Mechanism of protonation of [Pt(3)(mu-PBu(t)(2))3(H)(CO)2], yielding the hydride-bridged [Pt(3)(mu-PBu(t)(2))2(mu-H)(PBu(t)(2)H)(CO)2]OTf (Tf=CF(3)SO(2)), and the spectroscopic and theoretical characterization of a kinetic intermediate.
Mechanism of protonation of [Pt(3)(mu-PBu(t)(2))3(H)(CO)2], yielding the hydride-bridged [Pt(3)(mu-PBu(t)(2))2(mu-H)(PBu(t)(2)H)(CO)2]OTf (Tf=CF(3)SO(2)), and the spectroscopic and theoretical characterization of a kinetic intermediate.
复制标题
[Pt(3)(mu-PBu(t)(2))3(H)(CO)2] 的质子化机制，产生氢化物桥联 [Pt(3)(mu-PBu(t)(2)
DOI：
10.1021/ic001309m
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发表时间：
2001
影响因子：
4.6
通讯作者：
M. Selmi
中科院分区：
文献类型：
--
作者：
A. Fortunelli;P. Leoni;L. Marchetti;M. Pasquali;F. Sbrana;M. Selmi
Pt(I)Pt(I)Pt(II) 三角团簇 Pt(3)(micro-PBu(t)()(2))(3)(H)(CO)(2) (1) 与 TfOH (Tf = CF(3)SO(2)) 反应得到氢化物桥接的阳离子衍生物[Pt(3)(mu-PBu(t)()(2))(2)(mu-H)(PBu(t)()(2)H)(CO)(2)]OTf (2)。通过 TfOD，反应选择性地生成 [Pt(3)(mu-PBu(t)(2))(2)(mu-D)(PBu(t)(2)H)(CO)(2)]OTf (2-D(1))，这意味着质子转移到金属中心，同时通过桥联磷化物之一和试剂的末端氢化物配体的还原偶联形成 P-H 键。该反应通过形成热不稳定动力学中间体进行，该中间体在低温下表征，被认为是 CO-氢键（或质子化）[Pt(3)(mu-PBu(t)(2))(3)(H)(CO)(2)].HOTf (3)。从头算理论研究预测氢键配合物或质子转移紧密离子对可能是动力学中间体结构的候选者。
The reaction of the Pt(I)Pt(I)Pt(II) triangulo cluster Pt(3)(micro-PBu(t)()(2))(3)(H)(CO)(2) (1) with TfOH (Tf = CF(3)SO(2)) affords the hydride-bridged cationic derivative [Pt(3)(mu-PBu(t)()(2))(2)(mu-H)(PBu(t)()(2)H)(CO)(2)]OTf (2). With TfOD the reaction gives selectively [Pt(3)(mu-PBu(t)(2))(2)(mu-D)(PBu(t)(2)H)(CO)(2)]OTf (2-D(1)), implying that the proton is transferred to a metal center while a P-H bond is formed by the reductive coupling of one of the bridging phosphides and the terminal hydride ligand of the reagent. The reaction proceeds through the formation of a thermally unstable kinetic intermediate which was characterized at low temperatures, and was suggested to be the CO-hydrogen-bonded (or protonated) [Pt(3)(mu-PBu(t)(2))(3)(H)(CO)(2)].HOTf (3). An ab initio theoretical study predicts a hydrogen-bonded complex or a proton-transfer tight ion pair as a possible candidate for the structure of the kinetic intermediate.