42946-01-0

Upstream product

• 1079-66-9 chloro-diphenylphosphine 
• 109-73-9 N-butylamine 

Downstream Products

• 654066-09-8 [CpRuCl(Ph₂PN((n)Bu)PPh₂)(PPh₃)]Cl 
• 856243-88-4 dimethyl(n-butylbis(diphenilphosphine)amine-κP,κP)platinum(II) 

Relevant academic research and scientific papers

Ethylene Tetramerisation: A Structure-Selectivity Correlation

The effect of ethylene tetramerisation ligand structures on 1-octene selectivity is well studied. However, by-product formation is less understood. In this work, a range of PNP ligand structures are correlated with the full product selectivity and with catalyst activity. As steric bulk on the N-substituent increases, the product selectivity shifts from >10 % to 3% of both C6 cyclics and C16+ by-products. 1-Octene peaks at ca. 70%. Thereafter, only 1-hexene increases. Similar selectivity changes were observed for ortho-Ph-substituted PNP ligands. The C10-14 selectivity was less affected by the ligand structure. The ligand effect on the changes in selectivity is explained mechanistically. Lastly, an increase in ligand steric bulk was found to improve catalyst activity and reduce polymer formation by an order of magnitude. It is proposed that steric bulk promotes formation of cationic catalytic species which are responsible for selective ethylene oligomerisation.

Efficient catalytic transfer hydrogenation reactions of carbonyl compounds by Ni(II)-diphosphine complexes

The catalytic transfer hydrogenation reactions of a series of aromatic and aliphatic carbonyl compounds were investigated using divalent Ni(II)-diphosphine complexes, [L2NiCl2] (where L2 = 1,1-bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,1-bis(diphenylphosphino)ferrocene (dppf), and N-butyl-N-(diphenylphosphino)-1,1-diphenylphosphinamine (dppba)). This is a single-step reaction in the presence of potassium hydroxide and isopropyl alcohol to afford the corresponding alcohols. This protocol tolerates other sensitive functional groups like olefinic double bonds and also achieves high chemoselectivity. All the reactions were monitored by GC and GC–MS. The plausible mechanism is also discussed. The method reported in the present article is simple, cost-effective, and provides excellent conversions. Nickel-diphosphine complexes appear as a potential alternative to expensive transition metal complexes.

Polyhedral oligomeric silsesquioxane-conjugated bis(diphenylphosphino)amine ligand for chromium(III) catalyzed ethylene trimerization and tetramerization

Polyhedral oligomeric silsesquioxanes (POSSs) were attached to conventional bis(diphenylphosphino)amine (PNP) ligand as solubility-enhancing materials for catalytic ethylene trimerization and tetramerization. Differently functionalized arylphosphine ligands of the type (Ph)2PN(POSS)P(Ph)(ArR) (R = functional groups) were systematically developed, and their corresponding chromium(III) complexes were formed. The developed precatalysts exhibited excellent tolerance in solvents, including even low-carbon-number hydrocarbons such as n-pentane, n-hexane, or cyclohexane. In particular, the ortho-fluorophenyl-substituted complex showed higher stability even at higher temperatures above 120 °C. The ortho-OCF3-phenyl-substituted complex showed outstanding catalytic activity, which reached 2287 kg/g Cr/h at 30 bar.

Further studies in the rearrangement of bis(diphenylphosphino)amines upon chloramination

Chloramine reacts with a variety of bis(diphenylphosphino)amines in which the nitrogen atom bridging the two phosphorus atoms is also bonded to an alkyl group. It has been shown in all cases where the substituent is a hydrocarbon or hydrogen that the resulting phosphonium salt is rearranged to a structure in which the alkyl group is bonded to a nitrogen atom that is bound to only one phosphorus atom. Possible mechanisms for the chloramination reaction are discussed.