The Peculiarities of Ionization, Fragmentation and Association (Macrobicyclization) of Pseudoclathrochelate tris-Pyrazoloximates of Zinc(II), Cobalt(II), Iron(II) and Manganese(II) in the LDI Mass Spectra

Svitlana V. Kats,^a Olga V. Severynovskay^a,b Oleg A. Varzatskii,^c Ekaterina G. Lebed,^d@ and Vadim A. Pavlenko^a

^aTaras Shevchenko National University of Kyiv, 01601 Kyiv, Ukraine

^bChuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine, 03164 Kyiv, Ukraine

^cVernadskii Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, 03680 Kyiv, Ukraine

^dNesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow, Russia

^@Corresponding author E-mail: lebed@ineos.ac.ru

DOI: 10.6060/mhc150979l
Macroheterocycles 2015 8(3) 314-320

Main pathway of the ionization of the complexes [M(HPzOx)₃(BC₆H₅)]Cl is heterolytic dissociation of these ionic associates giving chloride ions and boron-capped tris-pyrazoloximate cations [M–Cl^–]⁺. The latters are thermodynamically unstable due to the destraction of a pseudomacrobicyclic framework and undergo the further fragmentation leading to the corresponding species and the cluster ions. Such a dissociative type of the fragmentation suggests a substantial stability of the coordination M−N bonds. The spectra of the oximehydrazonate macrobicyclic complexes with similar structure contain the peaks of the corresponding clathrochelate cations; and to their tris-dioximate analogs, giving the characteristic ion-molecular associates with alkali metal cations. The LDI mass spectra of the boron-capped tris-pyrazoloximate pseudoclathrochelate do not contain the peaks of the molecular ions and their associates with alkali metal ions, whereas the detachment of cross-linking chloride counterion is the main pathway of their fragmentation. The non-macrocyclic tris-pyrazoloximate formed particles are unstable and either undergo the fragmentation with an elimination of one of the three ribbed chelate fragments, or, as tripodal semiclathrochelate tris-pyrazol ligands, form the unusual binuclear complexes by their coordination to the corresponding metal ion.

References:

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1. Voloshin Y.Z., Kostromina N.A., Krämer R. Clathrochelates: Synthesis, Structure and Properties. Amsterdam: Elsevier, 2002. 432 p.

2. Varzatskii O.A., Penkova L.V., Kats S.V., Dolganov A.V., Vologzhanina A.V., Pavlov A.A., Novikov V.V., Bogomyakov A.S., Nemykin V.N., Voloshin Y.Z. Inorg. Chem. 2014, 53, 3062–3071.

http://dx.doi.org/10.1021/ic4029047

3. Novikov V.V., Varzatskii O.A., Negrutska V.V., Bubnov Y.N., Palchykovska L.G., Dubey I.Y., Voloshin Y.Z. J. Inorg. Biochem. 2013, 124, 42–45.

http://dx.doi.org/10.1016/j.jinorgbio.2013.03.005

4. Varzatskii О.А., Novikov V.V., Shulga S.V., Belov A.S., Vologzhanina A.V., Negrutska V.V., Dubey I.Y., Bubnov Y.N., Voloshin Y.Z. Chem. Commun. 2014, 50, 3166–3168.

http://dx.doi.org/10.1039/c3cc47018k

5. Varzatskii O.A., Shul'ga S.V., Belov A.S., Novikov V.V., Dolganov A.V., Vologzhanina A.V., Voloshin Y.Z. Dalton Trans. 2014, 43, 17934–17948.

http://dx.doi.org/10.1039/C4DT01557F

6. Voloshin Y.Z., Novikov V.V., Nelyubina Y.V. RSC Adv. 2015, 5, 72621–72637.

http://dx.doi.org/10.1039/C5RA10949C

7. Novikov V.V., Ananyev I.V., Pavlov A.A., Fedin M.V., Lyssenko K.A., Voloshin Y.Z. J. Phys. Chem. Lett. 2014, 5, 496–500.

http://dx.doi.org/10.1021/jz402678q

8. Novikov V.V., Pavlov A.A., Belov A.S., Vologzhanina A.V., Savitsky A., Voloshin Y.Z. J. Phys. Chem. Lett. 2014, 5, 3799–3803.

http://dx.doi.org/10.1021/jz502011z

9. Voloshin Y.Z., Mosin V., Korol E.N. Inorg. Chim. Acta 1991, 180, 189–193.

http://dx.doi.org/10.1016/S0020-1693(00)84931-2

10. Kats S.V., Varzatskii O.A., Penkova L.V., Vologzhanina A.V., Novikov V.V., Lebed E.G., Voloshin Y.Z. Macroheterocycles 2014, 7, 34–39.

http://dx.doi.org/10.6060/mhc140485v

11. Novikov V.V., Pavlov A.A., Nelyubina Y.V., Boulon M.-E., Varzatskii O.A., Voloshin Y.Z., Winpenny R.E.P. J. Am. Chem. Soc. 2015, 137, 9792−9795.

http://dx.doi.org/10.1021/jacs.5b05739

12. Azarkh M., Penkova L., Kats S., Varzatskii O., Voloshin Y., Groenen E. J. Phys. Chem. Lett. 2014, 5, 886−889.

http://dx.doi.org/10.1021/jz5000963

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The Peculiarities of Ionization, Fragmentation and Association (Macrobicyclization) of Pseudoclathrochelate tris-Pyrazoloximates of Zinc(II), Cobalt(II), Iron(II) and Manganese(II) in the LDI Mass Spectra

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