Phosphaalkynes—Syntheses, Reactions, Coordination Behavior [New Synthetic Methods (73)]

Abstract

Methods (73)Organophosphorus compounds have been applied in two ways in chemical synthesis. They can either be used as a reagent in a step of the synthesis (for example, in the Wittig reaction) or they can be incorporated directly into the target molecule. This second application, in particular, has expanded greatly in the last few years with the preparation of low-coordination phosphorus compounds. These include the phosphaalkynes, which are of great interest to organic and inorganic chemists. Phosphaalkynes have been employed in the synthesis of heterocyclic compounds, phosphaarenes and their valence isomers, and polycyclic compounds. Further applications have been the use of phosphaalkynes as new ligand systems in complex chemistry and their cyclooligomerization with organometallic reagents. While the chemical properties of phosphaalkynes have little in common with those of nitriles, they are in many ways very similar to those of the isoelectronic acetylenes.

Flexidentate Coordination Behavior and Chemical Non‐Innocence of a Bis(1,3‐Diphosphacyclobutadiene) Sandwich Anion

“…Aiming at the synthesis of the hypothetical triple-decker complex [CpNi(m-P 2 C 2 tBu 2 )Co(P 2 C 2 tBu 2 )] (Cp = C 5 H 5 ), we began with the reaction of [K(thf) 2 {Co(P 2 C 2 tBu 2 ) 2 }] [7] with Werner's classic complex [Ni 2 Cp 3 ]BF 4…”

“…[1,2] Both the 1,2-and 1,3diphosphacyclobutadiene isomersa re accessible. [1,2] Both the 1,2-and 1,3diphosphacyclobutadiene isomersa re accessible.…”

Recent Advances in the Chemistry of Anellated Azaphospholes

“…The reviews on heterophospholes in general include anellated azaphospholes, though in a limited manner [1][2][3][4][5]. The reviews dealing primarily with the synthetic uses of phosphaalkynes also include the synthesis of anellated azaphospholes through [3+2] cycloaddition [15][16][17]. The 31 P NMR chemical shifts of a large number of anellated azaphospholes are included in two reviews [11,18].…”

Transformation of an η1-coordinated phosphaalkyne into a bridging phosphinidene ligand

“…In conclusion, we have shown that t BuCP coordinates to a tripalladium cluster in a g 1 -coordination mode to form the cluster [Pd 3 (l-dppm) 3 (g 1 -PCBu t ) 2 ](PF 6 ) 2 (2). Storage of acetone solution of 2 for prolonged periods affords [Pd 3 (l-dppm) 3 (g 1 :l 3 -PCH 2 Bu t )(OCMe 2 )](PF 6 ) 2 (3) in which one of the t BuCP ligands has been displaced and the other converted to a bridging phosphinidene.…”

“…The kinetically stabilized phosphaalkyne Bu t CP, first prepared by Becker [1], has proven to be one of the most important and versatile building blocks during the recent renaissance in phosphaorganic chemistry [2]. Phosphaalkynes have been shown to be the precursors for a wide range of cyclic and acyclic organophosphorus compounds and the resemblance of these species to their isoelectronic and isostructural organic analogues has coined the ''phosphorus-the carbon copy'' analogy [3].…”