Electrospray Ionization Mass Spectrometry: Part III: Applications in Inorganic Chemistry and Synthetic Polymer Chemistry

Abstract

The introduction of electrospray ionization mass spectrometry (ESI-MS) in the mid-1980s started a new era in mass spectrometry and, currently, mass spectrometers of this type are present in virtually all pharmaceutical and biotechnology laboratories. Mass spectrometry has now become important for obtaining molecular weights as well as structural information for chemical substances including very large molecules, for example, biological substances such as proteins, carbohydrates, and oligonucleotides. This paper extends the applications of ESI-MS in this series to a variety of inorganic systems.

Synthesis and Characterisation of ν3‐Octahedral [Ni36Pd8(CO)48]6− and [Ni35Pt9(CO)48]6− Clusters Displaying Unexpected Surface Segregation of Pt Atoms and Molecular and/or Crystal Substitutional Ni/Pd and Ni/Pt Disorder

“…ESI mass spectrometry studies of [NBu 4 ] 6 [Ni 35 Pt 9 (CO) 48 ] and [NBu 4 ] 6 [Ni 36 Pd 8 (CO) 48 ] : The enormous potential of ESI‐MS (electrospray ionisation mass spectrometry) in studying sparingly volatile neutral organometallic compounds20 and clusters,21 as well as nonvolatile cluster salts, has widely been recognised 22–24. To our knowledge, the largest cluster so far studied by ESI‐MS is the [Os 20 (CO) 40 ] 2− dianion 25.…”

Molecular Gold—Multinuclear Gold(I) Complexes

“…Electrospray ionization (ESI), a “soft” ionization source for mass spectrometry, has proved to be an extremely powerful and versatile method for the characterization not only of multinuclear metal clusters but also in the identification of coordination compounds and organometallic complexes. It provides a convenient and effective way to produce intact ions from thermally labile complexes and from multiply charged metal clusters 9. Clusters 1 – 4 have been characterized by ESI mass spectrometry and shown to be intact in solution.…”

“…Clusters 1 – 4 have been characterized by ESI mass spectrometry and shown to be intact in solution. Details on the fragmentation pattern, dissociation behavior, as well as bond energies can be readily estimated using collision‐induced‐dissociation studies 9…”

Molekulares Gold – mehrkernige Gold(I)-Komplexe

“…Im Gegensatz zu den vielen bekannten Clustern der niedrigeren Homologen Kupfer(i) und Silber(i) sind mehrkernige Gold(i)-Chalkogenidcluster selten. In 5 konnte das Anion nicht identifiziert und lokalisiert werden, während in 4 eine Fehlordnung der CH 2 Cl 2 -Cokristallite festgestellt [*] [9] Die Cluster 1 ± 4 wurden durch ESI-MS charakterisiert, und es zeigte sich, dass sie auch in Lösung stabil sind. [5] Kürzlich wurden zwei Sulfid-Gold(i)-Cluster beschrieben: [Au 12 S 4 (dppm) 6 ](PF 6 ) 4 ) und [Au 10 S 4 {Ph 2 PN-(nPr)PPh 2 } 4 ](PF 6 ) 4 2, mit den Diphosphanliganden Bis(diphenylphosphanyl)methan (dppm) bzw.…”

“…[2] [3,4] Obwohl die Verwendung von Phosphan-Brückenliganden für den Aufbau mehrkerniger Cluster viel versprechend wirkt, sind diese nach wie vor äuûerst selten. [9] Abgesehen von Verbindungen mit weichen Chalkogenidliganden sind einige wenige Komplexe bekannt, bei denen harte Stickstoffdonoren die Gold(i)-Zentralatome verbrücken. Bis(diphenylphosphanyl)-n-propylamin (Ph 2 PN(nPr)PPh 2 ).…”