Synthesis and structural characterization of some molybdenum carbonyl nitrosyl complexes of diethyldithiocarbamate

Abstract

Ten complexes, M′[ Mo(Et 2NCS 2)(CO) 2(NO)X ] ( M′ + = PPN + or Et 4N + ; X − = NCS − ( 1), NO 3 − ( 2), N 3 − ( 3), Br − ( 4) or Cl − ( 5) and [ Mo(Et 2NCS 2)(CO)(NO)L 2 ] ( L 2 = py and CO ( 6); dppe ( 7); 2 PPh 3 ( 8); 2 P(OMe) 3 ( 10)) , have been prepared. Crystal structures of 1, 3, 4, 6, 7, 8 and 10 were determined from single crystal X-ray data. The structures show clearly that the stronger electron-withdrawing NO, compared with CO, prefers the location trans to the better electron donor such as NCS − in 1, N 3 − in 3 and Br − in 4, unless some other apparent counteracting factors are also involved. The two bulky phosphine ligands are as expected trans to each other in 8 and 10 and a chelate dppe found in 7. Although the structure of 6 has NO trans to py, the spectral data of 6 (and 7), both in solution and in the solid state, reveal the presence of two different structures. Crystal data: 1, space group P2 1/n, a = 9.879(2), b = 30.302(3), c = 14.858(4) A ̊ , β = 97.00(2)°, Z = 4 ; 3, space group P2 1/c, a = 16.806(5), b = 16.128(3), c = 18.025(4) A ̊ , β = 116.94(2)°, Z = 4 ; 4, space group Ia, a = 14.773(8), b = 8.982(2), c = 17.748(5) A ̊ , β = 96.49(5)°, Z = 4 ; 6, space group P2 1/c, a = 13.499(4), b = 10.033(5), c = 12.962(2) A ̊ , β = 91.66(2)°, Z = 4 ; 7, space group P2 1/n, a = 11.634(3), b = 19.881(4), c = 15.225(4) A ̊ , β = 111.10(2)°, Z = 4 ; 8, space group P2 1/n, a = 11.767(2), b = 18.851(4), c = 19.436(4) A ̊ , β = 107.12(2)°, Z = 4 ; 10, space group P2 1/n, a = 8.732(2), b = 23.98(3), c = 11.303(3) A ̊ , β = 97.66(2)°, Z = 4 .