83115-14-4

Upstream product

• 3975-77-7 1-bromo-2,4,6-tri-tert-butylbenzene 
• 83115-13-3 lithium 2,4,6-tris(tert-butyl)phenylphosphide 
• 83115-12-2 (2,4,6-tri-tert-butylphenyl)phosphine 
• 91425-17-1 (2,4,6-tri-tert-butylphenyl)(trimethylsilyl)phosphane 
• 79074-00-3 2,4,6-tri-t-butylphenylphosphonous dichloride 
• 21792-52-9 1,2-diethynylbenzene 
• 86120-24-3 (2,4,6-tri-tert-butyl)phenylmonochlorophosphane 
• 99532-18-0 (((CH₃)3Si)2CH)2Sn(F)P(H)C₆H₂(C(CH₃)3)3 
• 83466-54-0 Bis(2,4,6-tri-tert-butylphenyl)diphosphen 

Downstream Products

• 86539-31-3 1-Methyl-1,2-bis-(2,4,6-tri-tert-butyl-phenyl)-diphosphane 
• 86539-33-5 methyl(2,4,6-tri-tert-butylphenyl)phosphine 
• 83115-13-3 lithium 2,4,6-tris(tert-butyl)phenylphosphide 

Relevant academic research and scientific papers

REDUCTION OF DIPHOSPHENE: FORMATION OF d1- AND meso-DIPHOSPHANES

Bis(2,4,6-tri-tert-butylphenyl)diphosphene was reduced with aluminium hydrides to give d1- and meso-bis(2,4,6-tri-tert-butylphenyl)diphosphanes as stable compounds.

Atypical and Asymmetric 1,3-P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

Novel seven-membered cyclic imine-based 1,3-P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These “cycloiminophosphanes” possess flexible non-isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P-κ1- and P,N-κ2-tungsten(0) carbonyl complexes, by determining the IR frequency of the trans-CO ligands. Complexes with [RhCp*Cl2]2 demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ1 and κ2 species; treatment with AgOTf gives full conversion to the κ2 complex. The potential for catalysis was shown in the RuII-catalyzed, solvent-free hydration of benzonitrile and the RuII- and IrI-catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l-menthone, as well as their P,N-κ2-RhIII and a P-κ1-RuII complexes.

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.

Reaction of lithium (2,4,6-tri-tert-butylphenyl)silylphosphides with haloforms

The reaction of lithium (tert-butyldimethylsilyl)(2,4,6-tri-tert- butylphenyl)phosphide with chloroform afforded (Z)-2-(tert-butyldimethylsilyl)- 2-chloro-1-(2,4,6-tri-tert-butylphenyl)-1- phosphaethene. The NMR study revealed a secondary phosphine result

Towards the Synthesis of o-Diphosphaquinones: Benzodiphosphadihydropentalene - Naphthodihydrodiphosphete

o-Quinodimethanes 1 are important intermediates in organic synthesis that may be generated by thermal valence isomerization of benzocyclobutenes or octa-1,2,4,6,7-pentaenes.The preparation of a stable o-quinodimethane has not been reported so far.Whereas o-quinodiimines 2 containing strongly electron-withdrawing groups at the nitrogen atoms are isolable, o-diphosphaquinones 3 have not been detected. - Keywords: Propargyl rearrangement; DBU; Electrocyclization; Diphosphaquinone; Dihydrodiphosphete

Synthesis, Coordination Chemistry and Ligand Properties of Secondary Phosphines R(Ar*)PH with Bulky Aromatic Substituents - Molecular Structure of Ph(2,4,6-iPr3C6H2)PH, (2,4,6-iPr3C6H2)2PH and ClAu[PhP(2,4,6-tBu3C6H2)H]

The secondary phosphines R(Ar*)PH (R = Me, iPr, Ph, Mes, Ar*) (2a-2h) with bulky aromatic substituents Ar* (Ar* = 2,3,6-R′3C6H2, R′ = iPr, tBu) are obtained in good yields by reaction of RPCl2, PCl3, PBr3 or Ar*P(Cl,Br)2 with 2,4,6-tBu3C6H2Li or 2,4,6-iPr3C6H2MgBr and subsequent reduction of the intermediate halophosphines R(Ar*)PX (X = Cl, Br) with LiAlH4. The X-ray structural analysis of Ph(2,4,6-iPr3C6H2)PH (2g), space group P1, shows P-C-distances of 1.824(1) and 1.838(1)?. The lithium derivatives of 2a-2c are monomeric in solution as indicated by the 1 : 1 : 1 : 1-quartet 7Li-31P fine structure of the 31P{1H} NMR signals at low temperatures. 2a-2c and 2f-2h form Ni(0) and Fe(0) complexes (CO)3NiL (6a-6f) and Fe(CO)4L (7a-7d), respectively. The Tolman electronic parameters ν of the bulky ligands are almost identical. Within the series 2a-2h the spatial shielding of the P atoms has been estimated using advanced molecular modeling techniques. The bulky ligancl 2c forms coinage metal complexes [Cu(CH3CN)2(2c)2] [PF6] (8). Cu2Cl2(2c)2 (9) and Cl-Au(2c) (10). While 10 is monomeric in solution, in the solid state it forms pairs of head to tail oriented monomers with almost linear Cl-Au-P skeletons (Cl-Au-P 175.47(9)°) as shown by an X-ray structural analysis.

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.

THE REACTION OF DIBENZYLMERCURY WITH SECONDARY PHOSPHINES: PHOSPHORUS-PHOSPHORUS BOND FORMATION VERSUS BENZYL SUBSTITUTION

In an attempt to find a simple, high yield synthetic method to create a phosphorus-phosphorus bond from phosphorus-hydrogen bonds, we have investigated the reaction of dibenzylmerury DBM with secondary phosphines.The overall reaction is: DBM + R2PH -> toluene + Hg + R2P-PR2.Thus reaction of diphenylphosphine with DBM produces the desired coupled product tetraphenyl diphosphine in 85-90percent yield.In contrast, the reaction of DBM with 1,3-bis(phenylphosphino)propane Ph(H)P-(CH2)3-P(H)Ph produces the benzyl-substituted product rather than the expected cyclic compound 1,2-diphenyl-1,2-diphospholane PhP-(CH2)3-PPh.The dioxide or disulfide of Ph(H)P-(CH2)3P(H)Ph undergoes no reaction with DBM.The bulky 2,4,6-tris(tert-butyl)phenylphosphine ArPH2 with DBM yields diastereomers of the coupled disecondary diphosphine Ar(H)P-P(H)Ar.The reaction of DBM with diphenylchlorophosphine results in a high yield of tetraphenyl diphosphine, but with phenyldichlorophosphine produces the benzyl-substituted product phenylbenzylchlorophosphine.

Synthesis and Structures of Phosphinidene and Phosphido Complexes of Iron and Cobalt

Treatment of Na with R1PCl2 (R1=2,4,6-But3C6H2) result in a dicobalt phosphinidene complex, 1)>, of the 'open' type containing a trigonal-planar phosphorus, no metal-metal bond, and some degree of Co-P multiple bonding as established by an X-ray diffraction study.The attempted synthesis of di-iron phosphinidene complexes via the reaction of 2 with dichlorophosphines RPCl2 failed to produce an isolable species containing the desired phosphinidene fragment.For R=(Me3Si)2CH a large number of products were formed, two of which were isolated and identified within the same crystal structure by X-ray crystallography.Both complexes were found to contain a di-iron centre bridged by a phosphido ligand: > and di-nuclear iron species were observed by (31)P n.m.r. spectroscopy, these being 1)2>, t2>>>, 1)>, and also the diphosphine R1PHPHR1.In addition to the synthetic and structural studies, extended Hueckel molecular orbital calculations have been carried out on model phosphidine complexes in a attempt to understand their electronic and structural features.