Generation and reactivity of the fragment ion [B12I8S(CN)]- in the gas phase and on surfaces.

Gaseous fragment ions generated in mass spectrometers may be employed as "building blocks" for the synthesis of novel molecules on surfaces using ion soft-landing. A fundamental understanding of the reactivity of the fragment ions is required to control bond formation of deposited fragments in surface layers. The fragment ion [B12X11]- (X = halogen) is formed by collision-induced dissociation (CID) from the precursor [B12X12]2- dianion. [B12X11]- is highly reactive and ion soft-landing experiments have shown that this ion binds to the alkyl chains of organic molecules on surfaces. In this work we investigate whether specific modifications of the precursor ion affect the chemical properties of the fragment ions to such an extent that attachment to functional groups of organic molecules on surfaces occurs and binding of alkyl chains is prevented. Therefore, a halogen substituent was replaced by a thiocyanate substituent. CID of the precursor [B12I11(SCN)]2- ion preferentially yields the fragment ion [B12I8S(CN)]-, which shows significantly altered reactivity compared to the fragment ions of [B12I12]2-. [B12I8S(CN)]- has a previously unknown structural element, wherein a sulfur atom bridges three boron atoms. Gas-phase reactions with different neutral reactants (cyclohexane, dimethyl sulfide, and dimethyl amine) accompanied by theoretical studies indicate that [B12I8S(CN)]- binds with higher selectivity to functional groups of organic molecules than fragment ions of [B12I12]2- (e.g., [B12I11]- and [B12I9]-). These findings were further confirmed by ion soft-landing experiments, which showed that [B12I8S(CN)]- ions attacked ester groups of adipates and phthalates, whereas [B12I11]- ions only bound to alkyl chains of the same reagents.

Gas Phase Reactivity of [Mo6X14]2- Dianions (X = Cl - I).

We investigate collision-induced dissociation (CID) of [Mo6X14]2- (X = Cl, Br, I) and the reactivity of fragment ions of these precursors with background gases. Ion mobility measurements and theoretical calculations provide structural information for some of the observed ions. Sequential losses of MoX2 units dominate the dissociation pathways of [Mo6Cl14]2-. Meanwhile, loss of X radicals is the main channel for X = Br and I. Ion mobility measurements and computational investigations indicate minor structural changes in the octahedral Mo6 unit for [Mo6Im]- (m = 6-13) fragments. We observe that mass spectra obtained using CID substantially vary among mass spectrometers: Specifically, ions with molecular formula [Mo6Xm(O2)n]- (X = Br and I) are observed as dominant species produced through reactions with O2 in several mass spectrometers, but also adduct free fragment ions were observed in other instruments, depending on the background conditions. Ion-trap fragmentation combined with theoretical investigations indicates that spontaneous losses of X radicals occur upon binding of O2 to [Mo6Im]- fragments (m ≤ 12). Theoretical investigations indicate that both oxygen atoms are bound to the vacant sites of the Mo6 units. This study opens up a new vista to generate and study a large variety of hexanuclear Mo6Xm(O2)n anions.