1,1,1,2,2-Pentaiododiphosphanium cations, P2I5+EI4− (E = Al, Ga or In): synthesis and characterisation by 31P MAS NMR, IR and Raman spectroscopy

An Experimental and Theoretical Study on the Novel Tetraphosphorus Triselenide Boron Triiodide (P4Se3)·(BI3) Adduct

“…Moreover we have investigated the bonding and electron transfer within these species. [1 ], [2 ], [3 ] Previous work has shown that the donor behavior of phosphorus trihalides depends on the electronegativity of the halogen substituents. [4 ], [5 ] For the phosphorus trihalides, the order of stability for the 1:1 donor-acceptor complexes with boron trihalides is PCl 3 < PBr 3 < PI 3 .…”

A Spirocyclic PS Cage Cation: Synthesis and Formation of P7S6I2+

“…+ sulfonium cation: P 4 S 3 I + is likely formed by the interaction of the dissolved Ag-(CH 2 Cl 2 ) 3 + ion with the iodine atom of a-P 4 S 3 I 2 ; Figure 6 rationalizes its formation. In fact, this appears to be a HOMO-LUMO interaction of the HOMO of a-P 4 S 3 I 2 (mainly at iodine; À6.428 eV) with the LUMO of Ag-(CH 2 Cl 2 ) 3 + (Ag 5s 0 ; at À6.149 eV; orbitals deposited).…”

“…However, the anion bands differ slightly from the known pattern, probably because of lattice splitting. The area of the C(CF 3 ) 3 ) show this pattern to an even higher degree. [27] Discussion Thermodynamic quantities given in the following discussion approximate DG8 in CH 2 Cl 2 at 298 K and were taken from the MP2/TZVPP calculations that include approximate solvation free energies obtained by the COSMO model.…”

“…[1] The high reactivity of such phosphorus cations, which are not compatible with anions such as [SbF 6 ] À or [AsF 6 ] À [2,3] (formation of PF 3 ), may account for this. It appeared likely that such P x E y + or P x E y X z + species could be isolated given the right counterion.…”

“…Since the fluorinated [Al(OR F ) 4 ] À alkoxyaluminates allowed the synthesis of stable salts of phosphorus-rich cations such as P 3 I 6 + and P 5 X 2 + , it seemed likely that these anions are also suitable for stabilizing P x E y + or P x E y X z + . Ag-[Al(OR F 4 ] (R F = C(CF 3 ) 3 ), [4] tested in many halide abstraction reactions, [5][6][7][8][9][10][11] is a likely starting material to achieve this. Thus by reaction of Ag + with PX 3 and P 4 S 3 , the first [6] ternary P 5 S 3 X 2 + (1 ab), P 5 S 2 X 2 + (2 ab), and P 4 S 4 X + (3 ab) ions were recently obtained (X = Br, I).…”