Tantalum catalysts alkylidenation

Upon discovery of this mechanism, new catalysts have been developed, now presenting alkylidene ligands in the metal coordination sphere, such as [(=SiO) Ta(=CH Bu)Np2 and [(=SiO)Mo(=NAr)(=CH Bu)Np] [43, 88]. Table 11.4 presents results obtained with several catalysts prepared by SOMC. Although [(=SiO) Ta(CH3)3Cp (=SiOSi=)] is not active in alkane metathesis (the tantalum site would not be as electrophilic as required) [18], results obtained with [(=SiO)Mo(=NAr) (=CH Bu)Np] show that ancillary ligands are not always detrimental to catalytic activity this species is as good a catalyst as tantalum hydrides. Tungsten hydrides supported on alumina or siHca-alumina are the best systems reported so far for alkane metathesis. The major difference among Ta, Mo and W catalysts is the selectivity to methane, which is 0.1% for Mo and less than 3% for W-based catalysts supported on alumina, whereas it is at least 9.5% for tantalum catalysts. This... 

In retrospect it is not surprising that the niobium and tantalum alkylldene complexes we prepared are not good metathesis catalysts since these metals are not found in the "classical" olefin metathesis systems (2). Therefore, we set out to prepare some tungsten alkylidene complexes. The first successful reaction is that shown in equation 6 (L = PMe3 or PEt3) (11). These oxo... 

Probably the first isolated tungsten alkylidene complex active in metathesis and completely characterised is the one shown in Figure 16.10 reported by Wengrovius and Schrock the analysis included an X-ray structure determination by Churchill and co-workers [18], The alkylidene was transferred from a tantalum complex to yield the hexacoordinate tungsten complex containing two PEt3 ligands. One of these can be removed by the addition of half an equivalent of palladium chloride. The total turnover number of these catalysts with Lewis acids added was 50 in 24 hours. 

Analogously to the titanacycle catalyst, similar trisubstituted tantallacyclo-butanes were prepared, but with the use of tantalum alkylidene for the reaction with norbornene [100-102] ... 

Alkoxide ligands play an important spectator role in the chemistry of metal-carbon multiple bonds. Schrock and coworkers have shown that niobium and tantalum alkylidene complexes are active toward the alkene metathesis reaction. One of the terminating steps involves a j8-hydrogen abstraction from either the intermediate metallacycle or the alkylidene ligand. In each case the -hydrogen elimination is followed by reductive elimination. The net effect is a [1,2] H-atom shift, as shown in equations (73) and (74), and a breakdown in the catalytic cycle. Replacing Cl by OR ligands suppresses these side reactions and improves the efficiency of the alkylidene catalysts. ... 

The source of the one-carbon metal fragment was not addressed in the original Chauvin papers. However, groundbreaking work by Schrock showed that alkylidene complexes could be synthesized by treating tantalum precursors with alkyllithium reagents (Eq. 4.5) [3,57]. This tantalum alkylidene complex also does not catalyze olefin metathesis, but the synthesis and isolation of the first alkylidene complex was an important milestone in the development of well-defined olefin metathesis catalysts. 

Properties M.w. 184.31 sp.gr. 0.993-0.997 b.p. 95-97 C (13 mm Hg) ref. index 1.579 Toxicology TSCA listed Uses Reducing agent for prep, of silyl-substituted alkylidene complexes of tantalum, in ionic reduction of enones to sat. ketones, in reductive cyclization of unsat. ketones, for esters in presence of zinc hydride catalyst, for o-halo ketones in presence of Mo(0), reduction of thio esters to ethers, esters to alcohols with Rh catalysis, in assym. reduction of methyl ketones, reductive cleaving of allyl acetates Manuf./Distrib. ABCR http //www.abcr.de, Alfa Aesar http //www.aifa.com-. Digital Spec. Chems. http //www.digHaichem.com, Fluorochem USA... 

Tantalum complexes are excellent models in understanding how effective well-defined W and Mo catalysts might be designed that mimic metathesis catalysts based on W and Mo [6]. The first example of a stable M=CHR complex is the Ta(CH-t-Bu)(CH2-t-Bu)3 complex. In this complex, four bulk covalently bound ligands stabilize even an electronically unsaturated specie toward bimolecular decomposition. This compound is sensitive to oxygen, water, and a variety of functionalities, among them are ketones and aldehydes, with which it reacts to yield polymeric (t-BuCH2)3Ta=0 and the expected olefin [26]. It was established that d alkylidene species were responsible for olefin metathesis and drew attention to... 

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