Syntheses, Characterization, and Structures of Tri- and Tetraruthenium Clusters Containing Sulfido, Phenylimido, and (Phenylimino)thio Ligands

Reaction of Ru3(CO)12 with
the SO2 analog N-sulfinylaniline (PhNSO)
in refluxing toluene produces Ru3(CO)9(μ3-NPh)(μ3-S)
(1),
Ru3(CO)9(μ3-NPh)2
(2),
Ru4(CO)10(μ-CO)(μ4-η2-SNPh)(μ4-S)
(3), and
Ru4(CO)10(μ-CO)(μ4-η2-SNPh)(μ4-NPh)
(4) in low yields. Treatment of
Ru3(CO)10(NCMe)2 with
PhNSO at room
temperature affords 1 as the major product in good yield,
accompanied by CO2 formation. Compounds 1,
3, and
4 were characterized by mass, IR, and 1H NMR
spectroscopy, and their structures were determined by
single-crystal X-ray diffraction. Crystal data for 1: 
triclinic (P1̄), a = 9.585(2) Å,
b = 10.151(2) Å, c = 10.555(4)
Å,
α = 92.32(3)°, β = 93.21(3)°, γ =
98.84(2)°, Z = 2, R
(Rw) = 0.026 (0.030). Crystal data for
3:  monoclinic
(P21/n), a =
8.986(7) Å, b = 13.968(3) Å, c =
19.232(9) Å, β = 103.06(5) Å, Z = 4,
R (Rw) = 0.025
(0.025).
Crystal data for 4:  monoclinic
(P21/c), a =
10.319(4) Å, b = 23.354(6) Å, c =
23.329(7) Å, β = 100.43(3)°, Z
= 8, R (Rw) = 0.051
(0.040).