UV irradiation of [Et4N][Ta(CO)6] in the presence of 2- to 4-dentate phosphines, p(n), yields [Et4N][Ta(CO)4pn]. Ion exchange chromatography on silica gel affords the hydrido complexes HTa(CO)4p2 or HTa(CO)3pn (n = 3, 4), which can be photochemically converted into HTa(CO)2pn. The structure in solution as judged from spectroscopic data is probably an octahedron capped by the hydride. In the solid state, an X-ray diffraction study of trans-[HTa(CO)2(dppe)2] indicates the presence of a pentagonal bipyramid with H-, Ta and the four P in the pentagonal plane. 2-methyl-2-butene is "hydrotantalated", mainly in the anti-Markovnikov manner, to yield the sigma-alkyl complex Me2CH-H(Me)CTa(CO)4p2 (p2 = Ph2PCH2CH2PEt2). The complexes HTa(CO)4/3pn react with pentafulvenes to form eta-5-(C5H4CHR2)Ta(CO)2pn (R2 = Me2, Ph2, NMe2 + H; p(n) = PhP(CH2CH2 PPh2)2). The hepta-coordinated chloride complexes ClTa(CO)6-npn have been prepared photochemically from [Et4N]Cl and HTa(CO)4pn (n = 4, p(n) = 2 dppe), or by reductive carbonylation of TaCl4 in the presence of p(n) (n = 3, p(n) = MeP(CH2CH2CH2PMe2)2).
DOI:
10.1016/0022-328x(92)83042-g
作为产物:
描述:
cis-{Et4N}{Ta(CO)4(dppm)} 在
silica gel 作用下,
以
四氢呋喃 为溶剂,
以75%的产率得到cis-{HTa(CO)4(dppm)}
参考文献:
名称:
Aspects of carbonyltantalum chemistry
摘要:
UV irradiation of [Et4N][Ta(CO)6] in the presence of 2- to 4-dentate phosphines, p(n), yields [Et4N][Ta(CO)4pn]. Ion exchange chromatography on silica gel affords the hydrido complexes HTa(CO)4p2 or HTa(CO)3pn (n = 3, 4), which can be photochemically converted into HTa(CO)2pn. The structure in solution as judged from spectroscopic data is probably an octahedron capped by the hydride. In the solid state, an X-ray diffraction study of trans-[HTa(CO)2(dppe)2] indicates the presence of a pentagonal bipyramid with H-, Ta and the four P in the pentagonal plane. 2-methyl-2-butene is "hydrotantalated", mainly in the anti-Markovnikov manner, to yield the sigma-alkyl complex Me2CH-H(Me)CTa(CO)4p2 (p2 = Ph2PCH2CH2PEt2). The complexes HTa(CO)4/3pn react with pentafulvenes to form eta-5-(C5H4CHR2)Ta(CO)2pn (R2 = Me2, Ph2, NMe2 + H; p(n) = PhP(CH2CH2 PPh2)2). The hepta-coordinated chloride complexes ClTa(CO)6-npn have been prepared photochemically from [Et4N]Cl and HTa(CO)4pn (n = 4, p(n) = 2 dppe), or by reductive carbonylation of TaCl4 in the presence of p(n) (n = 3, p(n) = MeP(CH2CH2CH2PMe2)2).