Reactions of Triosmium Carbonyl Clusters with Thionylaniline. Crystal Structures of Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S), Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S), and Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S).
Reaction of Os(3)(CO)(12) with thionylaniline (PhN=S=O) in refluxing methylcyclohexane produces Os(3)(CO)(9)(&mgr;(3)-NPh)(&mgr;(3)-S) (1) in good yield. When Os(3)(CO)(10)(NCMe)(2) is treated with PhN=S=O at room temperature, compound 1 and Os(3)(CO)(9)(&mgr;(3)-eta(2)-(PhN)(2)SO)(&mgr;(3)-S) (2) result. Compound 1 reacts with trimethylamine oxide in the presence of acetonitrile to give Os(3)(CO)(8)(NCMe)(&mgr;(3)-NPh)(&mgr;(3)-S) (3). Compounds 1-3 were characterized by mass, IR, and NMR spectroscopies, and their structures were determined by single-crystal X-ray diffraction. Crystal data for 1: monoclinic (C2/c), a = 16.603(7) Å, b = 8.679(4) Å, c = 29.009(6) Å, beta = 102.08(2) degrees, Z = 8, R (R(w)) = 0.036 (0.039). Crystal data for 2: triclinic (P&onemacr;), a = 9.723(4) Å, b = 15.704(4) Å, c = 18.455(7) Å, alpha = 113.17(3) degrees, beta = 102.48(3) degrees, gamma = 89.97(3) degrees, Z = 4, R (R(w)) = 0.030 (0.026). Crystal data for 3: monoclinic (P2(1)/n), a = 18.792(3) Å, b = 8.856(3) Å, c = 26.210(9) Å, beta = 93.72(2) degrees, Z = 8, R (R(w)) = 0.066 (0.063).
Yeh
Wen-Yann
WY
Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113.
Stern
Charlotte L.
CL
Shriver
Duward F.
DF