Reaction of
(NEt4)2[WS4]
and
[S2PPh2]2
in acetonitrile results in the formation of diamagnetic, orange
syn-W2S2(µ-S)
2(S2PPh2)2
by an induced internal redox process. Crystals of the toluene solvate
W2S2(µ-S)
2(S2PPh2)2
. C7H8 are triclinic and belong to
space group P1– with a
13.845(5), b 16.536(7), c 8.387(2)
Å, α 99.75(3), β 95.51(3), γ 83.08(3)˚, and
Z 2. Refinement of 5445 data converged at
R 0.038 and
Rw 0.038. The complex possesses a
syn-[W V
2S2(µ-S)2]2+
core with a W–W bond of 2.8161(5) Å and two terminal W=S
bonds of 2.097(3) and 2.096(3) Å. The W-(µ-S) bond distances are
in the range 2.310(2)–2.315(2) Å. Each of the five-coordinate,
square-pyramidal tungsten atoms is further coordinated by a bidentate
dithiophosphinate ligand with W–S bond distances ranging from 2.464(2)
to 2.481(2) Å. Extended reaction of
(NH4)2[WSe4]
and
[S2CNEt2]2
in acetonitrile produces green
WS(Se2)(S2CNEt2)2
and red
WO(Se2)(S2CNEt2)2
in 40% and 15% yields, respectively. Crystals of
WO(Se2)(S2CNEt2)2
are monoclinic and belong to space group
P21/n
with a 9.609(6), b 15.053(7),
c 13.120(9) Å, β 100.08(4)˚, and
Z 4. Refinement of 2473 data converged at
R 0.039 and
Rw 0.039. The seven-coordinate,
pentagonal bipyramidal complex features C1
symmetry, an axial oxo ligand (W=O 1.705(6) Å), an equatorial,
side-on bonded diselenido ligand (W–Se(1) 2.509(1), W–Se(2)
2.547(1) Å, Se(1)–Se(2) 2.306(2) Å) and two bidentate
dithiocarbamate ligands.
