Enhanced 5f-δ bonding in [U(C7H7)2]−: Carbon K‑Edge X‑ray Spectroscopy, Magnetism and Electronic Structure Calculations

[U(C7H7)2]− is a singular molecule, as the only η7-cycloheptatrienyl sandwich compound, and the only homoleptic metallocene of a pentavalent f-element. Previous magnetic and theoretical studies of [U(C7H7)2]− have provided evidence...

A sandwich-type cluster containing Ge@Pd3 planar fragment flanked by aromatic nonagermanide caps

Sandwich-type clusters with the planar fragment containing a heterometallic sheet have remained elusive. In this work, we introduce the [K(2,2,2-crypt)]4{(Ge9)2[η6-Ge(PdPPh3)3]} complex that contains a heterometallic sandwich fragment. The title compound is structurally characterized by means of single-crystal X-ray diffraction, which reveals the presence of an unusual heteroatomic metal planar fragment Ge@Pd3. The planar fragment contains a rare formal zerovalent germanium core and a peculiar bonding mode of sp2-Ge@(PdPPh3)3 trigonal planar structure, whereas the nonagermanide fragments act as capping ligands. The chemical bonding pattern of the planar fragment consists of three 2c-2e Pd-Ge σ-bonds attaching Pd atoms to the core Ge atom, while the binding between the planar fragment and the aromatic Ge9 ligands is provided by six 2c-2e Pd-Ge σ-bonds and two delocalized 4c-2e σ-bonds. The synthesized cluster represents a rare example of a sandwich compound with the heteroatomic metal planar fragment and inorganic aromatic capping ligands.

Optical limiting properties, structure and simplified TD-DFT calculations of scandium tetra-15-crown-5 phthalocyaninates

The optical limiting properties of crown-ether-substituted scandium(III) phthalocyaninate complexes, bis-tetra-15-crown-5-phthalocyaninates Sc[(15C5)4Pc][Formula: see text] (I) and Sc[(15C5)4Pc][Formula: see text] (Ia), together with monophthalocyaninate [(15C5)4Pc]Sc(OAc) (II) were measured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns). It was revealed that expansion of the [Formula: see text]-system on moving from the monomeric Sc complex II to sandwich compound I and changing the electronic state of the sandwich compound from the anionic Ia species to the neutral radical I improves the optical limiting properties. The Im[[Formula: see text]] values obtained lie in the 10[Formula: see text]–10[Formula: see text] esu range that is consistent with those reported previously for other organic chromophores. The crystal structure of sandwich Sc(III) complex I was elucidated by means of single-crystal X-ray diffraction analysis and was used to guide a series of theoretical calculations. It was demonstrated that the application of simplified time-dependent density functional theory (sTD-DFT) calculations can provide reasonably accurate predictions for compounds of this type when the geometries of the complexes are clearly defined.

Ferrocene analogues of sandwich M(CrB6H6)2: a theoretical investigation

Ferrocene analogues of a new sandwich compound Cr(CrB6H6)2 following the 18-electron principle: the spd–π interaction.