μ-Peroxo-μ-oxo-bis[bis(trimethylsilylmethyl)tin]: the first structurally characterised main-group metal η2-peroxide, a formal tin analogue of an ozonide

The title compound is the first µ-η2-peroxodimetallic species to be characterised for a main group metal, possessing a long peroxo O–O bond, and large C–Sn–C angles, and is an unexpected product from the oxidation of [SnR2][R = CH(SiMe3)2], with a structure analogous to an organic ozonide.

Porphyrins with metal, metalloid or phosphorus atoms directly bonded to the carbon periphery

Organometallic porphyrins with a metal, metalloid or phosphorus fragment directly attached to their carbon framework emerged for the first time in 1976, and these macrocycles have been intensively investigated in the past decade. The present review summarises for the first time all reported examples as well as applications of these systems.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

[P,P-Di-tert-butyl-N-trimethylsilyl- P-(trimethylsilylamino)phosphineimidato-N,N]bis(pyridine-N)- lithium(I)

In the title compound, [Li(C14H36N2PSi2)(C5H5N)2], the bulky chelating monoanionic P,P-di-tert-butyl-N-trimethylsilyl-P-(trimethylsilylamino)phosphine imidate ligand and two pyridine ligands bind to Li in a pseudo-tetrahedral arrangement with twofold symmetry. The Li-N [phosphine]distance is 2.048 (5) Å, while the LiP distance is 2.520 (6) Å

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

New main group ligands for complexation with transition and inner transition elements

Symmetrical and unsymmetrical diphosphinoamines of the type X(2)PN(R)PX(2) and X(2)PN(R)YY' offer vast scope for the synthesis of a variety of transition metal organometallic complexes. Diphosphinoamines can be converted into their dioxides which are also accessible from appropriate (chloro)phosphane oxide precursors. The diphosphazane dioxides form an interesting series of complexes with lanthanide and actinide elements. Structural and spectroscopic studies have been carried out on a wide range of transition metal complexes incorporating linear P-N-P ligands and judiciously functionalized cyclophosphazanes and cyclo-phosphazenes.

Highly accurate quantum chemistry : spin-orbit splittings via multireference coupled-cluster methods and applications in heavy-atom main-group chemistry

Diese Dissertation demonstriert und verbessert die Vorhersagekraft der Coupled-Cluster-Theorie im Hinblick auf die hochgenaue Berechnung von Moleküleigenschaften. Die Demonstration erfolgt mittels Extrapolations- und Additivitätstechniken in der Single-Referenz-Coupled-Cluster-Theorie, mit deren Hilfe die Existenz und Struktur von bisher unbekannten Molekülen mit schweren Hauptgruppenelementen vorhergesagt wird. Vor allem am Beispiel von cyclischem SiS_2, einem dreiatomigen Molekül mit 16 Valenzelektronen, wird deutlich, dass die Vorhersagekraft der Theorie sich heutzutage auf Augenhöhe mit dem Experiment befindet: Theoretische Überlegungen initiierten eine experimentelle Suche nach diesem Molekül, was schließlich zu dessen Detektion und Charakterisierung mittels Rotationsspektroskopie führte. Die Vorhersagekraft der Coupled-Cluster-Theorie wird verbessert, indem eine Multireferenz-Coupled-Cluster-Methode für die Berechnung von Spin-Bahn-Aufspaltungen erster Ordnung in 2^Pi-Zuständen entwickelt wird. Der Fokus hierbei liegt auf Mukherjee's Variante der Multireferenz-Coupled-Cluster-Theorie, aber prinzipiell ist das vorgeschlagene Berechnungsschema auf alle Varianten anwendbar. Die erwünschte Genauigkeit beträgt 10 cm^-1. Sie wird mit der neuen Methode erreicht, wenn Ein- und Zweielektroneneffekte und bei schweren Elementen auch skalarrelativistische Effekte berücksichtigt werden. Die Methode eignet sich daher in Kombination mit Coupled-Cluster-basierten Extrapolations-und Additivitätsschemata dafür, hochgenaue thermochemische Daten zu berechnen.

Structural variations in aromatic 2 pi-electron three-membered rings of the main group elements

Structural variations of different Z pi-aromatic three-membered ring systems of main group elements, especially group 14 and 13 elements as compared to the classical description of cyclopropenyl cation has been reviewed in this article. The structures of heavier analogues as well as group 13 analogues of cyclopropenyl cation showed an emergence of dramatic structural patterns which do not conform, to the general norms of carbon chemistry. Isolobal analogies between the main group fragments have been efficiently used to explain the peculiarities observed in these three-membered ring systems.

Continuum in the X-Z-Y Weak Bonds: Z= Main Group Elements

The Continuum in the variation of the X-Z bond length change from blue-shifting to red-shifting through zero-shifting in the X-Z---Y complex is inevitable. This has been analyzed by ab-initio molecular orbital calculations using Z= Hydrogen, Halogens, Chalcogens, and Pnicogens as prototypical examples. Our analysis revealed that, the competition between negative hyperconjugation within the donor (X-Z) molecule and Charge Transfer (CT) from the acceptor (Y) molecule is the primary reason for the X-Z bond length change. Here, we report that, the proper tuning of X-and Y-group for a particular Z-can change the blue-shifting nature of X-Z bond to zero-shifting and further to red-shifting. This observation led to the proposal of a continuum in the variation of the X-Z bond length during the formation of X-Z---Y complex. The varying number of orbitals and electrons available around the Z-atom differentiates various classes of weak interactions and leads to interactions dramatically different from the H-Bond. Our explanations based on the model of anti-bonding orbitals can be transferred from one class of weak interactions to another. We further take the idea of continuum to the nature of chemical bonding in general. (C) 2015 Wiley Periodicals, Inc.

Chemical composition and reactivity of water on hexagonal Pt-group metal surfaces

The dissociation behaviour and valence-electronic structure of water adsorbed on clean and oxygen-covered Ru{0001}, Rh{111}, Pd{111}, Ir{111} and Pt{111} surfaces has been studied by high-resolution X-ray photoelectron spectroscopy with the aim of identifying similarities and trends within the Pt-group metals. On average, we find higher reactivity for the 4d metals (Ru, Rh, Pd) as compared to 5d (Ir, Pt), which is correlated with characteristic shifts in the 1b(1) and 3a(1) molecular orbitals of water. Small amounts of oxygen (<0.2 ML) induce dissociation of water on all five surfaces, for higher coverages (>0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.

Evaluation of selected platinum group metal complexes as chemiluminescence reagents

This research extends the investigations into the chemiluminescence and electrochemiluminescence of platinum group metal reagents and their applications. The effect of the chemical nature of tris(2,2'-bipyridyl)ruthenium(II) and selected analogues on the chemiluminescence reaction is further explored, and this chemistry is extended to include novel iridium(III) and osmium(II) based chemiluminescence reagents.

Testing the international linkage in the platinum-group metal futures markets

This study tests whether an international market exists in the platinum-group metal (PGM) futures markets. For this purpose, we tested the law of one price (LOP) and the causality between the U.S. and Japanese platinum and palladium futures markets. We also performed the test when structural breaks are considered. Long-run price relationships were found in both platinum and palladium markets but the LOP only sustained in the palladium market. The causality test revealed that it is the U.S. market that leads the price to transmit information between the U.S. and Japanese markets. Structural breaks had large impacts on the test results, suggesting that incorporating breaks is important when investigating the international price linkage in the PGM futures markets.

Manipulating charge-transfer character with electron-withdrawing main-group moieties for the color tuning of iridium electrophosphors

A new and synthetically versatile strategy has been developed for the phosphorescence color tuning of cyclometalated iridium phosphors by simple tailoring of the phenyl ring of ppy (Hppy=2-phenylpyridine) with various main-group moieties in [Ir(ppy-X)(2)(acac)] (X=B(Mes)(2), SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph). This can be achieved by shifting the charge-transfer character from the pyridyl groups in some traditional iridium ppy-type complexes to the electron-withdrawing main-group moieties and these assignments were supported by theoretical calculations.