Tungsten complexes with alkenes

The reaction of alkenes with alkenes or alkynes does not always produce an aromatic ring. An important variation of this reaction reacts dienes, diynes, or en-ynes with transition metals to form organometallic coordination complexes. In the presence of carbon monoxide, cyclopentenone derivatives are formed in what is known as the Pauson-Khand reaction The reaction involves (1) formation of a hexacarbonyldicobalt-alkyne complex and (2) decomposition of the complex in the presence of an alkene. A typical example Rhodium and tungsten ... 

Both W(CO)5[C(C6Hs)2] and the analogous di-p-tolylmethylene complex have been used in model studies of the olefin metathesis reaction.2 3 In contrast to heteroatom-stabilized carbene complexes such as W(CO)s [C(OCH3)(C6Hs)], pentacarbonyl(diphenylmethylene)tungsten(0) reacts with alkenes to give cyclopropanes and 1,1-diphenylalkenes.2 The compound W(CO)5 [C(C6H5)2] is the best reported catalyst for the metathetical polymerization of 1-methylcyclo-butene.4... 

However, the reaction was shown to be catalyzed by a methylidene tungsten-carbene complex rather than the Fischer tungsten carbene complex. They proposed that the reaction would proceed by [2 + 2] cycloaddition of the tungsten carbene complex with the alkyne in Equation (3), ring opening, and another [2 + 2] cycloaddition with the alkene moiety to finally give the cyclized product. 

Bis(adamantylimido) compounds, with monomeric chromium(VI) complexes, 5, 348 Bis(alkene) complexes conjugated, Rh complexes, 7, 214 mononuclear Ru and Os compounds, 6, 401 -02 in Ru and Os half-sandwich rj6-arenes, 6, 538 with tungsten carbonyls and isocyanides, 5, 685 Bis(u-alkenylcyclopentadienyl) complexes, with Ti(II), 4, 254 Bis(alkoxide) nitrogen-donor complexes, with Zr(IV), 4, 805 Bis(alkoxide) titanium alkynes, in cross-coupling, 4, 276 Bis(alkoxo) complexes, with bis-Cp Ti(IV), 4, 588 Bis[alkoxy(alkylamino)carbene]gold complexes, preparation, 2, 288... 

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... 

The chemistry of pyrrol-1-ylbenzylidene pentacarbonyl chromium, molybdenum and tungsten complexes was investigated. Reaction with electrophilic alkenes gives l-(phenylcyclo-propyl)pyrroles Under photolytic decarbonylation conditions 2 + 2 cycloaddition products were obtained with nucleophilic alkenes, cyclic dienes and imines. <950M2522>... 

A number of allylic chlorides have been reported to yield photoproducts characteristic of the alkene moiety and not of the C—X bond123. Allyl and crotyl halides undergo photochemical reactions with chromium, molybdenum and tungsten complexes, which involve C—X bond cleavage133. 

The anti addition of amines to the double bond of cationic (alkene)(cyclopentadienyl)di-carbonyliron complexes and to the analogous molybdenum and tungsten complexes has been reported31 33. The adducts underwent carbonyl insertion-cyclization to give chelate complexes, which were then oxidized to /8-lactams. For example, from the Fp complexes of ( )- and (Z)-2-butene the corresponding /8-lactams were obtained diastereoselectively in 10-15% yield by the direct oxidation of the benzylamine adducts with chlorine at low temperature33. The stereochemistry was determined by H-NMR spectroscopy. 

First, the sulfur atom from a thiirane is added to one of the carbon atoms of the thiirane ligand of the complex, with formation of a zwitterionic intermediate. The zwitterionic intermediate undergoes elimination of ethylene to yield a reactive alkene disulfide tungsten complex. The dithietane ligands from two or more molecules, then combine to form the cyclic polysulfides. If the macrocyclization of thiirane catalyzed by W(CO)s(SC2H4) is performed in the presence of DMAD, small quantities of polythioether macrocycles 156 and 157 are formed <1997OM1430>. 

Bis-nitrogen donor ligand-substituted alkylidyne complexes such as 78 were found to be good alternatives as starting materials to the thermally labile tetracarbonyl complexes 44). Substitution of one pyridine ligand in the bispyridine-substituted complexes 78 occurs in the presence of excess chloride [Eq. (64)] 103). The anionic complexes 79 are stable in the presence of excess chloride but are too labile to be isolated in pure form. These complexes were used in the synthesis of stable alkylidyne alkene tungsten complexes [Eq. (180), Section IV,G]. With phosphines both pyridine ligands in 78 are substituted [Eq. (65)] 44). For PMej the reaction of the tetracarbonyl complex W(CPh)Br(CO)4 had previously been shown to... 

Several alkylidyne alkene tungsten complexes were synthesized in our laboratory. The neutral complex 233 and the anionic complexes 235 were found to react with maleic anhydride and fumaronitrile to afford the products 234 and 236 [Eqs. (179) and (180)] (103). The tmeda-substituted... 

A methodology that constructs the ISQ core directly from pyridines using a 7t-basic tungsten complex to disrupt the aromatic stabilization of these inert heterocycles was recently reported [70]. For example, common pyridine derivatives, e.g., 2-dimethylaminopyridine, will undergo stereoselective Diels-Alder reactions with electron-deficient alkenes, e.g., acrylonitrile. 

Tungsten hexachloride reacts with dry silica gel to form a surface complex with average composition ( i02)WCl4. Van Roosmalen and associates reported that with tetramethyltin the complex yields a solid catalyst for the metathesis of alkenes with the same activity as the WOQ4-SnMe4 system, but is less active for the metathesis of methyl oleate. The supported complex can be used several times without additional SnMe4. ... 

The phenylcyclopropanes are formed consistently as stereoisomeric mixtures, but the configuration of the predominant isomer depends on the alkene. For monosubstituted alkenes there is a progressive change of the cisjtrans ratio to lower values as the substituent becomes sterically larger. Thus, when the tungsten complex is allowed to react with propene, but-l-ene, 3-methyl-but-l-ene and 3,3-dimethylbut-l-ene, the ratio for the cyclopropane 3 drops from 1.8 to 0.01. ... 

Pyrrol-1-ylcarbene complexes 18 effect the cyclopropanation of electron-deficient alkenes in good to very good yield. The C-H insertion products usually observed with aminocarbene complexes are only formed in low yields. Molybdenum and tungsten complexes are more favorable for cyelopropanation reactions than the analogous chromium complexes. The diaste-reoelectivity of the cycloaddition, however, was only moderate cisjtrans ratio of 1 1.6 to 3.4). 

Fischer-type carbenes are known as potential carbene transfer reagents to electron-rich and electron-deficient alkenes. Little is known about the chemistry of carbene complexes with silicon substituents at the carbene C-atom, whereas complexes with germanium, tin, or lead have not yet been prepared. The tungsten-carbene complexes 6 react with an excess of ethyl vinyl ether to give l,2-diethoxy-l-(trialkylsilyl)cyclopropanes 7." Only the f-isomers were formed and similar results can be achieved by using the corresponding molybdenum or chromium complexes. On the other hand, no reaction takes place with 2,3-dihydrofuran or ethyl ( )-but-2-enoate. ... 

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