摘要
The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]^- with phenthiolate [Et_4N]SΦ in 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 of 1a 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 in the 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 a single oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atom is a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linked to 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 was discussed also.
The reaction of Mo(0) complex [Mo(CO)_4(S_2CNEt_2)]^- with phenthiolate [Et_4N]SΦ in 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 of 1a 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 in the 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 a single oxo ligand coordinating to a molybdenum(Ⅳ) and the geometry around Me(Ⅳ) atom is a distorted square pyramid.Interestingly,the solvate molecule isopropanol of 1b is linked to 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 was discussed also.
基金
Project supported by the National Natural Science Foundation of China and the Natural Science Foundation of Chinese Academy of Sciences.
