86120-28-7

Upstream product

• 150163-23-8 1-(2,4,6-tri-t-butylphenyl)-2-<2,4,6-tris(trifluoromethyl)phenyl>diphosphene 
• 212079-68-0 [(2,4,6-tri-tert-butylphenyl)PPMe₃] 
• 212079-67-9 [(2,6-Mes₂C₆H₃)PPMe₃] 
• 538-75-0 dicyclohexyl-carbodiimide 
• 693-13-0 diisopropyl-carbodiimide 
• 119-61-9 benzophenone 
• 622-37-7 Phenyl azide 
• 1227476-15-4 Azobenzene 
• 983-79-9 benzophenone azine 
• 538-51-2 benzylidene phenylamine 
• 501-65-5 diphenyl acetylene 
• 83115-12-2 (2,4,6-tri-tert-butylphenyl)phosphine 
• 79074-00-3 2,4,6-tri-t-butylphenylphosphonous dichloride 
• 87437-16-9 (E)-1-(2,4,6-triisopropylphenyl)-2-(2,4,6-tri-tert-butylphenyl)diphosphene 

Relevant academic research and scientific papers

Experimental and Computational Studies on a Base-Free Terminal Uranium Phosphinidene Metallocene

The first stable base-free terminal uranium phosphinidene metallocene is presented; and its structure and reactivity have been studied in detail and compared to that of the corresponding thorium derivative. Salt metathesis reaction of the methyl iodide uranium metallocene Cp’’’2U(I)Me (2, Cp’’’=η5-1,2,4-(Me3C)3C5H2) with Mes*PHK (Mes=2,4,6-(Me3C)3C6H2) in THF yields the base-free terminal uranium phosphinidene metallocene, Cp’’’2U=PMes* (3). In addition, density functional theory (DFT) studies suggest substantial 5f orbital contributions to the bonding within the uranium phosphinidene [U]=PAr moiety, which results in a more covalent bonding between the [Cp’’’2U]2+ and [Mes*P]2? fragments than that for the related thorium derivative. This difference in bonding besides steric reasons causes different reactivity patterns for both molecules. Therefore, the uranium derivative 3 may act as a Cp’’’2U(II) synthon releasing the phosphinidene moiety (Mes*P:) when treated with alkynes or a variety of hetero-unsaturated molecules such as imines, thiazoles, ketazines, bipy, organic azides, diazene derivatives, ketones, and carbodiimides.

Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe3)2}] with KC8, or [Co(IPr){N(SiMe3)2}2] with mes?PH2, mes? = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe3)2}] with excess KC8 in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre.

Uranium versus Thorium: Synthesis and Reactivity of [η5-1,2,4-(Me3C)3C5H2]2U[η2-C2Ph2]

The synthesis, electronic structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Addition of diphenylacetylene (PhC≡CPh) to the uranium phosphinidene metallocene [η5-1,2,4-(Me3C)3C5H2]2U=P-2,4,6-tBu3C6H2 (1) yields the stable uranium metallacyclopropene, [η5-1,2,4-(Me3C)3C5H2]2U[η2-C2Ph2] (2). Based on density functional theory (DFT) results the 5f orbital contributions to the bonding within the metallacyclopropene U-(η2-C=C) moiety increases significantly compared to the related ThIV compound [η5-1,2,4-(Me3C)3C5H2]2Th[η2-C2Ph2], which also results in more covalent bonds between the [η5-1,2,4-(Me3C)3C5H2]2U2+ and [η2-C2Ph2]2? fragments. Although the thorium and uranium complexes are structurally closely related, different reaction patterns are therefore observed. For example, 2 reacts as a masked synthon for the low-valent uranium(II) metallocene [η5-1,2,4-(Me3C)3C5H2]2UII when reacted with Ph2E2 (E=S, Se), alkynes and a variety of hetero-unsaturated molecules such as imines, ketazine, bipy, nitriles, organic azides, and azo derivatives. In contrast, five-membered metallaheterocycles are accessible when 2 is treated with isothiocyanate, aldehydes, and ketones.

Evidence for Iron-Catalyzed α-Phosphinidene Elimination with Phenylphosphine

The ubiquitous half-sandwich iron complex [CpFe(CO)2Me] (Cp=η5-C5H5) appears to be a catalyst for α-phosphinidene elimination from primary phosphines. Dehydrocoupling reactions provided initial insight into this unusual reaction mechanism, and trapping reactions with organic substrates gave products consistent with an α elimination mechanism, including a rare example of a three-component reaction. The substrate scope of this reaction is consistent with generation of a triplet phosphinidene. In all, this study presents catalytic phosphinidene transfer to unsaturated organic substrates.

Flash vacuum pyrolysis of dichlorophosphines over magnesium: Generation and reactivity of simple phosphinidenes

Flash vacuum pyrolysis of dichlorophosphines over magnesium at 500-600 °C gives the products expected from intramolecular CH insertion of the corresponding phosphinidenes.

Photochemical Reactions of Diphosphenes Carrying 2,4,6-Tris(trifluoromethyl)phenyl Group

Photoreactions of 1,2-bisdiphosphene and 1-(2,4,6-tri-t-butylphenyl)-2-diphosphene were studied.The latter diphosphene gave formally an intramolecular cyclization product by photoirradi

Synthesis, Photochemical Behaviour and cis/trans Isomerisation of 1-(2,4,6-Triisopropylphenyl)-2-(2,4,6-tri-tert-butylphenyl)diphosphene

Irradiation of (E)-1-(3,4,6-triisopropylphenyl)-2-(2,4,6-tri-tert-butylphenyl)diphosphene (1a) yields its thermally unstable cis-isomer 1b, the diastereoisomeric cyclisation products 4a and 4b and the cleavage product 5.A mechanism for the formation of these products is proposed.The activation parameters for the thermal isomerisation reaction 1b -> 1a are experimentally determined as ΔH(excit.)=29.5 +/-1.4 kcal mol-1 and ΔS(excit.)=38 +/- 6 cal mol-1 K-1 (1 kcal=4.18 kJ); ΔH(excit.) is the first experimentally determined measure for the strength of the ?-component of a phosphorus-phosphorus double bond.

SYNTHESIS AND PHOTOREACTIONS OF E-1-(2,4,6-TRIISOPROPYLPHENYL)-2-(2,4,6-TRI-TERT-BUTYLPHENYL)DIPHOSPHENE

The synthesis and irradiation of the title compound E-1 are discussed.

GENERAL APPROACHES TO PHOSPHINIDENES VIA RETROADDITIONS

Retroadditions - thermal and photochemical decomposition of phosphiranes and 3-phospholenes - offer general routes to free phosphinidenes.