Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Chemistry. 2010 Apr 6;16(13):3962-9. doi: 10.1002/chem.200902742.
The ion-molecule reactions of dimethyl ether with cyclometalated Pt(bipy-H) were investigated in gas-phase experiments, complemented by DFT methods, and compared with the previously reported ion-molecule reactions with its sulfur analogue. The initial step corresponds in both cases to a platinum-mediated transfer of a hydrogen atom from the ether to the (bipy-H) ligand, and three-membered oxygen- and sulfur-containing metallacycles serve as key intermediates. Oxidative C--C bond coupling ("dehydrosulfurization"), which dominates the gas-phase ion chemistry of the Pt(bipy-H) ion with dimethyl sulfide, is practically absent for dimethyl ether. The competition in the formation of C(2)H(4) and CH(2)X (X=O, S) in the reactions of Pt(bipy-H) with (CH(3))(2)X (X=O, S) as well as the extensive H/D exchange observed in the Pt(bipy-H)/(CH(3))(2)O system are explained in terms of the corresponding potential-energy surfaces.
在气相实验中，研究了二甲基醚与环金属化[Pt（bipy-H）]（+）的离子-分子反应，并用 DFT 方法进行了补充，并与之前报道的其硫类似物的离子-分子反应进行了比较。在这两种情况下，初始步骤都对应于铂介导的从醚到（bipy-H）配体的氢原子转移，并且三原子氧和含硫金属环作为关键中间体。在[Pt（bipy-H）]（+）与二甲基硫的气相离子化学中占主导地位的 C-C 键偶联氧化（“脱硫”）在二甲基醚中实际上不存在。在[Pt（bipy-H）]（+）与（CH（3））（2）X（X=O，S）的反应中形成 C（2）H（4）和 CH（2）X（X=O，S）的竞争以及在[Pt（bipy-H）]（+）/（CH（3））（2）O 体系中观察到的广泛的 H/D 交换，可以根据相应的势能面来解释。
