Fragmentation of transition metal carbonyl cluster anions: Structural insights from mass spectrometry

被引：26

作者：

Butcher, CPG

Dyson, PJ

Johnson, BFG

Khimyak, T

McIndoe, JS

机构：

[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

[2] Ecole Polytech Fed Lausanne, ICMB, BCH, CH-1015 Lausanne, Switzerland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2003年 / 9卷 / 04期

关键词：

anions; carbonyl ligands; cluster compounds; mass spectrometry; metal-metal interactions;

D O I：

10.1002/chem.200390116

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The anionic clusters [HOs5-(Co)(15)](-), [PtRu5C(CO)(15)](2-), [Os10C-(CO)(24)](2-), [Os-17(CO)(36)](2-), [Os-20(CO)(40)](3-) [Co6C(CO)15]2-, [Pt3Ru10C2-(CO)(32)](2-) and [Pd6Ru6(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.

引用

页码：944 / 950

页数：7

共 47 条

[1] CLUSTER SYNTHESIS .41. NEW PLATINUM RUTHENIUM CLUSTER COMPLEXES FROM THE REACTION OF PHCCPH WITH PT2RU4(CO)18 - SYNTHESIS AND STRUCTURAL CHARACTERIZATIONS OF PT2RU3(CO)8(MU-3-ETA-2-PHC2PH)2(MU-4-ETA-2-PHC2PH), PT3RU6(CO)14(MU-3-ETA-2-PHC2PH)3, PT2RU4(CO)14(MU-3-ETA-2-PHC2PH)(MU-4-ETA-2-PHC2PH), PT3RU6(CO)18(MU-3-ETA-2-PHC2PH)3, AND PTRU2(CO)6(MU-3-ETA-2-PHC2PH)(DPPE) [J].