Synthesis and characterization of d0 imido complexes of vanadium. Crystal structure of [V(2,6-iPr2C6H3N)(S2CNC4H4)3]
作者:Francisco Montilla、Antonio Pastor、Angeles Monge、Enrique Gutiérrez-Puebla、Agustín Galindo
DOI:10.1039/a903507i
日期:——
Interaction of [V(NR)Cl3] compounds with 1,2-dimethoxyethane (dme) afforded [V(NR)Cl3(dme)] (R = 2,6-iPr2C6H3 1a or 1-adamantyl 1b) complexes in a nearly quantitative yield. Compounds 1 are suitable sources for the synthesis of other d0 imidovanadium complexes. Metathesis reactions of 1 with the sodium salt of the Kläui’s ligand, NaLOEt (LOEt = (η-C5H5)CoP(O)(OEt)2}3), yielded complexes [V(NR)Cl2(LOEt)] (R = 2,6-iPr2C6H3 2a or 1-adamantyl 2b). Treatment of 1 with several bidentate monoanionic dithio-ligands, –S2CR′, gave the corresponding imido complexes of general formulation [V(NR)(S2CR′)3] (for R = 2,6-iPr2C6H3; R′ = NC4H4 3a, NiPr2 4, OiPr 5a or SiPr 6a; for R = 1-adamantyl; R′ = NC4H4 3b, OiPr 5b or SiPr 6b). The molecular structure of [V(2,6-iPr2C6H3N)(S2CNC4H4)3] 3a has been determined by an X-ray study. Finally, the reaction of 1a with Na(acac), in a 1∶2 molar ratio, produces complex [V(2,6-iPr2C6H3N)Cl(acac)2] 7.
[V(NR)Cl3]化合物与1,2-二甲氧基乙烷(dme)的相互作用几乎定量地生成了[。V(NR)Cl3(dme)](R = 2,6-iPr2C6H3 1a 或 1-阿当提尔 1b)复合物。化合物1是合成其他d0亚胺钒复合物的合适来源。化合物1与Kläui配体的钠盐NaLOEt(LOEt = (η-C5H5)CoP(O)(OEt)2}3)的互变反应生成了复合物[V(NR)Cl2(LOEt)](R = 2,6-iPr2C6H3 2a 或 1-阿当提尔 2b)。将化合物1与几种双齿单阴离子二硫配体–S2CR'反应,得到了一般式为[V(NR)(S2CR')3]的相应亚胺复合物(对于R = 2,6-iPr2C6H3;R' = NC4H4 3a,NiPr2 4,OiPr 5a或SiPr 6a;对于R = 1-阿当提尔;R' = NC4H4 3b,OiPr 5b或SiPr 6b)。通过X射线研究确定了[V(2,6-iPr2C6H3N)(S2CNC4H4)3] 3a的分子结构。最后,1a与Na(acac)按1∶2的摩尔比反应,生成复合物[V(2,6-iPr2C6H3N)Cl(acac)2] 7。