Insertion reactions of metal carbonyl anions with methyl formate in the gas phase as revealed by (13)C- and D-labeling.

School of Chemistry, University of New South Wales, Kensington, Australia Institute of Mass Spectrometry, University of Amsterdam, Nieuwe Achtergracht The gas-phase reactions of coordinatively unsaturated metal carbonyl anions (M(CO) n (-) , M=Cr, Mn, Fe, Co; n=0-3 and Co(CO)nNO(-), n=0-2) with unlabeled and D- and (13)C-labeled methyl formate have been studied with Fourier transform ion cyclotron resonance mass spectrometry. The reactions proceed in most instances by loss of one or more CO molecules from the collision complex. In the reactions of the dicarbonyl and tricarbonyl anions with H(13)COOCH3, part of the eliminated carbon monoxide molecules contain the label revealing the occurrence of initial insertion of the metal center into the bonds adjacent to the carbonyl function of the substrate with formation of five- or six-coordinate intermediates, respectively. In addition, the MnCCO) 3 (-) , Fe(CO) 2 (-) , and CoCCO) 2 (-) ions react by the loss of methanol and a [C,H2,O] neutral species. The D- and (13)C-labeling show that methanol is expelled in a reductive elimination from a five- or six-coordinate species, whereas the [C,H2,O] loss is a more complex process possibly involving the competing losses of formaldehyde and CO + H2. In the reaction of Fe(CO) 3 (-) with H 13 (13) COOCH3, a facile consecutive exchange of all three CO ligands of the reactant ion for (13)CO is observed. This novel reaction appears to involve initial insertion into the H(13)CO-OCH3-bond followed by facile hydrogen shifts from the formyl ligand to a CO Hgand prior to the loss of unlabeled methyl formate.

Detection limits and surface interactions in quantitative negative chemical-ionization mass spectrometry Ultratrace determination of metals and organic compounds by means of their complexes.

Details are given of a selective negative-ion mass-spectrometric method appropriate for the ultratrace determination of metals and organic compounds by means of their complexes. Direct introduction of the sample into the ion-source, attachment of low-energy electrons, and selected-ion monitoring are described, and comparative data are given relating to surface effects at the tips of insertion-probes on detection limits. Detection limits for chromium and cobalt, determined as their tris(2,2,6,6-tetramethylheptane-3,5-dione) chelates, were respectively 1.0 and 0.16 pg, and that for nickel [as its bis(N,N-diethyldithiocarbamate) complex] was 1.0 pg. Detection limits of 2.0 and 1.0 ng are attainable for malathion and ethion by measurement of the nickel(II) complexes of their O,O'-dialkyldithiophosphate hydrolysis products.

Application of secondary-electron capture negative-ion (SECNI) mass spectrometry to the analysis of metal-organic compounds.

The application of secondary-electron capture negative-ion (SECNI) mass spectrometry to the analysis of metal-organic compounds is described and typical examples are discussed. Negative-ion mass spectra are simple, molecular anions and ligand ions being the predominant species. Metallic or ligand impurities are readily identified by this technique, which makes it extremely useful for the determination of purity and formulation of metal-organic compounds. Because of its sensitivity, the technique is also valuable for trace metal analysis.