Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η5-C5Me5)Ir(C2H4)(p-N2C6H4OMe)][BF4] and a comparison with the analogous nitrosyl complex [(η5-C5Me5)Ir(C2H4)(NO)][BF4]

[Cp*Ir(C2H4)(N2Ar)][BF4] (1BF4; Ar = p-N2C6H4OMe) has been synthesized by reacting [ArN2] [BF4] with Cp*Ir(C2H4)2 at low temperature. An initial electrophilic attack of the incoming diazonium ion at iridium, followed by expulsion of C2H4, is postulated to account for the mild reaction conditions that are in sharp contrast to the usual inertness of the bis(ethylene) compound toward ligand substitution. The IR and nitrogen NMR data for 1BF4 and its 15Nα derivative unambiguously establish that the ArN2 ligand has the singly bent geometry in this complex in solution. The X-ray crystal structure confirms this for the solid state, and establishes that the plane of the aryldiazenido ligand is approximately perpendicular to the plane defined by the Ir atom and the centers of mass of the Cp* and ethylene ligands. An extended Hückel molecular orbital analysis of the singly bent aryldiazenido ligand has been carried out and satisfactorily accounts for the observed orientation of the ArN2 ligand. An analysis of the variable-temperature 1H and 13C NMR of 1BF4 indicates that both restricted rotation of the C2H4 ligand and a conformational isomerization of the aryldiazenido ligand are occurring, and ΔG≠270 for the ethylene rotation barrier is estimated at ≤ 51.5 ± 0.4 kJ mol−1. This is lower than the barrier of ΔG≠353 = 68.7 ± 0.2 kJ mol−1 determined previously for the analogous nitrosyl complex [Cp*Ir(C2H4)(NO)] [BF4] (2BF4) and it is suggested that in these half-sandwich complexes both NO and ArN2 function as single-faced π-acceptors, and in these circumstances ArN2 is the better π-acceptor. The ethylene in 1BF4 is readily displaced by PPh3 to give [Cp*Ir(PPh3)(N2Ar)][BF4] (3BF4). This reacts with NaBH4 to yield Cp*IrH(PPh3)(N2Ar) (4) in which the ArN2 ligand has switched to the doubly bent geometry, on the basis of the 15Nα NMR chemical shift data. Attempts to synthesize the corresponding chloro analogue 5 resulted in only the chloride salt of the singly bent ArN2 cation 3. For example, reaction of 3BF4 with HCl yields the aryldiazene complex [Cp*IrCl(PPh3)(NHNAr)] [BF4] (6), but deprotonation of this with Et3N yields 3Cl, not 5. Compound 1BF4 crystallized in the space group P21/n with a = 8.5780(10) Å, b = 20.5310(23) Å, c = 12.0310(15) Å, β = 93.500(10)°, and Z = 4. The structure was refined to Rf = 0.0281 on the basis of 2611 observed reflections with I°> 2.5σ(Io) in the range 2θ = 0–50° (Mo-Kα). Keywords: iridium, cyclopentadienyl, aryldiazenido, nitrosyl, ethylene.