AI Article Synopsis
- The study investigates various anionic metal-carbonyl clusters using energy-dependent electrospray ionization mass spectrometry (EDESI-MS).
- Key findings include: orderly fragmentation of carbonyl ligands from clusters with compact metal cores and equal ion intensity for CO loss, the occurrence of electron autodetachment after significant CO elimination in multiply charged clusters, and irregular CO loss from clusters with open metal cores, indicating polyhedral core rearrangements.
- Some gas-phase transformations observed in the clusters reflect similar processes that occur in solution.
Article Abstract
The anionic clusters [HOs(5)(CO)(15)](-), [PtRu(5)C(CO)(15)](2-), [Os(10)C(CO)(24)](2-), [Os(17)(CO)(36)](2-), [Os(20)(CO)(40)](3-), [Co(6)C(CO)(15)](2-), [Pt(3)Ru(10)C(2)(CO)(32)](2-) and [Pd(6)Ru(6)(CO)(24)](2-) have been analysed by energy-dependent electrospray ionisation mass spectrometry (EDESI-MS). Three main features have emerged. Firstly, carbonyl ligands are fragmented from clusters with compact metal cores in an orderly fashion, with each of the ions generated by CO loss having approximately equal intensity. Secondly, electron autodetachment takes place in multiply charged anionic clusters, but only after elimination of a large proportion of their carbonyl ligands. Thirdly, clusters with open metal cores do not undergo CO loss in an orderly fashion, but certain peaks are considerably less intense. The appearance of these low-intensity peaks is believed to signify polyhedral core rearrangements, with open clusters folding to form more compact geometries. In some cases, the gas-phase transformations observed by EDESI-MS mirror those that are known to take place in solution.
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| http://dx.doi.org/10.1002/chem.200390116 | DOI Listing |
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