Phosphasilene mediated CO activation and deoxygenative homo coupling of CO molecules in reactions with metal carbonyls.

Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe)(PhC(N Bu)) (1) and its unprecedented reactivity with metal carbonyls (M = Fe, Mo, W). The reaction of 1 with Fe(CO) involves the deoxygenative homocoupling of two CO molecules, forming a rare ketene (μ-CCO) inserted Fe complex 2. Contrastingly, reactions with M(CO) (M = Mo, W) entail the deoxygenated activation of one CO molecule, with the second CO molecule being trapped between Si and P atoms.

Reducing hybrid ligand-based alane and chasing aluminium(I): dialane and unusual transient dialumene.

In this work, an alane, [DNIAlH] (1) (DNI = 3,3-dimethyl-2-[2-methyl-2-(2,6-diisopropyl-aniline)ethenyl]-3-indolenine), stabilised by a hybrid ligand was reduced by Jones's Mg(I) ([(BDIMg)]) and Roesky's Al(I) ([BDIAl:]). The resulting dialane compound [{DNI(H)Al}] (2) was characterised using NMR spectroscopy, mass spectrometry, DFT calculations and single-crystal XRD experiments. The reaction of aluminium dihydride [DNIAlH] (1) with [BDIAl:] at high temperatures gives an intramolecular C(sp)-H bond-activated compound 3.

Triplet carbenes with transition-metal substituents.

The extraordinary advances in carbene (R-C-R) chemistry have been fuelled by strategies to stabilize the electronic singlet state via π interactions. In contrast, the lack of similarly efficient approaches to obtain authentic triplet carbenes with appreciable lifetimes beyond cryogenic temperatures hampers their exploitation in synthesis and catalysis. Transition-metal substitution represents a potential strategy, but metallocarbenes (M-C-R) usually represent high-lying excited electronic configurations of the well-established carbyne complexes (M≡C-R).

Preparation of a high-coordinated-silicon-centered spiro-cyclic compound.

Silicon compounds containing silicon-silicon bond with a variety of unusual oxidation states are quite important, because their high reactivity leads to the formation of a variety of silicon compounds. The isolation of such compounds with unusual oxidation states requires a resilient synthetic strategy. Herein, we report the synthesis of a silicon based spirocyclic compound containing a hyper-valent silicon atom and a silicon-silicon bond.

Boron bis-(4-methylbenzoxazol-2-yl)-methanide complexes.

Boron compounds have attracted the attention of chemists because of their unique catalytic properties and potential wider material applications. Although group 13 metal compounds, which are based on the bis-(benzoxazol-2-yl)-methane system (Box, ({NCOCH}CH)), have been reported in the last several years, boron containing Box compounds were still missing. Now we report their successful syntheses and spectroscopic characterisation in this work.