The reaction of the tertiary phosphine sulfides R3PS (R = Ph, Me2N or C6H11) with X-2 (X-2 = I-2, Br-2, IBr or ICl); structural characterisation of the CT complexes (Me2N)(3)PSI2 and Ph3PS(I0.89Br0.11)Br and the ionic compound [{(Me2N)(3)PS}(2)S](2+) 2[Br-3](-)
Wi. Cross et al., The reaction of the tertiary phosphine sulfides R3PS (R = Ph, Me2N or C6H11) with X-2 (X-2 = I-2, Br-2, IBr or ICl); structural characterisation of the CT complexes (Me2N)(3)PSI2 and Ph3PS(I0.89Br0.11)Br and the ionic compound [{(Me2N)(3)PS}(2)S](2+) 2[Br-3](-), J CHEM S DA, (13), 1999, pp. 2225-2230
Citations number
20
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
The reactions of the tertiary phosphine sulfides R3PS (R=Ph, Me2N or C6H11)
with X-2 (X=I or Br) and IX (X=Br or Cl) have been studied. Reaction of R3
PS with I-2 or IX results in quantitative isolation of the CT complexes R3P
SIX (X=I, Br or Cl), except for Ph3PS with I-2 which produces the unusual c
ompound (Ph3PSI2)(2)I-2, which has been crystallographically characterised
by earlier workers. The crystal structure of (Me2N)(3)PSI2 has been determi
ned and compared to Ph3PSI2, previously described. The greater d(I-I) for (
Me2N)(3)PSI2, 2.856(1) Angstrom, compared to that of 2.823(1) Angstrom for
Ph3PSI2 clearly illustrates that d(I-I) in R3PSI2 compounds is sensitive to
R, although this effect is less pronounced when compared to that of analog
ous R3PSeI2 compounds. The crystal structure of the product from the reacti
on of Ph3PS with IBr has also been determined and represents the first exam
ple of a tertiary phosphine sulfide interhalogen CT complex. It has the for
mula Ph3PS(I0.89Br0.11)Br and is isomorphous with Ph3PSI2. The reaction of
R3PS with Br-2 is complex. In the case of Ph3PS, phosphorus-sulfur bond cle
avage occurs quantitatively to produce Ph3PBr2 and elemental sulfur. Reacti
on of (Me2N)(3)PS with Br-2 gives, as one product, [{(Me2N)(3)PS}(2)S][Br-3
](2) in moderate (ca. 30%) yield. This unusual dication is compared to the
previously reported [((Bu3PTe)-P-t)(2)Te][SbF6](2). Tricyclohexylphosphine
sulfide reacts with Br-2 in solvents of low relative permittivity (Et2O) to
produce the 1:1 addition complex (C6H11)(3)PSBr2; however, dissolution of
this material in solvents of higher relative permittivity results in phosph
orus-sulfur bond cleavage to produce (C6H11)(3)PBr2 and elemental sulfur.