Transition-Metal-Stabilized Heavy Tetraphospholide Anions.

Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP and PbP.

Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts.

Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step.

Photocatalytic Arylation of P and PH : Reaction Development Through Mechanistic Insight.

Detailed P{ H} NMR spectroscopic investigations provide deeper insight into the complex, multi-step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P ). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non-innocent behavior of the commonly employed terminal reductant Et N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy) ][PF ] (dtbbpy=4,4'-di-tert-butyl-2,2'-bipyridine) and 3DPAFIPN.

A Phosphinine-Derived 1-Phospha-7-Bora-Norbornadiene: Frustrated Lewis Pair Type Activation of Triple Bonds.

Invited for the cover of this issue are the groups of Ruth M. Gschwind and Robert Wolf (University of Regensburg), Christian Müller (Freie Universität Berlin), and J. Chris Slootweg (University of Amsterdam).

A Phosphinine-Derived 1-Phospha-7-Bora-Norbornadiene: Frustrated Lewis Pair Type Activation of Triple Bonds.

Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2. The C≡N triple bonds of nitriles insert into the P-B bond of 2 with concomitant C-B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ -phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs.

Direct catalytic transformation of white phosphorus into arylphosphines and phosphonium salts.

Phosphorus compounds are ubiquitous in the chemical sciences, finding applications throughout industry and academia. Of particular interest to synthetic chemists are organophosphorus compounds, which contain P-C bonds. However, state-of-the-art processes for the synthesis of these important materials rely on an inefficient, stepwise methodology involving initial oxidation of white phosphorus (P) with hazardous chlorine gas and the subsequent displacement of chloride ions.

Facile C=O Bond Splitting of Carbon Dioxide Induced by Metal-Ligand Cooperativity in a Phosphinine Iron(0) Complex.

New iron complexes [Cp*FeL] (1-σ and 1-π, Cp*=C Me ) containing the chelating phosphinine ligand 2-(2'-pyridyl)-4,6-diphenylphosphinine (L) have been prepared, and found to undergo facile reaction with CO under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L. Interaction of CO with the isomer 1-π, in which L binds to Fe through the phosphinine moiety in an η fashion, leads to the formation of 3-π, in which CO has undergone electrophilic addition to the phosphinine group.