SYNTHESIS AND REACTIONS OF (ETA-5-CYCLOPENTADIENYL)TRICARBONYLHYDRIDOVANADATE - A COMPARATIVE MECHANISTIC STUDY OF ITS ORGANIC HALIDE REDUCTION REACTIONS WITH THOSE OF TRI-NORMAL-BUTYLTIN HYDRIDE
SYNTHESIS AND REACTIONS OF (ETA-5-CYCLOPENTADIENYL)TRICARBONYLHYDRIDOVANADATE - A COMPARATIVE MECHANISTIC STUDY OF ITS ORGANIC HALIDE REDUCTION REACTIONS WITH THOSE OF TRI-NORMAL-BUTYLTIN HYDRIDE
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DOI：
10.1021/ja00493a020
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发表时间：
1978-01-01
影响因子：
15
通讯作者：
BERGMAN, RG
中科院分区：
文献类型：
--
作者：
KINNEY, RJ;JONES, WD;BERGMAN, RG
The complex PPN+[CpV (CO) 3H] _ (PPN-3; Cp t^-CsHs) has been prepared in 70% yield by sodium reduction of CpV (CO) 4 (1) followed by protonationof the resulting dianion [CpV (CO) 3] 2-(2) with water and cation exchange with PPN+ C1_. The physical properties and chemical reactions of 3 have been investigated. The sodium salt of 3 is contact ion paired in the solid state and in THF; dissociation of solvent-separated pairs occurs on conversion to the PPN+ salt or dissolution in polar solvents such as HMPA. Treatment of dianion 2 with methyl iodide gives the related salt PPN+[CpV (CO) 3-CH3]~, which may also be isolated and characterized. Hydride 3 reacts with a wide range of organic halides, resulting in sub-stitution of the halogen atom by the hydrogen of 3. The organometallic products of these reactions are the vanadium halides PPN+[CpV (CO) 3X]~(8). In some cases a second organometallic product is observed; this material is the binuclear bridging hydride PPN+[CpV (CO) 3] 2H~(10), and it is formed by reaction of the kinetic product 8 with starting 3 present in thereduction solutions. Irradiationof 1 in the presence of 3 provides an alternate route to bridging hydride 10. Competition experiments against PPh3 have shown that 3 reacts more rapidly thanthe phosphine with transient, coordinatively unsaturated CpV (CO) 3, but thermodynamically PPh3 is the better ligand. The borohydride salt PPN+[CpV (CO) 2BH4]~ has also been prepared, by
