Über metallorganische Derivate des Acetylens. II. Über die Darstellung und Eigenschaften des Bis‐(diphenyl‐phosphor)‐acetylens und einiger seiner Derivate

Abstract

Die Darstellung und die Eigenschaften des Bis‐(diphenyl‐phosphor)‐acetylens werden beschrieben. Das Acetylid ist in der Lage, je ein Atom Sauerstoff bzw. Schwefel an den einsamen Elektronenpaaren des Phosphors anzulagern. Durch Addition von 1 Mol Alkylhalogenid an ein Phosphoratom der Verbindung entstehen salzartige “Onium”‐Verbindungen. Sowohl die Sauerstoff‐ bzw. Schwefelanlagerungsprodukte als auch die Onium‐Verbindungen sind hydrolyseempfindlicher als die reine Acetylen‐Verbindung. Der Verlauf der Hydrolyse sowie die entstehenden Produkte werden diskutiert.

The Phosphonous Acids and Their Derivatives.

“…(a) Phosphinous compounds Phosphinous halides are often by-products of the synthesis of phosphonous dihalides. With the use of more severe reaction conditions it is possible to convert phosphonous dichlorides to phosphinous chlorides in good yield, as in the reaction with organolead com-pounds (32), organozinc compounds (338), or organomercury compounds (63,109,206,224,231,238,248,274,287,337):…”

“…CeHsPCl, + RsHg -> C.H.RPC1 + RHgCl An attempt to use an organolithium reagent failed because even when the lithium compound was added slowly to a large excess of the phosphonous dichloride in ether solution, the only products were the tertiary phosphine and unreacted dichloride (109).…”

“…Tertiary phosphines may also be prepared with organolithium compounds (95,109,187). The novel heterocyclic compound "pentaphenylphosphole" was prepared by this method, using a dilithium compound derived from diphenylacetylene (187).…”

Synthesis of Some New Phosphino Acetylenes

“…These include trialkynylphosphines P(C=CR), (2)(3)(4), dialkyl or diary1 alkynylphosphines R,'PC=CR (5-lo), aryldialkynylphosphines RfP(C_CR), (3), acetylenic diphosphines R,PC_CPR, (5,(11)(12)(13), and a variety of organometal phosphines with aacetylenic substituents (14). Our interest in the coordinating properties of acetylenic phosphines and diphosphines (15) prompted us to attempt the synthesis of several ligands having substituents of varying electronegativity on the phosphorus atom or hydrocarbon residue.…”

The Influence of Stepwise P-Oxidation on the Coordination and Redox Behavior of W–Bisphosalkyne Complex Ligands

“…Although oxidized dppa derivatives have been known for about 60 years from Hartmann, the corresponding side-on complexes are limited to dicobalt systems presented by Hong . They could show that BPMOs (Chart ) react with Pd­(II) to form a trinuclear complex with a Co → Pd interaction leaving the P­(O)­Ph 2 group out of coordination.…”