86212-05-7

Upstream product

• 1079-66-9 chloro-diphenylphosphine 
• 73785-70-3 Lithium-bis(diphenylphosphanyl)amid 
• 153647-81-5 C₅₀H₄₂P₄ 
• 28926-61-6 Lithium-bis(diphenylphosphanyl)methanid 

Relevant academic research and scientific papers

Polyfunctional Ligands: Comparative Oxidative Coupling of - (E = CH, N) with Iodine

Iodine oxidation of the isoelectronic anions - and - affords the structurally characterized P-P coupling product Ph2P-N=PPh2-PPh2=N-PPh2 and the P-C coupling product (Ph2P)2C=PPh2-CH2-PPh2, respectively; the P-P heterocoupling product

Polyfunctional ligands: carbon-carbon oxidative coupling of - and crystal structure of the new tetraphosphine ligand (Ph2P)2CH-CH(PPh2)2

Oxidation of a THF solution of Li with iodine affords the isomeric products Ph2P-CH=PPh2-PPh2=CH-PPh2 2, (Ph2P)2C=PPh2-CH2-PPh2 4 and (Ph2P)2CH-CH(PPh2)2 1, which result from P-P, P-C and C-C coupling, respectively.The latter pathway has now been established for the first time and the crystal structure of the resulting new chiral tetraphosphine 1 has been determined by X-ray diffraction.Keywords: bis(diphenylphosphino)methanide / carbon-carbon coupling / phosphorus ylide / tetraphosphine / chiral ligand

Oxidative Verknuepfung von Phosphinomethanidliganden and Titanocen- und Bismutzentren: selektive C-C-, P-C- und P-P-Bindungsbildung

The reaction of Cp2TiCl2 with two equivalents of Lithium-phosphinomethanides is described.The reaction with LiCH2PMe2 leads to a C-C coupling product Cp2Ti, whereas with >2, the P-C coupling product Me3SiCH2PMe2=C(PMe2)(SiMe3), a P-ylide, is formed.An anlogous P-C coupling is observed with Li, whereby a novel titanocene heterocycle >, with an agostic Ti...H...C interaction, may be characterized as an intermediate.In contrast, with Li (without TMEDA) P-P coupling, yielding PMe2>2, is observed exclusively.An analogous result is obtained with Li, leading to 2, and, likewise, in the similar reaction of Cp2TiCl2 with Li, P-P coupling is observed leading to 2 and III(Me2P)2C(SiMe3)>>.With (TMEDA)Li, both P-P (34percent) and P-C (66percent) coupling are observed, yielding the P-ylides 2 and Ph2PCH2PPh2=C(PPh2)2, respectively.The results are compared with the respective coupling reactions at bismuth centers: BiCl3 reacts with LiCH2PMe2 to give Bi(CH2PMe2)3; with >2 only 5percent of the P-C coupling product Me3SiCH2PMe2=C(PMe2)(SiMe3) are found, whereas 95percent of the P-P coupling product 2 are obtained.Exclusive P-P coupling is also observed from BiCl3 and (TMEDA)Li and Li, respectively.The results clearly indicate that a metal-centered process, sensitive to steric and coordination effects, is active.Selective C-C, P-C and P-P coupling reactions are possible by selecting the appropriate combinations of reagents.The novel P-ylides are characterized by use of NMR spectroscopy; III> and 2 are further characterized by X-ray structure determinations.

The Sequence PCPCP as a Basic Structural Moiety for Phosphonium Salts, Ylides, and Their Alkali Complexes

Bis(diphenylphosphino)methane (1) reacts with CH3I to yield the phosphonium salt CH3(C6H5)2P(+)CH2P(C6H5)2 I(-) (2) which is transformed into the ylide CH3(C6H5)2P=CHP(C6H5)2 (3) by transylidation using (CH3)3P=CH2. 3 can be metallated at the CH3 group by