A Convenient and Selective Palladium‐Catalyzed Aerobic Oxidation of Alcohols

An efficient procedure for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, with molecular oxygen under ambient conditions has been achieved. By applying catalytic amounts of Pd(OAc)₂ in the presence of tertiary phosphine oxides (O?PR₃) as ligands, a variety of substrates are selectively oxidized without formation of ester byproducts. Spectroscopic investigations and DFT calculations suggest stabilization of the active palladium(II) catalyst by phosphine oxide ligands.     

A Silyliumylidene Cation Stabilized by an Amidinate Ligand and 4‐Dimethylaminopyridine

The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [ L Si:]₂ ( 1 ; L =PhC(NtBu)₂) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe₂C₅H₄NSiMe₃]OTf and two equivalents of DMAP in THF afforded [ L Si(DMAP)]OTf ( 2 ). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [ L′ ₂( L )Si]OTf ( 3 ; L′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)₃}] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(NtBu)₂C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography.     

S‐Alkylation of Soft Scorpionates

The alkylation reactions of soft scorpionates are reported. The hydrotris(S‐alkyl‐methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of Tm^Me anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C?S versus B? H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo‐μ‐aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ³‐S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S‐alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B? N bond in soft scorpionates, which has implications for their use in more advanced chemistry.     

Impact of the Synergistic Collaboration of Oligothiophene Bridges and Ruthenium Complexes on the Optical Properties of Dumbbell‐Shaped Compounds

The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the ³π? π* state of the conjugated bridge below the ³MLCT‐emitting states of the end‐capping Ru^II complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10^?78 cm⁶ s² at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications.     

Theoretical Insights into the Nature of Halogen Bonding in Prereactive Complexes

Benchmark quality geometries and interaction energies for the prereactive halogen‐bonded complexes of dihalogens and ammonia, including hypothetical astatine containing dihalogens, have been produced via explicitly correlated coupled cluster methods. The application of local electron correlation partitioning reveals dispersion, electrostatics and ionic substitutions all contribute significantly to the interaction energy, with a linear relationship between the ionic substitutions and the degree of charge transfer. Potential energy curves for H₃N???ClF show that as the relative orientations of the two subunits are manipulated appreciable interactions can be found at considerably angular displaced geometries, signifying lower directionality in halogen bonding than previously supposed.     

Heptametallic,Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

New complexes with six ferrocenyl (Fc) groups connected to Zn^II or Cd^II tris(2,2′‐bipyridyl) cores are described. A thorough characterisation of their BPh₄^? salts includes two single‐crystal X‐ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(Fe^II)→π* metal‐to‐ligand charge‐transfer (MLCT) bands accompany the π→π* intraligand charge‐transfer absorptions in the near UV region. Each complex shows a single, fully reversible Fe^III/II wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper‐Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β₀ reaching as high as approximately 10^?27 esu and generally increasing with π‐conjugation extension. Z‐scan cubic NLO measurements reveal high two‐photon absorption cross‐sections σ₂ of up to 5400 GM in one case. DFT calculations reproduce the π‐conjugation dependence of β₀, and TD‐DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature.     

Unprecedented Electron‐Poor Octahedral Ta6 Clusters in a Solid‐State Compound: Synthesis,Characterisations and Theoretical Investigations of Cs2BaTa6Br15O3

The crystal structure of Cs₂BaTa₆Br₁₅O₃ has been elucidated by using synchrotron X‐ray powder diffraction and absorption experiments. It is built from edge‐bridged octahedral [(Ta₆${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]^4? cluster units with a singular poor metallic electron (ME) count equal to thirteen. This leads to a paramagnetic behaviour related to one unpaired electron. The arrangement of the Ta₆ clusters is similar to that of Cs₂LaTa₆Br₁₅O₃ exhibiting 14‐MEs per [(Ta₆${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]^5? motif. The poorer electron‐count cluster presents longer metal–metal distances as foreseen according to the electronic structure of edge‐bridged hexanuclear cluster. Density functional theory (DFT) calculations on molecular models were used to rationalise the structural properties of 13‐ and 14‐ME clusters. Periodic DFT calculations demonstrate that the electronic structure of these solid‐state compounds is related to those of the discrete octahedral units. Oxygen–barium interactions seem to prevent the geometry of the octahedral cluster to strongly distort, allowing stabilisation of this unprecedented electron‐poor Ta₆ cluster in the solid state.     

Conformational Isomerism in Monomeric,Low‐Coordinate Group 12 Complexes Stabilized by a Naphthyl‐Substituted m‐Terphenyl Ligand

The synthesis and characterization of the first series of low‐coordinate bis(terphenyl) complexes of the Group 12 metals, [Zn(2,6‐Naph₂C₆H₃)₂] ( 1 ), [Cd(OEt₂)(2,6‐Naph₂C₆H₃)₂] ( 2 ) and [Hg(OEt₂)(2,6‐Naph₂C₆H₃)₂] ( 3 ) (Naph=1‐C₁₀H₇) are described. The naphthyl substituents of the terphenyl ligands confer considerable steric bulk, and as a result of limited flexibility introduce multiple conformations to these unusual systems. In the solid state, complex 1 features a two‐coordinate Zn centre with the ligands oriented in a syn/anti conformation, whereas the three‐coordinate distorted T‐shaped complexes 2 and 3 feature the ligands in the syn/syn configurations. The results of DFT calculations are in good agreement with the solid‐state configurations for these complexes and support the spectroscopic measurements, which indicate several conformers in solution.     

Like (CO)4, Do (CS)4 and (CSe)4 Have a Triplet Ground State?

Cyclobutane‐1,2,3,4‐tetraone, (CO)₄, was computationally predicted and, subsequently, experimentally confirmed to have a triplet ground state, in which a b_2g σ MO and an a_2u π MO were each singly occupied. In contrast, the (U)CCSD(T) calculations reported herein found that cyclobutane‐1,2,3,4‐tetrathione, (CS)₄, and cyclobutane‐1,2,3,4‐tetraselenone, (CSe)₄, both had singlet ground states, in which the b_2g σ MO was doubly occupied and the a_2u π MO was empty. Our calculations showed that both the longer C?X distances and smaller coefficients on the carbon atoms in the b_2g and a_2u MOs of (CS)₄ and (CSe)₄ contributed to the difference between the ground states of these two molecules and the ground state of (CO)₄. An experimental test of the prediction of a singlet ground state for (CS)₄ is proposed.