Experimental and computational studies of two new mono- and dinuclear iridium complexes containing a Buchwald biphenyl phosphine ligand

The reaction of [(η⁴-1,5-C₈H₁₂)₂Ir₂(μ-Cl)₂] with 2-di-t-butylphosphino-2′-methylbiphenyl (t-Bu₂Pbiph^Me) in the presence of AgBF₄ afforded the dichlorido-bridged Ir–Ag complex [(η⁴-1,5-C₈H₁₂)Ir(μ-Cl)₂Ag(t-Bu₂Pbiph^Me)] (1) which was fully characterized by a single crystal X-ray diffraction study. Sequential treatment of the diiridium precursor first with the silver salt and then with the phosphine yielded cyclometalated [(η⁴-1,5-C₈H₁₂)Ir(t-Bu₂Pbiph^Me–H⁺)] (2). Detailed DFT calculations gave evidence that the phosphine ligand of 2 forms a strained four-membered iridaheterocycle through orthometalation rather than a sterically congested six-membered chelate structure through C–H activation on the remote phenyl ring. The phosphonium salt [t-Bu₂P(H)biph^Me]BF₄ was isolated as a by-product of the preparations of 1 and 2; its crystal structure was determined.