1,3-Cyclopentadiene tungsten complexes

In addition to the reaction shown in Scheme 53, some other related reactions that are thought to proceed via cyclic carbometallation have also been reported (Scheme 54). In the cyclization reaction of 2-ethenyl-2 -ethynylbiphenyl, both Cr and W carbyne complexes must undergo the same cyclic carbometallation as that shown in Scheme 53 to give the corresponding metallacyclohexadiene intermediates, but the final products obtained were different.256 Some tungsten-carbyne complexes have been shown to undergo a stepwise [2 + 2 + 2]-cyclization via formal cyclic carbometallation that can be followed by reductive elimination to produce cyclopentadiene-tungsten complexes.2... 

C4H 2OSi, Silane, methoxytrimethyl-, 26 44 CH4N, Propane, 2-isocyant-2-methyl-ruthenium complex, 26 275 C][l,4]-dithiin-2-thione, 26 389 CHfc, 1,3-Cyclopentadiene cobalt complex, 26 191-197, 309 chromium, molybdenum, and tungsten complexes, 26 343 iron complex, 26 232-241 mercury-molybdenum-ruthenium complex, 26 333... 

Summary Thermal rearrangement of the short-lived phosphinidene complex [(OC)5W PCH(SiMe3)2 ] yielded stereoselectively an ri -f-phosphaalkene tungsten complex via 1,2-silyl shift this product was isolated and unambiguously characterized by multinuclear NMR spectroscopy. We also report preliminary studies on the reactivity of this T] - -phosphaalkene complex toward (Me2N)3P, cyclopentadiene and DMAD. 

The tungsten complex undergoes a Diels Alder reaction with cyclopentadiene <9SCB1S7>. The preparation of the highly reactive ketipin acid dilactone (19) was reported <94LA961>. 

The synthesis of the silanol-fiinctionalized tungsten complexes 8a,b starts with the deprotonation of the cyclopentadiene 6a, followed by the reaction with W(CO)g to give the metallate 7. Final... 

Chemical routes involving the use of tungsten salts have been reported. W2C was claimed to be formed by the pyrolysis of an organometallic complex containing cyclopentadiene and carbonyl groups.8 The W2C formed was useful for ceramic applications such as wear resistant surfaces and cutting tools. The same phase was also prepared by the reduction of WC14 with sodium triethylborohydride.9 The material was formed as 1-5 nm-sized crystallites as shown by SEM and TEM. 

Upon UV irradiation in hydrocarbon solution, the hexacarbonyls of chromium, molybdenum, and tungsten react differently with conjugated dienes like 1,3-butadiene (la), ( )-l,3-pentadiene (lb), 2-methyl-1,3-butadiene (lc), ( , )-2,4-hexadiene (Id), ( )-2-methyl-l,3-pentadiene (le), 2-ethyl-1,3-butadiene (If), or 1,3-cyclohexadiene (Ig). Chromium hexacarbonyl (2) yields, with the acyclic dienes la-lf, tetracarbonyl-r/2-dienechromium(0) complexes (3a-3f) in a smooth reaction (8-10). With 1,3-cyclohexadiene, in addition to 3g, dicarbonylbis(>/4-l,3-cyclohexadiene)chromium(0) (4g) is obtained [Eqs. (7) and (8)j. During chromatography on silica gel, the 1,3-cyclohexadiene complex 3g dismutates readily to [Cr(CO)6] and 4g [Eq. (9)]. Under the same conditions with 2 1,3-cyclopentadiene (lh) yields, in a hydrogen-transfer reaction, the stable dicarbonyl- / 5-cyclopentadienyl-r/ 3-cyclopent-enylchromium (5) (11-13) [Eq. (10)]. 

The chemistry of (l-alkynyl)carbene iron complexes is different from that of chromium and tungsten compounds. [4+2] cycloaddition of cyclopentadiene to a (l-alkynyl)carbene iron complex 11,m (R = SiMe3, r-Bu, c-QHn, n-Pr, Ph) affords (l-alkenyl)carbene Fe(CO)4 complexes 55, but these are readily isomerized at 50°C to Fe(CO)2 complexes 57 by insertion of carbon monoxide into the Fe = C bond of an intermediate Fe(CO)3... 

Acylmetallates lp,q generated by addition of lithio prop-2-ynylic ethers to hexacarbonyl chromium or tungsten afford oxacyclopenten-2-ylidene complexes 173 on contact with wet silica gel (Scheme 73).194 The chromium complex 173 (M = Cr) undergoes a condensation with tolane to give a 1,4-dioxy aromatic compound 174. Addition of cyclopentadiene to 173 (M = W) affords a Diels-Alder adduct 176 in a 1 3 exo/endo ratio,195 while addition of dimethylamine quite unexpectedly does not lead to production of an aminocarbene complex but to formation of 5,5 -diphenyl-2,2 -bifuran 175 (Scheme 73).196... 

Since many organometallics behave as Lewis bases due to electron-rich metals, protonation is a common reaction. For example, the tungsten hydride 3 undergoes reversible protonation at the metal, forming the water-soluble cationic hydride 4 (Eq. 5). In nickelocene 5, a 20e complex, protonation occurs at the jr-bonded cyclo-pentadienyl ligand the intermediate 6 has a stable, isolable counterpart in the fully methylated derivative. Consecutive loss of cyclopentadiene forms the cation 7, which adds to unchanged nickelocene forming the tripledecker sandwich 8 (Scheme 3). 

C,2H, )N2, Azobenzene, cobalt and palladium complexes, 26 175,176 manganese complex, 26 173 C,2H N, Pyridine, 2-(phenylmethyl)-, palladium complex, 26 208-210 C,2H, P, Phosphine, diphenyl-, manganese complex, 26 158,226-230 ruthenium complex, 26 264 C 2H,2, Toluene, a-2,4-cyclopentadiene-l-yl-, chromium, molybdenum and tungsten hexacaibonyl complexes, 28 148... 

Fig. 3.5 Reaction of 3.2 equivalents of exo adduct (M) of cyclopentadiene and maleic anhydride with 1 equivalent of W[=C(CH2)3CH2](Br)2(OCH2CMe3)2 (I) to give the tungsten-carbene complex Pi and then P (n > 1). Solvent CD2CI2,21°C. The values of [P ] and [I] at the maximum in [Pi] give i,/fcp = 3.8 (Ivin 1988).

Moreover, the presence of the metal auxiliary may increase the stereoselectivity of the cycloaddition. Reaction of the isomeric tungsten propenylcarbene complexes 24 and 25 with cyclopentadiene afforded good chemical yields (> 85%) combined with an endolexo selectivity of 90 10 for the trans complex 24 and of 84 16 for the cis isomer 25 (Scheme 13). [24] For comparison, the isolobal... 

The diastereoselectivity of Diels-Alder reactions with acyclic sugar-vinylcarbene complexes depends on the nature of the diene. Whereas the tungsten vinylcar-bene 222 gives all four possible diastereomers of cydoadduct 296 upon reaction with cyclopentadiene, only one pair of diastereomers of 297 is observed with 2,3-dimethylbutadiene (Scheme 11.61) [110]. 

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