Ten‐Electron Donor Indenyl Anion in Binuclear Transition‐Metal Sandwich Complexes: Electronic Structure and Bonding Analysis

Abstract

International audienceWhereas dinuclear sandwich complexes of pentalene, azulene and naphthalene are not uncommon, their bis-indenyl counterparts are scarce, with only two M2(indenyl)2 examples known so far. This paper investigates by the means of DFT calculations the possibility for such compounds to exist for the M=Sc−Ni and Y-(Re)-Pd series. Stable diamagnetic species are predicted for total valence electron counts (TNE) of 34 and 40. The most favored situation corresponds to TNE = 34. For this electron count, which exhibits full ligand hapticity, no formal metal-metal bond exists, but only weak non-bonding attraction. Adding supplementary electrons (TNE \textgreater 34) results in partial ligand decoordination. When TNE \textless 34, metal-metal bonding is predicted to compensate electron deficiency, with the largest formal bond order for TNE = 26. However, in the case of the series of the first-row metals, the metal-metal interaction is rather weak, thus favoring the existence of low-lying high-spin states. On the other hand, all the second-row (and Re) complexes are computed to be diamagnetic. It is concluded that there is no specific reason for M2(indenyl)2 complexes not being isolabl

Terminal and bridging ligand effects on M(I)M(I) multiple bonding: ADFTinvestigation of the coordination in (X)[M2Cl]L2complexes (M = Cr,Fe,L = CO,PEt3,X = Cl, allyl,Cp, and indenyl)

“…In order to explore and to understand the electronic structure, bonding properties, and chemical stability of the aforementioned binuclear complexes (Scheme 1), we provide a complete rationalization of their bonding by means of a theoretical DFT analysis using the generalized gradient approximation (BP86) and the hybrid B3LYP* levels and supported by the energy decomposition analysis (EDA) [50–52] exploiting the σ‐donation (L → M) and π‐backdonation (L ← M) capabilities of the interacting ligands [53, 54]. These functionals have been proved to reproduce the available experimental data and investigate the electronic properties of related mono‐ and dinuclear transition metal complexes [29, 55–69].…”

“…M) and π-backdonation (L M) capabilities of the interacting ligands [53,54]. These functionals have been proved to reproduce the available experimental data and investigate the electronic properties of related mono-and dinuclear transition metal complexes [29,[55][56][57][58][59][60][61][62][63][64][65][66][67][68][69].…”

Experimental and theoretical investigation of cyclometallated platinum(ii) complex containing adamantanemethylcyanamide and 1,4-naphthoquinone derivative as ligands: synthesis, characterization, interacting with guanine and cytotoxic activity

“…Moreover, this complex was studied by theoretical calculations and in an experimental evaluation for its interaction with guanine. The theoretical study was performed on both complexes cis-Pt(1,4-NQ)(1-ADpcyd)(H 2 O), 1, and cis-Pt(1,4-NQ)(1-ADpcyd)(G), 2, in order to obtain information about their molecular structures by analyzing their molecular orbitals, electronic structures, natural charges, Wiberg bond indices (WBI), and interaction energies using the BP86-D and B3LYP methods, [44][45][46][47][48][49][50][51][52] which have proved their reliability for metallic complexes in many previous studies. We endeavor herein to compare our results with those available experimentally in the literature of related systems.…”