Rosenthal's reagent is a metallocene

bis(trimethylsilyl)acetylene Bis(trimethylsilyl)acetylene (BTMSA) is an organosilicon compound with the formula Me3SiC≡CSiMe3 (Me = methyl). It is a colorless liquid that is soluble in organic solvents. This compound is used as a surrogate for acetylene. BTMSA is prepared ...

complex with zirconium ( Cp₂Zr) or titanium (Cp₂Ti) used as central atom of the metallocene fragment Cp₂M. Additional

ligands In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electro ...

such as pyridine or THF are commonly used as well. With zirconium as central atom and pyridine as ligand, a dark purple to black solid with a melting point of 125–126 °C is obtained. Synthesizing Rosenthal's reagent of a titanocene source yields golden-yellow crystals of the titanocene bis(trimethylsilyl)acetylene complex with a melting point of 81–82 °C. This reagent enables the generation of the themselves unstable titanocene and

zirconocene Zirconocene is a hypothetical compound with 14 valence electrons, which has not been observed or isolated. It is an organometallic compound consisting of two cyclopentadienyl rings bound on a central zirconium atom. A crucial question in researc ...

under mild conditions. The

reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...

is named after the German chemist (born 1950) and was first synthesized by him and his co-workers in 1995.

Synthesis

Rosenthal's reagent can be prepared by reduction of titanocene or zirconocene dichloride with magnesium in the presence of bis(trimethylsilyl)acetylene in THF. The illustrated product for a titanocene complex can be represented by the resonance structures A and B. If zirconium is used as central atom, additional ligands (e.g. pyridine) are necessary for stabilization. Synthesis of rosenthal reagent with titanocene

Application and reactions

The main area of application is the synthesis of synthetically challenging organic structures such as macrocycles and heterometallacycles. Rosenthal's reagent allows the selective preparation of these compounds with high yields. Currently, Rosenthal's reagent is often used instead of Negishi's reagent (1-butene)zirconocene to generate zirconocene fragments as it offers a number of compelling advantages. Unlike Negishi's reagent, Rosenthal's reagent is stable at room temperature and can be stored indefinitely under an

inert Inert may refer to: * Chemically inert, not chemically reactive ** Inert gas ** Noble gas, historically called inert gas * Inert knowledge, information which one can express but not use * Inert waste, waste which is neither chemically nor biol ...

atmosphere. A much more precise control over the

stoichiometry Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equal ...

of reactions is possible, especially because the instable (1-butene)zirconocene cannot be formed quantitatively. Stoichiometric and catalytic reactions can be performed and influenced by the use of different ligands, metals and substrate

substituent A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and ''functional group'', as well as ''side ...

s. While for titanium complexes, a dissociative reaction mechanism has been observed, zirconium complexes favor an

associative In mathematics, the associative property is a property of some binary operations, which means that rearranging the parentheses in an expression will not change the result. In propositional logic, associativity is a valid rule of replacement f ...

pathway. The combination of these

organometallic Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...

complexes with different suitable substrates (e.g. carbonyl compounds, acetylenes, imines, azoles, etc.) often leads to novel bond types and reactivities. A particularly interesting aspect is the novel C–C coupling reaction of

nitrile In organic chemistry, a nitrile is any organic compound that has a functional group. The prefix ''cyano-'' is used interchangeably with the term ''nitrile'' in industrial literature. Nitriles are found in many useful compounds, including met ...

s to form precursors for the realization of so far unknown heterometallacycles. As main side products of coupling reactions with Rosenthal's reagent, pyridine and bis(trimethylsilyl)acetylene are obtained. These compounds are soluble and volatile, and therefore easy to remove from the product mixture.

References

{{Zirconium compounds Organozirconium compounds Organotitanium compounds Trimethylsilyl compounds Zirconium(IV) compounds Titanium(IV) compounds Reagents for organic chemistry