Benzene metal vapor synthesis

Bis(benzamidinate)zirconium catalysts, for stereoselective propylene polymerization, 11, 708 Bis(r -benzene)tungsten, as metal vapor synthesis milestone, 1, 236... 

There are just few examples of authentic lanthanide complexes in the oxidation state zero. Bis(arene) complexes of the lanthanides (l,3,5- Bu3C6H3)2Ln (Ln = Sc, Y, La, Nd, Pr, Sm, Gd, Tb, Dy, Ho, Er, Lu) have been synthesized by cocondensation of metal vapors (see Metal Vapor Synthesis of Transition Metal Compounds) with 1,3,5-tri(ferf-butyl)benzene at 75 K. A sandwich structure with coplanar arene ligands has been proven by X-ray crystal structure analysis of the Gd and Ho complexes (Figure 86a). 

Another route to bis( -arene)vanadium(0) compounds is the cocondensation of arenes with vaporized vanadium metal (see Metal Vapor Synthesis of Transition Metal Compounds) On treatment with 1,3-cyclohexadiene and butyllithium, 15-electron vanadocene (5) is converted to 16-electron ( -benzene)( -cyclopentadienyl)vanadium(l) (6) (Scheme 3). Use of potassium naphthalenide affords the corresponding naphthalene complex. 

The synthetic potential of transition metal atoms in organometallic chemistry was first demonstrated by the formation of dibenzenechrom-ium (127). Apart from chromium, Ti, V, Nb, Mo, W, Mn, and Fe atoms each form well-defined complexes with arenes on condensation at low temperatures. Interaction has also been observed between arenes and the vapors of Co, Ni, and some lanthanides. Most important, the synthesis of metal-arene complexes from metal vapors has been successful with a wide range of substituted benzenes, providing routes to many compounds inaccessible by conventional reductive preparations of metal-arene compounds. 

Unsupported Floating Metal Cluster Catalysts The term floating catalyst implies the incorporation of a catalyst precursor in the form of a vapor into the reaction chamber, where it decomposes and generates the active catalyst under reaction conditions (76). It was employed by Sen, Govindaraj, and Rao (77) in 1997 to prepare carbon nanotubes by decomposition of ferrocene, cobaltocene, and nickelocene under reductive conditions. In this case, the precursor provides both the carbon and the metal to catalyze the synthesis reaction, but later, benzene or hexane was added to the ferrocene precursor to improve the carbon yield (78). 

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