3040-71-9

Upstream product

• 822-68-4 cyclohexylphosphine 
• 2844-89-5 dichlorocyclohexylphosphine 
• 86012-32-0 Dibromcyclohexylphosphan 
• 6372-48-1 methylphenylphosphine 
• 90050-09-2 Methyl-cyclohexylphosphin 

Downstream Products

• 3040-79-7 1.2-Diaethyl-1.2-dicyclohexyl-biphosphin 
• 1199269-74-3 C₆H₁₁PCl₃⁽¹⁺⁾*GaCl₄^(1-)=C₆H₁₁PCl₃GaCl₄ 
• 1227465-26-0 (PC₆H₁₁)4SbCl₂⁽¹⁺⁾*Al₂Cl₇^(1-)=(PC₆H₁₁)4SbCl₂(Al₂Cl₇) 
• 1227465-23-7 [(CyP)4(AN)][OSO₂CF₃] 

Relevant academic research and scientific papers

Hydrogen/Halogen Exchange of Phosphines for the Rapid Formation of Cyclopolyphosphines

The hydrogen/halogen exchange of phosphines has been exploited to establish a truly useable substrate scope and straightforward methodology for the formation of cyclopolyphosphines. Starting from a single dichlorophosphine, a sacrificial proton "donor phosphine"makes the rapid, mild synthesis of cyclopolyphosphines possible: reactions are complete within 10 min at room temperature. Novel (aryl)cyclopentaphosphines (ArP)5 have been formed in good conversion, with the crystal structures presented. The use of catalytic quantities of iron(III) acetylacetonate provides significant improvements in conversion in the context of diphosphine (Ar2P)2 and alkyl-substituted cyclotetra- or cyclopentaphosphine ((AlkylP)n, where n = 4 or 5) formation. Both iron-free and iron-mediated reactions show high levels of selectivity for one specific ring size. Finally, investigations into the reactivity of Fe(acac)3 suggest that the iron species is acting as a sink for the hydrochloric acid byproduct of the reaction.

Cationic 5-phosphonio-substituted N-heterocyclic carbenes

2-Phosphanyl-substituted imidazolium salts 2-PR2(4,5-Cl-Im)[OTf] (9a,b[OTf]) (4,5-Cl-Im = 4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolium) (a: R = Cy, b: R = Ph) are prepared from the reaction of R2PCl (R = Cy, Ph) with NHC 8 (4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolin-2-ylidene) in the presence of Me3SiOTf. 5-Phospanyl-substituted imidazolium salts 5-PR2(2,4-Cl-Im)[OTf] (10a,b[OTf]) are obtained in quantitative yield when a slight excess of the NHC 8 is used. 5-Phosphonio-substituted imidazolium salts 5-PR2Me(2,4-Cl-Im)[OTf]2 (14a,b[OTf]2) and 5-PR2F(2,4-Cl-Im)[OTf]2 (16a,b[OTf]2) result from methylation reaction or oxidation of 10a,b[OTf] with XeF2 and subsequent fluoride abstraction. According to our quantum chemical studies the Cl1 atom at the 2-position at the imidazolium ring of dication 14b2+ carries a slightly positive charge and is therefore accessible for nucleophilic attack. Accordingly, the reaction of 14a,b[OTf]2 and 16a,b[OTf]2 with R3P (R = Cy, Ph) affords cationic 5-phosphonio-substituted NHCs 5-PR2Me(4-Cl-NHC)[OTf] (17a,b[OTf]) and 5-PR2F(4-Cl-NHC)[OTf] (18a,b[OTf]) via a SN2(Cl)-type reaction. A series of transition metal complexes such as [AuCl(5-PPh2Me(4-Cl-NHC))][OTf] (19[OTf]), [CuBr(5-PPh2Me(4-Cl-NHC))][OTf] (20[OTf]), [AuCl(5-PPh2F(4-Cl-NHC))[OTf] (21[OTf]) and [RhCl(cod)(5-PPh2Me(4-Cl-NHC))][OTf] (23[OTf]) are prepared to prove the coordination abilities of carbenes 17b[OTf] and 18b[OTf]. The isolation of a rare example of a tricationic bis-carbene silver complex [Ag(5-PPh2Me(4-Cl-NHC))2][OTf]3 (22[OTf]3) is achieved by reacting 14b[OTf] with Cy3P in the presence of AgOTf. NHC 17b[OTf] represents a very effective dehydrocoupling reagent for secondary (R2PH, R = Ph, Cy, iBu) and primary (RPH2, R = Ph, Cy) phosphanes to give diphosphanes of type R4P2 (R = Ph, Cy, iBu) and oligophosphanes R4P4, R5P5 (R = Ph, Cy), respectively. Methylation of 17b+ and subsequent deprotonation reaction with LDA affords the cationic NHO (N-heterocyclic olefin) 35+ of which the gold complex 36+ is readily accessible via the reaction with AuCl(tht).

Selectivity effects in zirconium-catalyzed heterodehydrocoupling reactions of phosphines

Zirconium compounds are known to dehydrocouple phosphines catalytically. An exploration of the factors that may promote selective heterodehydrocoupling was performed, revealing that steric factors are important but do not provide substantial selectivity. It was observed that 5-(Me3SiNCH2CH2)2N(CH2CH2NSiMe2CH2)Zr (1) may be sufficiently Lewis acidic to perform Lewis acid or frustrated Lewis pair catalysis.

On Organophosphorus Compounds, XXII. 1,2-Diaryl-1,2-dibromodiphosphanes

1,2-Diaryl-1,2-dibromodiphosphanes R(Br)P-P(Br)R 2 (R = C6H5; 4-XC6H4, X = CH3O, F, Cl) were prepared by dehalogenation of RPBr2 with magnesium in a one-batch procedure.While solid 2 presumably consists of only one diastereomer there exists an equilibrium between meso-2, rac-2 and their disproportionation products RPBr2 and (RP)5 in solutions of 2.The influence of temperature, R and solvent on this equilibrium was investigated. - The reaction products of the dissolved phenyl compound 2a correspond to a reaction of its disproportionation products PhPBr2 and (PhP)5, the former preferably reacting on nucleophilic substitution, the latter with electrophilic agents.Under heterogenous conditions diphosphanes Ph(R)P-P(R)Ph can be obtained from 2a and LiR.