The coordination chemistry of 2,4,6-oxy functionalised 1,3,5-triphosphinines.

A number of stable group 6 metal complexes bearing 2,4,6-oxy functionalised 1,3,5-triphosphinines, phosphorus containing heterocyclic ligands with a central CP core, were synthesised such that a complete series of [M{PC(OX)}(CO)] compounds is obtained [M = Cr(0), Mo(0), W(0); X = H, SiBuPh, B(ipc)]. In all complexes, the triphosphinine coordinates in a η-binding mode the delocalized 6π-system of the ring. The ligand properties can be tuned by changing the substituent on the oxygen centre.

Solid-State Investigation, Storage, and Separation of Pyrophoric PH and P H with α-Mg Formate.

Phosphane, PH -a highly pyrophoric and toxic gas-is frequently contaminated with H and P H , which makes its handling even more dangerous. The inexpensive metal-organic framework (MOF) magnesium formate, α-[Mg(O CH) ], can adsorb up to 10 wt % of PH . The PH -loaded MOF, PH @α-[Mg(O CH) ], is a non-pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane.

Organocatalyzed Phospha-Michael Addition: A Highly Efficient Synthesis of Customized Bis(acyl)phosphane Oxide Photoinitiators.

Addition of the P-H bond in bis(mesitoyl)phosphine, HP(COMes) (BAPH), to a wide variety of activated carbon-carbon double bonds as acceptors was investigated. While this phospha-Michael addition does not proceed in the absence of an additive or catalyst, excellent results were obtained with stoichiometric basic potassium or caesium salts. Simple amine bases can be employed in catalytic amounts, and tetramethylguanidine (TMG) in particular is an outstanding catalyst that allows the preparation of bis(acyl)phosphines, R-P(COMes) , under very mild conditions in excellent yields after only a short time.

Reduction of Nitrogen Oxides by Hydrogen with Rhodium(I)-Platinum(II) Olefin Complexes as Catalysts.

The nitrogen oxides NO , NO, and N O are among the most potent air pollutants of the 21 century. A bimetallic Rh -Pt complex containing an especially designed multidentate phosphine olefin ligand is capable of catalytically detoxifying these nitrogen oxides in the presence of hydrogen to form water and dinitrogen as benign products. The catalytic reactions were performed at room temperature and low pressures (3-4 bar for combined nitrogen oxides and hydrogen gases).

Hydrogenolysis of Polysilanes Catalyzed by Low-Valent Nickel Complexes.

The dehydrogenation of organosilanes (R SiH ) under the formation of Si-Si bonds is an intensively investigated process leading to oligo- or polysilanes. The reverse reaction is little studied. To date, the hydrogenolysis of Si-Si bonds requires very harsh conditions and is very unselective, leading to multiple side products.