Tungsten complexes with alkynes

Reaction of [S(CCPh)2] with [Co2(CO)g] afforded 2 jhe crystallographically characterised adduct [(PhCC)S Co2(CO)6(Ti2-CCPh) ] which, on treatment with further [Co2(CO)g] afforded [S Co2(CO)6(Tl2-CCPh) 2l. The reaction of pentacarbonyl allyloxy((4-methylphenyl)ethynyl)carbene) chromium and tungsten complexes with dicobalt octacarbonyl afforded 63 tpe alkyne complexes (62) (M = Cr, W), which failed to undergo intramolecular Pauson-Khand reactions instead, at room temperature, a 1,2-elimination occurs, regenerating the metal hexacarbonyl with predominant formation of dinuclear cobalt complexes (63) - (65). 

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... 

Tungsten(O) pentacarbonyl-methylene chloride complex and alkynes form vinylidene complexes by photo-irradiation, which react with an imine or a dialkylcarbodimide to afford /3-lactams after decomplexation of the metal.233... 

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of 2-butyne affords the complexes 75 and 76, respectively, where the lone carbonyl remaining after alkyne insertion had been replaced by a third molecule of the alkyne. 

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... 

Related tungsten complexes have been prepared by diverse routes. Phosphine, phosphite, and isonitrile W(CO)2(RC=CR)LI2 complexes form from W(CO)4LI2 and alkyne [Eq. (3)] (44). Parent acetylene (HC2H) complexes were isolated as m-dicarbonyl derivatives for L equal to PMe3 or AsMe3, and both cis- and Pms-dicarbonyl derivatives were characterized with phenylacetylene in the coordination sphere. 

For cyclopentadienyl tungsten(II) derivatives barriers of 18-19 kcal/mol characterize alkyne rotation in both the alkyl and acyl cases (67,69,161). Extended Huckel calculations indicate that steric factors play a role in these complexes in addition to the standard dir orbital electronic factors (147). Smaller barriers attend replacement of CO in CpW(CO)-(HC=CH)X complexes with either P(OMe)3 or PMe3. No alkyne rotation... 

As stated in the Introduction, Templeton7 published a comprehensive review entitled Four Electron Alkyne Ligands in Molybdenum(II) and Tungsten(II) Complexes, including halocarbonyl complexes, which dealt with the literature up to 1987. Hence, this section of the review deals with the literature on halocarbonyl alkyne and alkene complexes published from 1987 to mid-1995. The vast majority of papers that have appeared during this period are concerned with the reactions of [MI2(CO)3(NCMe)2] (M = Mo, W) and their derivatives with alkynes, which begin this section of the review. 

Thus far, the reactions of the diiodo-complexes [MI2(CO)3(NCMe)2] with alkynes have been described. In this section the reactions of other seven-coordinate molybdenum(II) and tungsten(II) halocarbonyls with alkynes are described. 

Scheme 16. Formation of tungsten perethyl-Cp complexes (and modifications) from a tungstenacyclobutadiene complex and alkynes (37,81-84). The generalized reaction indicates the formation of different isomers (more than two are possible) when three or more different substituents R are present. The WfC BuXdmeJQj complex also reacts with alkynes to give bulky Cp derivatives (82) (dme = dimethoxyethane). Molecule drawings are schematic.

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