Triple dehydrofluorination as a route to amidine-functionalized, aromatic phosphorus heterocycles.

An unexpected route to hitherto unknown amidine-functionalized phosphinines has been developed that is rapid and simple. Starting from primary amines and CF-substituted λ,σ-phosphinines, a cascade of dehydrofluorination reactions leads selectively to -amidinephosphinines. DFT calculations reveal that this unusual transformation can take place a series of nucleophilic attacks at the electrophilic, low-coordinate phosphorus atom.

Immobilization of an Iridium Pincer Complex in a Microporous Polymer for Application in Room-Temperature Gas Phase Catalysis.

An iridium dihydride pincer complex [IrH (POCOP)] is immobilized in a hydroxy-functionalized microporous polymer network using the concepts of surface organometallic chemistry. The introduction of this novel, truly innocent support with remote OH-groups enables the formation of isolated active metal sites embedded in a chemically robust and highly inert environment. The catalyst maintained high porosity and without prior activation exhibited efficacy in the gas phase hydrogenation of ethene and propene at room temperature and low pressure.

Phosphinine-Based Ligands in Gold-Catalyzed Reactions.

A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%V ) was calculated to get insight into the steric properties, [LNi(CO) ] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L-M interaction.

Cyaarside (CAs ) and 1,3-Diarsaallendiide (AsCAs ) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs ).

Reaction of the trivalent uranium complex [(( ArO) N)U(DME)] with one molar equiv [Na(OCAs)(dioxane) ], in the presence of 2.2.2-crypt, yields [Na(2.

Phosphinines versus mesoionic carbenes: a comparison of structurally related ligands in Au(i)-catalysis.

Gold(i) complexes based on a 2,4,6-triarylphosphinine and a mesoionic carbene derivative have been prepared and characterized crystallographically. Although structurally related, both heterocycles differ significantly in their donor/acceptor properties. These opposed electronic characteristics have been exploited in Au(i)-catalyzed cycloisomerization reactions.

Expanding the phosphorus-carbon analogy: formation of an unprecedented 5-phosphasemibullvalene derivative.

We could access for the first time a 5-phosphasemibullvalene derivative via quantitative and selective photochemical di-π-methane rearrangement from the corresponding phosphabarrelene. Due to the striking analogy between phosphorus and carbon, this hitherto unknown transformation of vinyl-phosphorus species provides the possibility to prepare novel, chiral and conformationally rigid organophosphorus cage compounds in a straightforward manner.