OXIDATIVE ADDITION-REACTIONS OF DICARBONYL-[1,1,1-TRIS((DIPHENYLPHOSPHINO)METHYL)ETHANE]RUTHENIUM(O) - ELIMINATION OF KETENE FROM AN ACETYLMETAL COMPOUND
OXIDATIVE ADDITION-REACTIONS OF DICARBONYL-[1,1,1-TRIS((DIPHENYLPHOSPHINO)METHYL)ETHANE]RUTHENIUM(O) - ELIMINATION OF KETENE FROM AN ACETYLMETAL COMPOUND
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DOI：
10.1021/om00133a002
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发表时间：
1986-02-01
期刊：
影响因子：
2.8
通讯作者：
BAIRD, MC
中科院分区：
文献类型：
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作者：
HOMMELTOFT, SI;BAIRD, MC
[RuH(CO)2(三磷)]+和[RuR(CO)2(三磷)]+(R=Me，Et，PhCH2，烯丙基)。大多数化合物的化学性质似乎都是“正常”的，但氢化物具有惊人的酸性，这可能是因为氢化物配体被迫进入了一个不寻常的配位位置，反式为磷原子，这将在反式影响系列中居于较高位置。虽然乙酰氯的氧化加成似乎得到了乙酰基络合物[Ru(Come)(CO)2(Triphos)]+，但后者是不稳定的，它消除了烯酮，形成了上述氢化物络合物。乙酰基络合物的不同寻常的不稳定性也可能部分归因于叔膦的高反式影响和显著的反式键减弱特性。
[RuH (CO) 2 (triphos)]+, and [RuR (CO) 2 (triphos)]+(R= Me, Et, PhCH2, allyl). Most of thecompounds appear to exhibit “normal” chemical properties but the hydride is surprisingly acidic, possibly because the hydride ligand is forced into an unusual (for it) coordination position, trans to a phosphorus atom, which would lie high in the trans influence series. While oxidative addition of acetyl chloride appears to give the acetyl complex [Ru (COMe)(CO) 2 (triphos)]+, the latter is unstable and eliminates ketene to form the above-mentioned hydride complex. The unusual instability of the acetyl complex is perhaps also to be attributed in part to the high trans influence and pronounced trans bond weakening properties of tertiary phosphines.