An Operationally Unsaturated Iridium-Pincer Complex That C-H Activates Methane and Ethane in the Crystalline Solid-State.

The known complex [Ir(Bu-PONOP)MeH][BAr], [Bu-PONOP κ-2,6-(BuPO)CHN); Ar = 3,5-(CF)(CH); 131, 8603], is a robust precursor for single-crystal to single-crystal (SC-SC) C-H activation of methane and ethane at 80 °C. This contrasts with the reported solution (CDCl) behavior, where decomposes by methane loss. Crystalline is accessed as a single polymorph on a gram scale.

A Gold(I)-Acetylene Complex Synthesised using Single-Crystal Reactivity.

Using single-crystal to single-crystal solid/gas reactivity the gold(I) acetylene complex [Au(L1)(η-HC≡CH)][BAr ] is cleanly synthesized by addition of acetylene gas to single crystals of [Au(L1)(CO)][BAr ] [L1=tris-2-(4,4'-di-tert-butylbiphenyl)phosphine, Ar=3,5-(CF)CH]. This simplest gold-alkyne complex has been characterized by single crystal X-ray diffraction, solution and solid-state NMR spectroscopy and periodic DFT. Bonding of HC≡CH with [Au(L1)] comprises both σ-donation and π-backdonation with additional dispersion interactions within the cavity-shaped phosphine.