Arylamido complexes

Arylallenes, in rhodium complexes, 7, 221—222 Arylallyl ethers, isomerization, 10, 88 Arylamido complexes with Zr(IV), 4, 771... 

Arylamido complexes of a general formula of Cp Zr[N(Ar)SiMe3]Cl2 can be obtained in a similar fashion. Thus, the reaction of Cp MCl3 with 1 equiv. of Li[N(Ar)SiMe3] produces complexes 31248 and 313.252 The difluoride 312 was prepared by metathesis reaction of the dichloride and Me3SnF. Upon activation with MAO, all complexes are active for polymerization of ethylene within complexes 312, the zirconium complexes are much more active than the analogous hafnium complexes, whereas within complexes 313, the zirconium complex exhibits poor activity as compared with the analogous titanium complex. 

The zirconocene bis(arylamido) complex 787 was obtained by the reaction of Cp2ZrCl2 with 2 equiv. of the lithium amide605 (Scheme 195). When the reaction is carried out in a 1 1 ratio, the monoamide zirconocene chloride is generated as the major product. Reaction of in situ-generated Cp 2Zr with 2-(methylmercapto)aniline yields monoamido zirconocene hydride 788, the spectroscopic data of which suggest an interaction between the S atom and the Zr center in this complex. The bis(amido) complex 787 serves as a precursor for the synthesis of amido rhodium and iridium complexes. 

A number of bis(arylamido)- and bis(diarylamido)ruthenium(IV) porphyrin complexes have been reported. In general, these complexes can be prepared by the reduction of [Ru(0)2(por)] with corresponding aromatic amines or by the oxidative deprotonation of [Ru (por)(ArNH2)2], as shown in Scheme 18. 

Bis(arene)zirconium complexes, characteristics, 4, 697 Bis(arylamido)pyridines, with Hf(IV), 4, 792 Bis(aryl) bridges, in complexes with chromium(VI), 5, 346... 

To fine-tune the metal complex sterics, electronics, and geometries, as well as the stability of the resulting cationic catalysts with respect to ligand degradation due to C-H activation, a series of Zr(iv) and Hf(iv) diamide, dichloride, and dialkyl complexes incorporating tridentate bis(arylamido)amines 145134 135 and a bis(arylamido)pyridine 146136 137 has been synthesized using a combination of standard salt metathesis, amine elimination, and alkylation... 

Late-transition-metal-amido complexes have been prepared by metathetical substitution reactions, or-bonded ligand exchange, deprotonation of amine complexes, and oxidative addition of N-H bonds. Metathetical substitution is the most common route to late-metal-alkylamido complexes, whereas metathetical substitution and a-bonded ligand exchange have both been used commonly to prepare arylamido compounds. 

The same group synthesized the phosphido (phosphanido) complex [Re(PPh2)(CO)3(phen)j and carried out preliminary studies of its reactivity. In contrast with the reactions of alkoxo, hydroxo, or arylamido... 

Hartwig JF, Bergman RG, Andersen RA (1991) Insertion reactions of CO and CO2 with ruthenium benzyl, arylamido, and aryloxide complexes a comparison of the reactivity of ruthenium-carbon, ruthenium-nitrogen, and ruthenium-oxygen bonds. J Am Chem Soc 113 6499-6508... 

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