AbstractHerein, we report the employment of the MoMo quintuple bonded amidinate complex to stabilize Group 10 metal fragments {(Et3P)2M} (M=Pd, Pt) and give rise to the isolation of the unprecedented δ complexes. X‐ray analysis unambiguously revealed short contacts between Pd or Pt and two Mo atoms and a slight elongation of the MoMo quintuple bond in these two compounds. Computational studies show donation of the MoMo quintuple‐bond δ electrons to an empty σ orbital on Pd or Pt, and back‐donation from a filled Pd or Pt dπ orbital into the MoMo δ* level (LUMO), consistent with the Dewar–Chatt–Duncanson model.

AbstractMetal‐metal triple bonds featuring s‐block element have not been reported until now. Only Be−Be double bonds between have been predicted theoretically based on the intuitive electron donation from four s1 type electron‐donating ligands. Herein, we theoretically predicted a novel species featuring a Be−Be triple bond in the Li6Be2 molecule. The molecule was found to be thermodynamically stable. The presence of the triple bond was confirmed by adaptive natural density partitioning (AdNDP), electron localization function (ELF), and atoms in molecules (AIM) analyses. Moreover, the mechanical strength of the Be−Be triple bond was analyzed by using compliance matrix, pointing towards its ultra‐weak nature.

The trans-bent Be₂X₄Y₂ structures are explained through ESP of Be₂X₄ and a perfect BeBe triple bond is confirmed in D_4h-Be₂Na₄K₂.

The triplet and singlet potential curves of Be2 generated by single and double excitations from 2σu into 3σg and (or) 1πu are studied with a multireference configuration interaction (MRD-CI) method. Relative to X1Σg+(2σg2 σu2) with Re = 4.72 bohr and ωe = 258 cm−1 (calculated here), these antibonding MO → bonding MO excitations lead to average decreases in bond distance (in bohr) of 0.55 (2σu → 3σg), 0.88 (2σu → 1πu), 0.93 (2σu2 → 3σg1πu), and 1.22 (2σu2 → 1πu2). The increase in vibrational frequencies ranges from 240 to 600 cm−1. The 3σg MO is found to be less bonding than 1πu, confirming predictions made by Bader et al. The experimental states A1Πu and B1Σu+ correspond to doubly excited 11Πu (2σu2 → 3σg1πu) and singly excited 11Σu+(2σu → 3σg), respectively. The 13Σg− and 11Δg states, both 2σu2 → 1πu2, preserve their doubly excited structure up to dissociation. Within the Franck–Condon region, 13Πu changes from bound (2σu2 → 3σg1πu) to repulsive (mixed 2σu → 1πg/2σg → 1πu), thereby creating the unusual situation of a strongly bound potential (short Re, high ωe) with an adiabatic dissociation energy near zero. The singlet counterpart 11Πu, however, behaves regularly as its doubly excited character is maintained up to large R(Be—Be). Key words: ab initio calculations, beryllium dimer, doubly excited states, electronic transitions, potential curves.