Preparation of Benzyl Azide Complexes of Iridium(III)

Abstract

Hydride complexes IrHCl(2)(PiPr(3))P(2) (1) and IrHCl(2)P(3) (2) [P = P(OEt)(3) and PPh(OEt)(2)] were prepared by allowing IrHCl(2)(PiPr(3))(2) to react with phosphite in refluxing benzene or toluene. Treatment of IrHCl(2)P(3), first with HBF(4).Et(2)O and then with an excess of ArCH(2)N(3), afforded benzyl azide complexes [IrCl(2)(eta(1)-N(3)CH(2)Ar)P(3)]BPh(4) (3, 4) [Ar = C(6)H(5), 4-CH(3)C(6)H(4); P = P(OEt)(3), PPh(OEt)(2)]. Azide complexes reacted in CH(2)Cl(2) solution, leading to the imine derivative [IrCl(2){eta(1)-NH=C(H)C(6)H(5)}P(3)]BPh(4) (5). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [IrCl(2)(eta(1)-N(3)CH(2)C(6)H(5)){P(OEt)(3)}(3)]BPh(4) (3a) and [IrCl(2){eta(1)-NH=C(H)C(6)H(5)}{P(OEt)(3)}(3)]BPh(4) (5a). Both solid-state structure and (15)N NMR data indicate that the azide is coordinated through the substituted Ngamma [Ir]-Ngamma(CH(2)Ar)NNalpha nitrogen atom.

Azo Complexes of Osmium(II): Preparation and Reactivity of Organic Azide and Hydrazine Derivatives

“…The CN bond distance, 1.19(2) Å, is also shorter than that found for other benzylideneamido complexes with W, 41 Re, 42 Fe, 43 Ru, 37d or Ir. 7 The C(1)−N(3)−Os angle, 134(1)°, and the N(3)− C(1)−C(2) angle, 135(2)°, are also very imprecise and also surprisingly large for an sp 2 -hybridized N atom, but similar values have been found for the above-mentioned W, Re, Fe, Ru, and Ir complexes. The Os−P bond lengths are in two sets.…”

“…The high ν N 3 values of our complexes, compared with those of azide complexes whose X-ray structures are known, 6,7 suggest the η Variable-temperature NMR spectra of azide complexes 5−7 showed that the compounds are fluxional. The two broad signals observed at room temperature in the 31 P NMR spectra, already at −30°C, resolved into one triplet and one doublet, which could be simulated with an AB 2 model, indicating that the two phosphine ligands are magnetically equivalent and different from the third.…”

“…A mixed-metallic zirconium(IV)−iridium(III) complex containing a bridging PhNNN [D] group is also reported. 8b We are interested in the chemistry of diazo and triazo complexes of transition metals and have reported the synthesis and reactivity of hydrazine, diazene, diazenido, and triazene derivatives of Mn 10 and Fe 11 triads and, recently, the first benzylazide complexes of iridium 7 stabilized by phosphites P(OR) 3 as supporting ligands. We thought of extending our studies on azo complexes with the additional aim of preparing organic azide complexes of the iron triad.…”

Geometrically Specific Imino Complexes of the [Re6(μ3‐Se)8]2+ Core‐Containing Clusters

“…Similar H-migration has previously been reported in the photolysis of Ir-N 3 CH 2 Ph, a mononuclear metal-azide complex, under daylight at room temperature, producing the corresponding imino complex IrÀNH=CHPh. [20] The exclusive migration of one of the two H atoms in the photo-decomposition step can be explained by using the calculated PGSC of the cluster-azido intermediate ( Figure 5). …”

Trichlorostannyl complexes of iridium with both P-donor and N-donor ligands: Preparation and activity as hydrogenation catalysts

“…The chlorocomplex precursors mer-and fac-IrHCl 2 (PPh 3 ) 3 , IrHCl 2 (P i Pr 3 ) 2 , IrHCl 2 (HRpz)P 2 (P = PPh 3 , P i Pr 3 ; R = H, 3-Me), IrHCl 2 P 3 [P = P(OEt) 3 , PPh(OEt) 2 ] and the aryltriazenide IrHCl(g 2 -1,3-PhNNNPh)(PPh 3 ) 2 were prepared following previously reported methods [9][10][11][12][13].…”