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Issue 18, 1997
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Reactions of iridium and ruthenium complexes with organicazides


Interaction of N 3 R with Ir(mes) 3 (mes = mesityl, C 6 H 2 Me 3 -2,4,6) gave products dependent on the nature of the azide. When R = mes, the tetrazenido amide complex 1 is obtained in which dehydrogenative coupling of the mesityl groups via the o-methyls has occurred; thermolysis of 1 in toluene resulted in cleavage of the tetrazene ring and formation of amide complex 2. When R = Ph, the aryl tetrazenido amide complex 3 is formed. Photolysis of a mixture of N 3 (mes) and [RuCl 2 (PPh 3 ) 3 ] followed by phosphine exchange gave the tetrazene complex [Ru II Cl 2 {N 4 (mes) 2 }(PMe 3 ) 2 ] 4. Thermal reaction of [RuCl 2 H 2 (PPr i 3 ) 2 ] with N 3 (mes) gave the triazenophosphorane complex [RuCl 3 (PPr i 3 ){N 3 (mes) PPr i 3 }] 5. The ruthenium allyl amide [Ru(PMe 3 ) 3 {NHC 6 H 3 Pr i 3 -CH 2 CCH 2 )}] 6 bearing a new hybrid ligand was obtained by interaction of trans-[RuCl 2 (PMe 3 ) 4 ] with Li[NH(C 6 H 3 Pr i 2 -2,6)] in di-n-butyl ether. Plausible reaction mechanisms accounting for the formation of the new compounds are proposed. Finally, the crystal structures of the complexes 1–6 have been determined. Complexes 1 and 2 have pseudo-square planar geometries involving the olefin formed by the coupled methyl groups of two mesityls and three (1) or two (2) amide nitrogens and a chlorine atom (2). Compound 3 has a trigonal bipyramidal metal centre with the axial Ir–N amide bonds longer than the equatorial ones; 4 has an octahedral structure with a bidentate tetragonal ligand and trans phosphines whilst 5 is distorted octahedral with a N,N-chelating phosphazide ligand. Complex 6 is also octahedral with the allyl groups occupying cis sites and the three Ru–P bonds in a facial arrangement.

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Article type: Paper
DOI: 10.1039/A703028B
Citation: J. Chem. Soc., Dalton Trans., 1997,0, 3177-3184
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    Reactions of iridium and ruthenium complexes with organic azides

    A. A. Danopoulos, R. S. Hay-Motherwell, G. Wilkinson, S. M. Cafferkey, T. K. N. Sweet and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1997, 0, 3177
    DOI: 10.1039/A703028B

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