A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, 119991, Moscow, Russia.
Dalton Trans. 2010 Feb 28;39(8):2008-15. doi: 10.1039/b916084a. Epub 2010 Jan 11.
The interaction of the carbonyl hydride complex CpMo(PMe(3))(2)(CO)H with Brønsted (fluorinated alcohols, (CF(3))(n)CH(3-n)OH (n = 1-3), and CF(3)COOH) and Lewis (Hg(C(6)F(5))(2), BF(3).OEt(2)) acids was studied by variable temperature IR and NMR ((1)H, (31)P, (13)C) spectroscopies in combination with DFT/B3LYP calculations. Among the two functionalities potentially capable of the interaction - carbonyl and hydride ligands - the first was found to be the preferential binding site for weak acids, yielding CO...HOR or CO...Hg complexes as well as CO...(HOR)(2) adducts. For stronger proton donors ((CF(3))(3)COH, CF(3)COOH) hydrogen-bonding to the hydride ligand can be revealed as an intermediate of the proton transfer reaction. Whereas proton transfer to the CO ligand is not feasible, protonation of the hydride ligand yields an (eta(2)-H(2)) complex. Above 230 K dihydrogen evolution is observed leading to decomposition. Among the decomposition products compound Cp*Mo(PMe(3))(3)(CO)(CF(3))(3)CO.2HOC(CF(3))(3) resulting from a phosphine transfer reaction was characterized by X-ray diffraction. Reaction with BF(3).OEt(2) was found to produce [CpMo(PMe(3))(2)(CO)BF(4)] via initial attack of the hydride ligand.
CpMo(PMe(3))(2)(CO)H 与布朗斯台德（氟化醇，(CF(3))(n)CH(3-n)OH（n = 1-3）和 CF(3)COOH）和路易斯（Hg(C(6)F(5))(2)，BF(3).OEt(2)）酸的相互作用通过变温 IR 和 NMR（（1）H、（31）P、（13）C）光谱学与 DFT/B3LYP 计算相结合进行了研究。在两个可能具有相互作用的功能团 - 羰基和氢化物配体 - 中，发现第一个是弱酸的优先结合位点，生成 CO...HOR 或 CO...Hg 配合物以及 CO...(HOR)(2)加合物。对于更强的质子供体（(CF(3))(3)COH，CF(3)COOH），可以揭示与氢化物配体的氢键作为质子转移反应的中间体。由于 CO 配体不能进行质子转移，因此氢化物配体的质子化生成（eta(2)-H(2)）配合物。在 230 K 以上观察到氢气的释放，导致分解。在分解产物中，通过磷转移反应得到的化合物 Cp*Mo(PMe(3))(3)(CO)(CF(3))(3)CO.2HOC(CF(3))(3) 通过 X 射线衍射进行了表征。与 BF(3).OEt(2) 的反应被发现通过氢化物配体的初始攻击生成 [CpMo(PMe(3))(2)(CO)BF(4)]。
