REACTIONS OF SULFUR-CONTAINING MOLECULES (CS2, C2H4S) ON THE AMINOCARBENE GROUP OF [FE2(CO)7(MU-RCCNET2)] (R = ME, C3H5, SIME3)

Reaction of CS2 with diiron aminocarbene complexes [Fe2(CO)7{mu-RCCNEt2}] (R = Me (1), C3H5 (2), SiMe3 (3)) leads to C-S bond rupture and insertion of an S atom into the Fe = C (aminocarbene) bond to give binuclear complexes [Fe2(CO)6{RCCNEt2}S] (R = Me (4), C3H5 (5), SiMe3 (6)). Similar insertion of sulfur is observed when C2H4S is reacted with 1-3. Complexes 4-6 were characterized by X-ray diffraction studies. They contain a sulfur-containing ligand that bridges both iron atoms. The Fe atoms are thus incorporated into two fused ferrathiete rings sharing the C2S fragment. The following crystal data were obtained. Compound 3: monoclinic, P2(1)/n, a = 9.975 (3) angstrom, b = 14.009 (2) angstrom, c = 15.802 (4) angstrom, beta = 92.50 (2)-degrees, R(w) = 0.036 for 2840 reflections. Compound 4: triclinic, P1BAR, a = 9.627 (3) angstrom, b = 7.623 (2) angstrom, c = 12.594 (3) angstrom, alpha = 100.70 (2)-degrees, beta = 95.69 (2)-degrees, gamma = 104.81 (2)-degrees, R(w) = 0.0392 for 3566 reflections. Compound 5: triclinic, P1BAR, a = 7.553 (1) angstrom, b = 9.591 (3) angstrom, c = 14.444 (2) angstrom, alpha = 73.62 (2)-degrees, beta = 72.46 (2)-degrees, gamma = 75.99 (2)-degrees, R(w) = 0.0286 for 2195 reflections. Compound 6: monoclinic, P2(1)/n, a = 16.219 (2) angstrom, b = 10.175 (1) angstrom, c = 13.558 (4) angstrom, beta = 107.64 (3)-degrees, R(w) = 0.0416 for 2545 reflections.