van Beelen Eric S E, Ingemann Steen
Swammerdam Institute for Life Sciences, Faculty of Science, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.
Rapid Commun Mass Spectrom. 2005;19(3):317-22. doi: 10.1002/rcm.1787.
The gas-phase reactions of a series of (di)manganese carbonyl positive ions with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me(3)TACN) have been examined with the aid of Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. The monomanganese carbonyl ions, Mn(CO)(n) (n = 2-5), react predominantly by ligand exchange and to a minor extent by electron transfer with the formation of the radical cation of Me(3)TACN. For the Mn(CO)(n) (n = 2-4) ions, the ligand exchange results in the exclusive formation of a Mn(Me(3)TACN) complex, whereas small amounts of Mn(CO)(Me(3)TACN) ions are also generated in the reactions of the Mn(CO)(5) ion. The Mn(2)(CO)(n) ions (n = 2, 4 and 5) react also by competing electron transfer and ligand exchange. The reaction of the Mn(2)(CO)(2) and Mn(2)(CO)(4) ions is associated with cleavage of the Mn--Mn bond as evidenced by the pronounced formation of Mn(Me(3)TACN) ions. For Mn(2)(CO)(5), the ligand exchange leads mainly to the formation of Mn(2)(CO)(n)(Me(3)TACN) (n = 1-3) ions. These primary product ions react subsequently by the incorporation of a second Me(3)TACN molecule to afford Mn(2)(CO)(Me(3)TACN)(2) and Mn(2)(CO)(2)(Me(3)TACN)(2) ions. Both of these latter species incorporate an oxygen molecule with formation of ions with the assigned composition of Mn(2)(O(2))(CO)(Me(3)TACN)(2) and Mn(2)(O(2))(CO)(2)(Me(3)TACN)(2).
借助傅里叶变换离子回旋共振（FTICR）质谱法，研究了一系列二羰基锰正离子与1,4,7-三甲基-1,4,7-三氮杂环壬烷（Me(3)TACN）的气相反应。单羰基锰离子Mn(CO)(n)（n = 2 - 5）主要通过配体交换反应，少量通过电子转移反应，生成Me(3)TACN的自由基阳离子。对于Mn(CO)(n)（n = 2 - 4）离子，配体交换反应仅生成Mn(Me(3)TACN)配合物，而在Mn(CO)(5)离子的反应中还会生成少量的Mn(CO)(Me(3)TACN)离子。Mn(2)(CO)(n)离子（n = 2、4和5）也通过竞争电子转移和配体交换进行反应。Mn(2)(CO)(2)和Mn(2)(CO)(4)离子的反应伴随着Mn - Mn键的断裂，这可通过Mn(Me(3)TACN)离子的显著生成得到证明。对于Mn(2)(CO)(5)，配体交换主要生成Mn(2)(CO)(n)(Me(3)TACN)（n = 1 - 3）离子。这些初级产物离子随后通过结合第二个Me(3)TACN分子进行反应，生成Mn(2)(CO)(Me(3)TACN)(2)和Mn(2)(CO)(2)(Me(3)TACN)(2)离子。这两种后一种物质都结合了一个氧分子，形成了组成确定为Mn(2)(O(2))(CO)(Me(3)TACN)(2)和Mn(2)(O(2))(CO)(2)(Me(3)TACN)(2)的离子。
