Reactivity of low-valent iridium, rhodium, and platinum complexes with Di- and tetrasubstituted hydrazines

Jessica M. Hoover, John Freudenthal, Forrest E. Michael, James M. Mayer

Research output: Contribution to journalArticlepeer-review

20 Scopus citations


Three complexes, IrCl(PEt3)3, Rh(NNN)Cl (NNN = 2,6-(CyN=CH)2C5H3N), and (NN)PtMe2 [NN = 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy)], have been investigated for N-N oxidative addition reactivity with di- and tetrasubstituted hydrazines. The reaction of IrCl(PEt3)3with 1,2-diphenylhydrazine (PhNHNHPh) forms the cyclometalated azobenzene complex (Et3P)2Cl(H)Ir(C6H4N=NPh) (1) and the 2:1 complex [(Et3P)2Cl(H)Ir]2(μ-C 6H4N=NC6H4) (2). The Rh(NNN)Cl pincer complex catalyzes the disproportionation of PhNHNHPh to azobenzene and aniline with no change in the Rh complex. The reaction of (bpy)PtMe2 with the hydrazine AcNHNHC(O)CH2CH2CH=CH2 (3) yields the platinum metallacycle (bpy)Pt(η2-AcN-NC(O)(CH 2)2CHCH2 (4). Although IrCl(PEt 3)3, Rh(NNN)Cl, and (NN)PtMe2 all undergo facile oxidative addition of other X-Y bonds, such reactivity is not observed for hydrazines; in the Ir and Pt systems there is a clear preference for cleavage of the stronger N-H bond over the N-N bond. The tetrasubstituted hydrazines tetraphenylhydrazine, 1,2-diphenyl-1,2-dimethylhydrazine, bisuccinimide, biphthalimide, and N-dimethylamino phthalimide do not react with IrCl(PEt3)3, Rh(NNN)Cl, and (NN)PtMe2. This lack of reactivity appears to be due to kinetic rather than thermochemical factors.

Original languageEnglish (US)
Pages (from-to)2238-2245
Number of pages8
Issue number10
StatePublished - May 26 2008
Externally publishedYes


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