and a study of their synthesis, properties, and reactions constitutes an important new branch of organotransition metal chemistry. Fluoroalkyltransition metal compounds were first described in 1959 J 8), while perfluoroary 1-transition metal derivatives were discovered in 1963 201, 234). Some typical syntheses of fluorocarbon-transition, metal compounds are shown below ... 

Reviews (a) K. Suzuki and T. Matsumoto, CpjMClj-AgX (M = Zr, Hf) A reagent for glycosidation, 7. Synth. Chem. Soc. Jpn. 48 1026 (1990) (b) K. Suzuki and T. Matsumoto, New methods in glycoside synthesis by using early transition metal-derived reagent, J. Synth. Chem. Soc. Jpn. 51 718 (1993) (c) K. Suzuki, Novel Lewis acid catalysis in organic synthesis. Pure Appl. Chem. 66 1557 (1994). 

Undecamethylcyclohexasilanyl potassium 1, is a well known starting material for the synthesis of a variety of cyclic silane and silane transition metal derivatives [1-3]. A novel and convenient way to obtain 1 has been described recently [4, 5]. 

This volume presents procedures to compounds that illustrate the scope of modern inorganic and organometallic synthesis. Following the tradition of Inorganic Syntheses, emphasis has been placed on useful compounds and methods. Reflecting my own interests, transition metal derivatives are featured. 

---