Tungsten complexes with imidos

Schrock and coworkers have generated and tested more than forty molybdenum and tungsten imido complexes with pincer iridium complex for AM [59]. In general, tungsten complexes perform better than molybdenum complexes, presumably due to... 

Group 4, surface chemistry on oxides, 12, 515 Group 5, surface chemistry on oxides, 12, 524 molybdenum, surface chemistry on oxides, 12, 529 into nickel complexes, 8, 59-60 with palladium, GO insertion, 8, 200 tungsten, surface chemistry on oxides, 12, 531 on zinc compounds, 2, 366 Alkoxido-imido tungsten complexes structure and properties, 5, 754—755 synthesis, 5, 750/... 

Bishomoallyl alcohols, via allyindium reagents, 9, 703 Bis(hydrostannation), in tin-carbon bond formation, 3, 814 Bis(imidazolyl) ligands, chromium complexes, 5, 359 Bis(imido) systems, with chromium(VI), as models, 5, 377 Bis(imido)tungsten complexes, synthesis, 5, 749 Bis(imido)uranium(VI) complexes, synthesis, 4, 216-217 Bis(imino)carbenes, with Zr(IV), 4, 798 Bis(iminooxazolidine) complexes, biaryl-bridged, with Zr(IV) and Hf(IV), 4, 811-812... 

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... 

Scheme 1 gives a postulated reaction pathway for all these metathesis like reactions. The heteroallenes or the heteroalkenes are supposed to react in a 2 + 2 cycloaddition reaction with Cl3(dme)WCtBu to form metalla cyclobutene derivatives. Electrocyclic ringopening reactions of these (not isolated) metallacycles yield tungsten imido or 0X0 complexes with sigma bonded vinyl, iminyl, ketenyl or keteniminyl ligands. 

Imido Complexes. The reaction of azitidines with tungsten(II) complexes leads to the formation of tungsten(IV) imido complexes (332) ... 

A unique series of mixed guanidinato/alkylimido/azido tungsten(VI) complexes has been synthesized and structurally characterized. As illustrated in Scheme 133, the syntheses start with the readily accessible imido precursor WCl2(NBu )2py2, which is treated successively with either appropriate lithium... 

Inter- and intramolecular (cyclometallation) reactions of this type have been ob-.served, for instance, with titanium [408,505,683-685], hafnium [411], tantalum [426,686,687], tungsten [418,542], and ruthenium complexes [688], Not only carbene complexes but also imido complexes L M=NR of, e.g., zirconium [689,690], vanadium [691], tantalum [692], or tungsten [693] undergo C-H insertion with unactivated alkanes and arenes. Some illustrative examples are sketched in Figure 3.37. No applications in organic synthesis have yet been found for these mechanistically interesting processes. 

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