Synthesis and Structural Studies of -Substituted Acenaphthenes with Tertiary Phosphine and Stibine Groups.

Two mixed -substituted phosphine-chlorostibines, Acenap(PPr)(SbPhCl) and Acenap(PPr)(SbCl) (Acenap = acenaphthene-5,6-diyl) reacted cleanly with Grignard reagents or BuLi to give the corresponding tertiary phosphine-stibines Acenap(PPr)(SbRR') (R, R' = Me, Pr, Bu, Ph). In addition, the Pt(II) complex of the tertiary phosphine-stibine Acenap(PPr)(SbPh) as well as the Mo(0) complex of Acenap(PPr)(SbMePh) were synthesised and characterised. Two of the phosphine-stibines and the two metal complexes were characterised by single-crystal X-ray diffraction. The -substituted species act as bidentate ligands through both P and Sb atoms, forming rather short Sb-metal bonds. The tertiary phosphine-stibines display through-space (CP) couplings between the phosphorus atom and carbon atoms bonded directly to the Sb atom of up to 40 Hz. The sequestration of the P and Sb lone pairs results in much smaller corresponding (CP) being observed in the metal complexes. QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis employing Naturalised Orbitals for Chemical Valence) computational techniques were used to provide additional insight into a weak n(P)→σ*(Sb-C) intramolecular bonding interaction (pnictogen bond) in the phosphine-stibines.