Synthesis,structure and electrochemistry of dithiocarbamato phenthiolate oxo-molybdenum(Ⅳ)complexes[MoO(SΦ)_2(S_2CNEt_2)]

The reaction of Mo(0) complex Mo(CO)_4(S_2CNEt_2)]~- with phenthiolate Et_4N]SΦin acetonitrilo in the presence of small amount of air affords a new oxo-molybdenum com-plex MoO(SΦ)_2(S_2CNEt_2)]~-,which crystallizes in two forms of crystals,Et_4N]MoO(SΦ)_2(S_2CNEt_2)](1a) and Et_4N]MoO(SΦ)_2(S_2CNEt_2)]·(CH_3)_2CHOH (1b).The structures of1a and 1b were determined from three-dimensional X-ray data.1a crystallizes in the mo-noclinie,space group C_c with a=12.321(4),b=15.245(4),c=16.087(9);β=98.44(4)°.V=2989~3,Z=4,D_c=1.35 g/cm~3 and R=0.031 for 2434 reflections I>3(I)].1b crystallizes inthe monoclinic,space group P2_1/n with a=9.861(1),b=20.357(3),c=17.122(5)A;β=92.27(2)°,V=3434.3~3,Z=4;D_c=1.29 g/cm~3 and R=0.051 for 2852 independeut reflections I>3σ(I)],The structures of 1a and 1b reveal that the anion MoO(SΦ)_2(S_2CNEt_2)]~- contains asingle oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atomis a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linkedto oxo group by a hydrogen-bond of 1.928A,leading to the increase of Mo=O bond distance(1.718).Mo—S distances are 2.44 and 2,39.The electrochemical behavior of 1 wasdiscussed also.