Tungsten alkyne molybdenum complex

The symmetrical dienyne 58a was converted to a fused bicyclo [4.3.0] ring in 95% yield [17] (Eq. 27). With substrate 58c containing an unsymmetrical diene tether, two different products, 59c and 59c, were obtained in a ratio of 1 to 1 (Eq. 28). The reaction course in the formation of the different bicyclic rings is shown in Scheme 8. This dienyne metathesis is also catalyzed by tungsten or molybdenum complex 62 or 63 (Fig. 1), and a dienyne bearing terminal alkyne 58b could be cyclized to give 59b in 97% yield. 

Schrock and Fischer type carbyne tungsten or molybdenum complexes are very interesting catalysts for alkene metathesis or alkyne polymerisation reactions. Within the first reaction steps they form carbene complexes and on these carbene complexes further metathesis or polymerisation occur. 

Chromium cyclopropylcarbene complexes react with alkynes to provide cyclopentenone derivatives in a formal [2c+2s+lCo] cycloaddition process (see Sect. 3.2). However, tungsten and molybdenum cyclopropylcarbene complexes... 

In the early 1980s, Schrock prepared a series of tungsten- and molybdenum-based carbyne complexes, and demonstrated that they are viable catalysts for performing stoichiometric and catalytic alkyne metathesis [7]. With the defined carbyne complexes, he laid the foundation for the mechanistic understanding of alkyne metathesis, and was the first to demonstrate that vinyl-substituted carbyne complexes are stable [8] and that alkyne metathesis could be performed in the presence of C=C double bonds. 

Molybdenum and tungsten carbyne (alkylidyne) complexes frequently undergo 2+2 cycloaddition reactions with alkynes to give the corresponding metallacyclobutadiene... 

A number of authors have reported successful alkyne metathesis reactions catalysed by either tungsten " molybdenum" complexes. 

Alkyne metathesis is catalysed by alkylidene complexes of tungsten and molybdenum, but not by all alkylidene complexes of these metals. Complexes which do not catalyse metathesis catalyse polymerization of acetylenes to give polypropynes. 

The NMR characterisation of fBA adducts formed in the reaction of tungsten and molybdenum seven-coordinate compounds leaves little doubt concerning their formulation. However, we were unable to separate such compounds and to prepare a crystalline sample. To obtain a more stable terminal alkyne compound, we introduced two phosphine ligands into the coordination sphere of tungsten(II). In this way a cationic complex of tungsten(II), [WCl(CO)( BuC=CH)(NCMe)(PPh3)2]2[SnCl6], was prepared [45]. The crystal structure of this compound consists of two independent cations and a... 

The role of transition-metal carbonyls and particularly those of the Group 6 metals in homogeneous photocatalytic and catalytic processes is a matter of considerable interest [1]. UV irradiation especially provides a simple and convenient method for generation of thermally active co-ordinately unsaturated catalyst for alkenes or alkynes transformation. By using tungsten and molybdenum carbonyl compounds as catalysts, alkenes and alkynes can be metathesized, isomerised and polymerized. Photocatalytic isomerization of alkenes in the presence of molybdenum hexacarbonyl was observed by Wringhton thirty years ago [2]. Carbonyl complexes of molybdenum catalyze not only... 

Another class of transition metal complexes studied by our group consists of alkyne and vinylidene complexes of tungsten and molybdenum in high oxidation states. Alkyne complexes are interesting from a theoretical point of view because they may be considered to be either side-on coordinated ligand complexes or metallacyclopropenes. They are also important as possible intermediates in the cyclooligomerization and polymerization of alkynes. o " Scheme 3 shows the two types of alkyne complex that were studied. 

Reactions of the bis(alkyne) carbaborane complexes of molybdenum and tungsten of the type [Mo(CO)(ri3-MeCCMe)(Ti5-7,8-Me2-7,8-C2B9H9)] with terf-butylisocyanide have been... 

As part of a study of the reactions of metallacyclic y-ketovinyl complexes of molybdenum and tungsten with acetylenes, directed toward the synthesis of complexed -/-lactones, Stone has reported92 the isolation of several vinyl-ketene complexes. When complex 72 was heated with 2-butyne, one molecule of the alkyne was incorporated into the complex with concomitant carbonylation. X-ray analysis of the product (73) has shown unequivocally that the C-l to C-4 vinylketene fragment is bonded in a planar, rj4-configu-ration. In contrast to the thermal reaction, ultraviolet irradiation of 72 or 74 in the presence of 2-butyne affords the complexes 75 and 76, respectively, where the lone carbonyl remaining after alkyne insertion had been replaced by a third molecule of the alkyne. 

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