1448792-72-0

Upstream product

• 1165952-91-9 cyclohexa-1,3-diene 
• 250285-32-6 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride 
• 1314657-40-3 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1h-imidazole 
• 1080030-15-4 C₂₇H₃₆Cl₃N₂P 
• 1582259-98-0 N,N'-1,3-bis(2,6-diisopropylphenyl)-2,2-dichloroimidazol-2-ylidene 
• 244187-81-3 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene 

Relevant academic research and scientific papers

N-heterocyclic carbene-phosphinidyne transition metal complexes

The N-heterocyclic carbene-phosphinidene adduct IPr=PSiMe3 is introduced as a synthon for the preparation of terminal carbene-phosphinidyne transition metal complexes of the type [(IPr=P)MLn] (MLn=(η6-p-cymene)RuCl) and (η5-C5Me5)RhCl). Their spectroscopic and structural characteristics, namely low-field 31P NMR chemical shifts and short metal-phosphorus bonds, show their similarity with arylphosphinidene complexes. The formally mononegative IPr=P ligand is also capable of bridging two or three metal atoms as demonstrated by the preparation of bi-and trimetallic RuAu, RhAu, Rh2, and Rh2Au complexes.

Direct Access to Inversely Polarized Phosphaalkenes from Elemental Phosphorus or Polyphosphides

Phosphorus-containing multiple-bond systems have received great interest in various applications but often require elaborate syntheses and special precursors. In this paper, we describe simple methods for the synthesis of imidazoyl phosphinidenes and bis(

A donor-stabilized zwitterionic half-parent phosphasilene and its unusual reactivity towards small molecules

The stabilization of the labile, zwitterionic half-parent phosphasilene 4 LSi-PH (L=CH[(C=CH2)CMe(NAr)2]; Ar=2,6-iPr 2C6H3) could now be accomplished by coordination with two different donor ligands (4-dimethylaminopyridine (DMAP) and 1,3,4,5-tetramethylimidazol-2-ylidene), affording the adducts 8 and 9, respectively. The DMAP-stabilized zwitterionic half-parent phosphasilene 8 is capable of transferring the elusive parent phosphinidene moiety (:PH) to an unsaturated organic substrate, in analogy to the free phosphasilene 4. Furthermore, compounds 4 and 8 show an unusual reactivity of the Si=P moiety towards small molecules. They are capable of adding dimethylzinc and of activating the S-H bonds in H2S and the N-H bonds in ammonia and several organoamines. Interestingly, the DMAP donor ligand of 8 has the propensity to act as a leaving group at the phosphasilene during the reaction. Accordingly, treatment of 8 with H2S affords, under liberation of DMAP, the unprecedented thiosilanoic phosphane LSi=S(PH2) 16 (L=HC(CMe[2,6-iPr2C6H3N])2). Compounds 4 and 8 react with ammonia both affording LSi(NH2)PH 2 17, respectively.

Synthesis, spectroscopic characterisation and transmetalation of lithium and potassium diaminophosphanide-boranes

A secondary diaminophosphane-borane (Et2N)2PH(BH3) was prepared from a chlorophosphane precursor and LiBH4 and metalated by reaction with anion bases (n-BuLi, KN(SiMe3)2) to yield the corresponding metal diaminophosphanide-boranes [(Et2N)2P(BH3)]M (M = Li, K). Multinuclear NMR studies permitted the first spectroscopic characterisation of the metalation products and revealed the presence of monomeric (for M = Li) contact ion pairs in solution. NMR spectroscopic evidence that the ions in each pair interact via Li?P- rather than Li?H3B-interactions as had been inferred for a Ph-substituted analogue was confirmed by DFT studies, which revealed also that the borane coordination plays a decisive role in boosting the PH-acidity of the original secondary diaminophosphane precursor. Transmetalation of the potassium and lithium diaminophosphanide-boranes with Cu(i) and Zn(ii) chlorides afforded the first functional transition metal complexes of a P-heteroatom-functionalised phosphanide-borane ligand. Both products were fully characterised. Thermolysis of the Cu-complex induced a reaction which involved transfer of an NHC ligand from the metal to the phosphorus atom and yielded a phosphaalkene NHCPH (NHC = N-heterocyclic carbene) as the major phosphorus-containing product.

Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]?Butterfly Anion

Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4? BPh3] (Mes=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.

A fragile zwitterionic phosphasilene as a transfer agent of the elusive parent phosphinidene (:PH)

The simplest parent phosphinidene,:PH (1), has been observed only in the gas phase or low temperature matrices and has escaped rigorous characterization because of its high reactivity. Its liberation and transfer to an unsaturated organic molecule in solu