Tantalum complexes carbonyls

Aza[3]ferrocenophanes, synthesis, 6, 187 Azaheterocycles, alkynylation with Ir catalysts, 7, 340 7-Azaindole, in trinuclear Ru and Os clusters, 6, 725 Azametallacyclobutane, tantalum complexes, 5, 168 Azametallacyclopropane, with niobium, 5, 87 Aza-oxo ligands, chromium complexes, 5, 353 Azaphosphirenes, with tungsten carbonyls, 5, 623 2H-Azaphosphirenes, with tungsten carbonyls, 5, 679 Aza-titanacyclopentenes, synthesis, 4, 407-408 Azavinylidenes... 

Homoleptic platinum carbonyl anions, characteristics, 8, 410 Homoleptic tantalum complexes, preparation and characteristics, 5, 108... 

Reduction of Ta(silox)3Cl2 with Na/Hg leads to a three-coordinate alkoxide complex Ta(silox)3. The coordinatively unsaturated tantalum complex is capable of cleaving H2 and O2 bonds resulting in the hydride and 0x0 complexes as illustrated in Scheme 7.14. Carbon monoxide is also split upon carbonylation of Ta(silox)3 generating the 0x0 and p-dicarbide complexes. This reaction models the C—O bond cleavage and C—C bond formation believed to occur in the Fischer-Tropsch reaction, and the ketenylidene complex Ta(silox)3(=C=C=0) was postulated as the key intermediate. On the other hand, when Ta(silox)3 was treated with pyridine and benzene, remarkable T -coordinated complexes were formed. 

Many carbonyl and carbonyl metallate complexes of the second and third row, in low oxidation states, are basic in nature and, for this reason, adequate intermediates for the formation of metal— metal bonds of a donor-acceptor nature. Furthermore, the structural similarity and isolobal relationship between the proton and group 11 cations has lead to the synthesis of a high number of cluster complexes with silver—metal bonds.1534"1535 Thus, silver(I) binds to ruthenium,15 1556 osmium,1557-1560 rhodium,1561,1562 iron,1563-1572 cobalt,1573 chromium, molybdenum, or tungsten,1574-1576 rhe-nium, niobium or tantalum, or nickel. Some examples are shown in Figure 17. 

It is particularly interesting, that some titanium and tantalum carbene complexes olefinate derivatives of carboxylic acids. These reagents are, moreover, much less basic than phosphorus ylides, and thus enable the olefination of strongly C-H acidic carbonyl compounds. 

Similarly, neither zirconium, tantalum, molybdenum, nor tungsten carbene complexes have been applied extensively by organic chemists for carbonyl olefination [609,727-729], probably because of the difficulty of their preparation and the high price of some of these compounds. These reagents can, however, have appealing chemo- and stereo-selectivity (Table 3.11). 

The monomeric carbonyl complexes of d M1 isolated so far are mainly the seven-coordinated [MX(CO)2(dmpe)2] compounds (M = Nb, X = Cl, Br, N3 697 M = Ta, X = H, Cl, Br, CN, Me, Et, Pr ) (53) has been obtained by reduction of [TaCl2(dmpe)2] with one equivalent of sodium naphthalenide under CO the other tantalum derivatives were generally prepared by oxidative additions to [Ta(CO)2(dmpe)2] formed in situ by reduction of (53 Scheme 10). The niobium analogs were formed by reductive carbonylation of [NbCU(dmpe)2].698... 

Imidazolium ligands, in Rh complexes, 7, 126 Imidazolium salts iridium binding, 7, 349 in silver(I) carbene synthesis, 2, 206 Imidazol-2-ylidene carbenes, with tungsten carbonyls, 5, 678 (Imidazol-2-ylidene)gold(I) complexes, preparation, 2, 289 Imidazopyridine, in trinuclear Ru and Os clusters, 6, 727 Imidazo[l,2-a]-pyridines, iodo-substituted, in Grignard reagent preparation, 9, 37—38 Imido alkyl complexes, with tantalum, 5, 118—120 Imido-amido half-sandwich compounds, with tantalum, 5,183 /13-Imido clusters, with trinuclear Ru clusters, 6, 733 Imido complexes with bis-Gp Ti, 4, 579 with monoalkyl Ti(IV), 4, 336 with mono-Gp Ti(IV), 4, 419 with Ru half-sandwiches, 6, 519—520 with tantalum, 5, 110 with titanium(IV) dialkyls, 4, 352 with titanocenes, 4, 566 with tungsten... 

No cationic carbonyl complexes of niobium and tantalum have been reported. 

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