In solution the PCy3/B(C6F5)3 pair is rapidly deactivated by nucleophilic aromatic substitution. In the solid state (or in a fluorous liquid), however, it serves as an active frustrated Lewis pair to effectively split dihydrogen.

Al/P‐ and Ga/P‐based frustrated Lewis pairs (FLPs) reacted with an azirine under mild conditions under cleavage of the heterocycle on two different positions. Opening of the C−C bond yielded an unusual nitrile–ylide adduct in which a C−N moiety coordinated to the FLP backbone. Cleavage of a C−N bond afforded the thermodynamically favored enamine adduct with the N atom bound to P and Al or Ga atoms. Ring closure was observed upon treatment of an Al/P FLP with electronically unsaturated substrates (4‐(1‐cyclohexenyl)‐1‐aza‐but‐1‐en‐3‐ynes) and yielded by C−N bond formation hexahydroquinoline derivatives, which coordinated to the FLP through P−C and Al−C bonds. Diphenylcyclopropenone showed a diverse reactivity, which depending on steric shielding and the polarizing effect of Al or Ga atoms afforded different products. An AltBu2/P FLP yielded an adduct with the C=O group coordinated to P and Al. The dineopentyl derivative gave an equilibrium mixture consisting of a similar product and a simple adduct with O bound to Al and a three‐coordinate P atom. Both compounds co‐crystallize. The Ga/P FLP only formed the simple adduct with the same substrate. Rearrangement resulted in all cases in C3‐ring cleavage and migration of a mesityl group from P to a former ring C atom by C−C bond formation. Diphenylthiocyclopropenone (evidence for the presence of P=C bonds) and an imine derivative afforded similar products.

The first comprehensive solid-state nuclear magnetic resonance (NMR) characterization of geminal alanephosphane frustrated Lewis pairs (Al/P FLPs) is reported. Their relevant NMR parameters (isotropic chemical shifts, direct and indirect 27 Al-31 P spin-spin coupling constants, and 27 Al nuclear electric quadrupole coupling tensor components) have been determined by numerical analysis of the experimental NMR line shapes and compared with values computed from the known crystal structures by using density functional theory (DFT) methods. Our work demonstrates that the 31 P NMR chemical shifts for the studied Al/P FLPs are very sensitive to slight structural inequivalences. The 27 Al NMR central transition signals are spread out over a broad frequency range (> 200 kHz), owing to the presence of strong nuclear electric quadrupolar interactions that can be well-reproduced by the static 27 Al wideband uniform rate smooth truncation (WURST) Carr-Purcell-Meiboom-Gill (WCPMG) NMR experiment. 27 Al chemical shifts and quadrupole tensor components offer a facile and clear distinction between three-and four-coordinate aluminum environments. For measuring internuclear Al•••P distances a new resonance-echo saturation-pulse double-resonance (RESPDOR) experiment was developed by using efficient saturation via frequency-swept WURST pulses. The successful implementation of this widely applicable technique indicates that internuclear Al•••P distances in these compounds can be measured within a precision of � 0.1 Å.

The synthesis and characterization of the bis(h 6benzene)lithium cation, the benzene metallocene of the lightest metal, is reported. The boron compound FmesBCl 2 [Fmes: 2,4,6-tris(trifluoromethyl)phenyl]r eacted with three molar equivalents of the lithio-acetylene reagent Li-C C-Fmxyl [Fmxyl:3 ,5-bis(trifluoromethyl)phenyl].S ubsequent crystallization from benzene gave the [bis(h 6 -benzene)Li] + cation with the [{FmesB(-CC-Fmxyl) 3 } 2 Li] À anion. This parent [(arene) 2 Li] + cation shows an eclipsed arrangement of the pair of benzene ligands at the central lithium cation with uniform carbon-lithium bond lengths.The corresponding [(h 6toluene) 2 Li] + and [(h 6 -durene) 2 Li] + containing salts were similarly prepared. The bis(arene)lithium cations were characterized by X-ray diffraction, by solid-state 7 Li MAS NMR spectroscopyand their bonding features were analyzed by DFT calculations.