Tantalum complexes with imidos

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... 

Imido dialkyl complexes, with tantalum, 5, 120 Imido-dicarbenes, with palladium, 8, 228-229 Imido groups, in Ru-Os mixed-metal clusters, 6, 1078 Imido hydrocarbyl complexes, with Re(VII), 5, 945 Imido ligands... 

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. 

Mechanistically, the unusual reactivity of the starting tantalum hydrides [(sSiO)2Ta H] and [(=SiO)2Ta (H)3] towards ammonia to yield the amido imido complex [(=SiO)2Ta(=NH)(NH2)] can be fully rationalized in terms of classical molecular organometallic elementary steps. Scheme 2.21 offers an example of a such sequence of elementary steps with the noteworthy close analogy with methane activation by the same hydrides described above. 

Figure 2.10 (a) 2D H- N HETCOR correlation spectrum of fully N-labeled complex [(=SiO)2Ta(=NH) (NHj)] and [=Si- NH2] and comparison with 2D double quantum (b) and triple quantum (c) correlation spectra. An exponential line broadening of 100 Hz was applied to all the proton dimensions before Fourier transform. The dotted gray lines correspond to the resonances of the tantalum NH, NH2 and NH3 protons. The dotted circles underline the absence of auto-correlation peaks for the imido proton in the double quantum spectrum (b), and for the amido proton in the triple quantum, spectrum (c) (from Reference [9]). 

In summary, the tantalum hydride system adds to the few previously reported well-defined organometallic complexes capable of cleaving N-H bonds of ammonia to yield either an amido or an imido complex, and achieves unprecedented dinitrogen N=N triple bond cleavage with dihydrogen on isolated tantalum atoms to yield reduction of both N atoms. 

Wolczanski also investigated the chemistry of a tantalum imido system. In this system, elimination of hydrocarbon from the bis-amido imido complex occurs with difficulty at 183°C to give an amido bis-imido complex. The elimination is reversible, with the bis-imido species not being directly observed (Scheme 10). Under methane pressure, the phenyl complex loses benzene and adds methane. Neopentane, benzene, and toluene (benzylic activation) were also found to undergo activation, but not cyclohexane. The authors conclude from their equilibrium studies that the differences in metal-carbon bond strengths are approximately equal to the differences in carbon-hydrogen bond... 

In contrast to the tantalum compounds considered above, the niobium complexes can exist as conformers of different stability at low temperatures. For example, in the H NMR spectrum of complex 4, the intensity ratio between the signals of the conformers is about 3 1 [ 32 ]. The crystal structures of the bis-amido compound 5 and the methylamido compound 6 all show that the lone pair of the amido ligand lies preferentially in the equatorial binding plane of the cyclopentadienyl and imido ligands, a conformation due to the ir bonding interaction of the lone pair with the niobium centre. If rotation about the Nb-Namido bond becomes slow on the NMR time scale then two conformers will be observed, one with the amido proton oriented toward the cyclopentadienyl ring and one with it oriented away. It is supposed that the major conformer is that with the amido proton oriented toward the cyclopentadienyl ring, which minimizes the steric interactions present [32]. 

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