Triphenylphosphine-Stabilized Salts
Organometallics, Vol. 26, No. 25, 2007 6113
Syntheses. A mixture of triphenylphosphine and thallium(I)
hexafluorophosphate in dichloromethane (30 mL) was treated with
a solution of the halodiphenyl-arsine, -stibine, or -bismuthine in
dichloromethane (10 mL). A milky suspension of thallium(I) halide
formed. After being stirred for ca. 1 h, the mixture was filtered
and the solvent evaporated from the filtrate to give the crude product
as a colorless solid, which was purified by recrystallization from
dichloromethane-diethyl ether.
tions were carried out with use of the Amsterdam Density
Functional (ADF) program, version ADF2004.01,24 and employed
the Perdew-Burke-Ernzerhof (PBE) gradient-corrected func-
tional25 with small-core, Slater-orbital basis sets of triple-ú plus
polarization (TZP) quality. Previous calculations on a series of
diiodomethyl- and diiodophenyl-arsine−tertiary arsine adducts
indicated that the PBE functional performs well in modeling the
bonding between group 15 atoms.17 Optimized geometries were
obtained, both with and without ZORA scalar relativistic correc-
tions,18 using the gradient algorithm of Versluis and Ziegler.26
Energy, gradient, and displacement cutoffs for the optimizations
were set a factor of 2 tighter than the ADF defaults to improve the
reliability of the optimized structures. Further single-point calcula-
tions used a fragment-based approach to characterize contributions
to the E-P bond of interest. Vibrational frequency calculations for
the species surveyed here were not pursued. Note that a principal
purpose of frequency calculations is to probe whether any stationary
points found are genuine minima. In the present instance, where
all of the optimized stationary points were observed to be markedly
asymmetric and since unconstrained asymmetric stationary points
located through energy minimization are almost without exception
minima, it was not judged necessary or desirable to perform lengthy
frequency calculations on these large asymmetric structures. All
calculations were performed in a spin-restricted fashion and in the
absence of symmetry constraints.
Crystal Structures. Crystallographic data and experimental
parameters for the X-ray structural analyses are given in Table 1.
Data were processed using Denzo and Scalepack software and
corrected for absorption by the Gaussian integration method
implemented in maXus.27 The structures were solved by direct
methods (SIR92)28 and refined by full matrix on F with use of
CRYSTALS.29 All non-hydrogen atoms were refined with
anisotropic displacement parameters. Hydrogen atoms were included
at calculated positions and allowed to ride on the atoms to which
they are attached. Molecular graphics were produced with
ORTEP-3.30
(Triphenylphosphine-P)diphenylarsenium Hexafluorophos-
phate. Iododiphenylarsine (1.43 g, 4.01 mmol), triphenylphosphine
(1.05 g, 4.01 mmol), and thallium(I) hexafluorophosphate (1.47 g,
4.21 mmol) were used. Yield: 1.53 g (60%); mp 220 °C dec. Anal.
Calcd for C30H25AsF6P2:C, 56.6; H, 4.0. Found: C, 56.9; H, 4.1.
1
13C{1H} NMR: δ 129.0 (d, JCP ) 20.5 Hz, Cipso of PPh3), 130.6
2
(s, Cortho of Ph2As+), 130.9 (d, JCP ) 12.5 Hz, Cortho of PPh3),
132.5 (s, Cpara of Ph2As+), 134.3 (d, 3JCP ) 9.1 Hz, Cmeta of PPh3),
135.1 (s, Cmeta of Ph2As+), 135.6 (d, 4JCP ) 3.3 Hz, Cpara of PPh3).
1
31P{1H} NMR: δ -143.9 (septet, JPF ) 709.9 Hz, PF6), 13.6 (s,
PPh3). FAB MS: m/z 491 amu ([M]+, 25%).
(Triphenylphosphine-P)diphenylstibenium Hexafluorophos-
phate 1-Dichloromethane. Chlorodiphenylstibine (0.55 g, 1.78
mmol), triphenylphosphine (0.47 g, 1.78 mmol), and thallium(I)
hexafluorophosphate (0.64 g, 1.84 mmol) were used. Yield: 0.55
g (40%); mp 147 °C dec. Anal. Calcd C31H27Cl2F6P2Sb: C, 48.5;
H, 3.5. Found: C, 49.0; H, 3.5. 13C{1H} NMR: δ 127.4 (d, 1JCP
)
2
23.8 Hz, Cipso of PPh3), 129.4 (d, JCP ) 8.0 Hz, Cortho of PPh3),
129.8 (s, Cmeta of Ph2Sb+), 130.6 (s, Cpara of Ph2Sb+), 130.9 (s,
3
Cpara of PPh3), 133.7 (d, JCP ) 14.6 Hz, Cmeta of PPh3), 136.2 (s,
Cortho of Ph2Sb+), 139.1 (s, Cipso of Ph2Sb+). 31P{1H} NMR: δ
1
-143.7 (septet, JPF ) 711.4 Hz, PF6), -4.2 (s, PPh3). FAB MS:
m/z 537 amu ([M]+, 100%).
(Triphenylphosphine-P)diphenylbismuthenium Hexafluoro-
phosphate 1-Dichloromethane. Chlorodiphenylbismuthine (0.94
g, 2.36 mmol), triphenylphosphine (0.62 g, 2.36 mmol), and
thallium(I) hexafluorophosphate (0.86 g, 2.47 mmol) were used.
Yield: 0.91 g (50%); mp 177 °C dec. Anal. Calcd for C31H27-
BiCl2F6P2: C, 43.5; H, 3.2. Found: C, 43.8; H, 3.2. 13C{1H}
Acknowledgment. R.S. and S.B.W. gratefully acknowledge
the Australian Research Council (ARC) for financial support.
NMR: δ 124.5 (d, 1JCP ) 37.4 Hz, Cipso of PPh3), 130.0 (d, 3JCP
)
10.6 Hz, Cmeta of PPh3), 130.3 (s, Cpara of PPh3), 132.6 (s, Cmeta of
Ph2Bi+), 133.2 (s, Cpara of Ph2Bi+), 133.9 (d, 2JCP ) 11.1 Hz, Cortho
of PPh3), 138.4 (s, Cortho of Ph2Bi+). 31P{1H} NMR: δ -143.6
(septet, 1JPF ) 713.6 Hz, PF6), -3.9 (s, PPh3). FAB MS: m/z 625
amu ([M]+, 100%).
Supporting Information Available: Crystallographic data for
the four complexes (CIF). This material is available free of charge
OM700512H
Bis(triphenylphosphine-P)diphenylstibenium Hexafluoro-
phosphate. Chlorodiphenylstibine (0.65 g, 2.07 mmol), triph-
enylphosphine (1.09 g, 4.15 mmol), and thallium(I) hexafluoro-
phosphate (0.76 g, 2.16 mmol) were used. Yield: 0.98 g (50%);
mp 157 °C dec. Anal. Calcd for C48H40F6P3Sb: C, 61.0; H, 4.3.
Found: C, 60.4; H, 4.4. 13C{1H} NMR: δ 130.6 (br, Cortho of PPh3,
Cmeta of Ph2Sb+), 131.9 (s, Cpara of Ph2Sb+), 134.1 (br, Cmeta of
PPh3), 135.6 (s, Cortho of Ph2Sb+), 137.2 (s, Cpara of PPh3). 31P{1H}
NMR: δ -143.7 (septet, 1JPF ) 712.5 Hz, PF6), -4.5 (br, PPh3).
FAB MS: m/z 537 amu ([M - PPh3]+, 100%).
(24) Fonseca Guerra, C.; Snijders, J. G.; te Velde, G.; Baerends, E. J.
Theor. Chem. Acc. 1998, 99, 391-403. te Velde, G.; Bickelhaupt, F. M.;
Baerends, E. J.; Fonseca Guerra, C.; van Gisbergen, S. J. A.; Snijders, J.
G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931-967. Baerends, E. J.;
Autschbach, J.; Be´rces, A.; Bo, C.; Boerrigter, P. M.; Cavallo, L.; Chong,
D. P.; Deng, L.; Dickson, R. M.; Ellis, D. E.; Fan, L.; Fischer, T. H.; Fonseca
Guerra, C.; van Gisbergen, S. J. A.; Groeneveld, J. A.; Gritsenko, O. V.;
Gruning, M.; Harris, F. E.; van den Hoek, P.; Jacobsen, H.; van Kessel,
G.; Kootstra, F.; van Lenthe, E.; McCormack, D. A.; Osinga, V. P.;
Patchkovskii, S.; Philipsen, P. H. T.; Post, D.; Pye, C. C.; Ravenek, W.;
Ros, P.; Schipper, P. R. T.; Schreckenbach, G.; Snijders, J. G.; Sola, M.;
Swart, M.; Swerhone, D.; te Velde, G.; Vernooijs, P.; Versluis, L.;
Visser, O.; van Wezenbeek, E.; Wiesenekker, G.; Wolff, S. K.; Woo, T.
K.; Ziegler, T. Amsterdam Density Functional, version 2004.01; S. C. M.,
Vrije Universiteit, Theoretical Chemistry: Amsterdam, The Netherlands,
2004.
(25) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. ReV. Lett. 1997, 78,
1396.
(26) Versluis, L.; Ziegler, T. J. Chem. Phys. 1988, 88, 322-328.
(27) Mackay, S.; Gilmore, C. J.; Edwards, C.; Stewart, N.; Shankland,
K. maXus Computer Program for the Solution and Refinement of Crystal
Structures; Nonius, Delft, The Netherlands, MacScience, Japan, and
University of Glasgow, Glasgow, Scotland, 1999.
Bis(triphenylphosphine-P)diphenylbismuthenium
Hexa-
fluorophosphate. Chlorodiphenylbismuthine (0.74 g, 1.86 mmol),
triphenylphosphine (0.97 g, 3.72 mmol), and thallium(I) hexafluo-
rophosphate (0.68 g, 1.96 mmol) were used. Yield: 0.91 g (50%);
mp 188 °C dec. Anal. Calcd for C48H40BiF6P3: C, 55.7; H, 3.9.
1
Found: C, 55.8; H, 3.9. 31P{1H} NMR: δ -143.4 (septet, JPF
)
714.9 Hz, PF6), -4.21 (br, PPh3). FAB MS: m/z 625 amu ([M+ -
PPh3]+, 60%); 262 amu ([PPh3]+, 100%). A quantity of (triph-
enylphosphine-P)diphenylbismuthenium
hexafluorophosphate
was isolated from the filtrate. Yield: 0.40 g (25%).
(28) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Burla,
M. C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435.
(29) Betteridge, P. W.; Caruthers, J. R.; Cooper, R. I.; Prout, K.; Watkin,
D. J. J. Appl. Crystallogr. 2003, 36, 1487.
Theoretical Methods. Density functional theory calculations
were performed on Linux-based Pentium computers and in parallel
mode on the SGI Altix AC supercomputer operated by the
Australian Partnership for Advanced Computing (APAC). Calcula-
(30) Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565.