INQUIMAE   12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
Electrospray ionization mass spectrometry of a novel family of complexes in which various nitroso compounds are stabilized via coordination to [IrCl5]2
Autor/es:
NATALIA ESCOLA, FLORENCIA DI SALVO, RENATO HADDAD, LAURA PERISSINOTTI, MARCOS NOGUEIRA EBERLIN AND FABIO DOCTOROVICH
Revista:
INORGANIC CHEMISTRY
Editorial:
ACS Publications
Referencias:
Lugar: Washington DC; Año: 2007 vol. 46 p. 4827 - 4834
ISSN:
0020-1669
Resumen:
Electrospray ionization mass spectrometry (ESI-MS) and
tandem mass spectrometry (ESI-MS/MS) data of a unique family of complexes of
nitroso compounds coordinated to pentachloroiridate(III), [Cl5IrN(O)XR]2-
(X ) NH, S, CH and R ) alkyl, aryl) are presented. These novel complexes are
obtained by nucleophilic attack of primary amines, thiols. and alkenes to the
coordinated nitrosyl. Despite their lability and low volatility, MS analysis of
complexes of the type MN(O)X was done for the first time, complementing other
spectroscopic techniques. The intrinsic dissociation chemistry of the gaseous
diagnostic ions was studied via ESI-MS/MS and found to be very useful to
confirm the proposed connectivities of the parent complexes. In particular, ESI-MS
of their solutions allows the detection of series of diagnostic ions, mainly,
[M - Cl]-, [M + K]-, [M - NO]- ·, and [M - Cl + AcN]-
(AcN ) acetonitrile), which confirmed the identity of the analyzed complexes to
be M ) [Cl5IrN(O)XR]2-. Major fragments were formed by
losses of NO or N(O)XR. ESI-MS and ESI-MS/MS measurements are therefore shown
to be the proper techniques to complement the spectroscopic characterization of
this important class of nitroso complexes. An interesting rearrangement that
does not take place in solution was observed in the gaseous phase, and a
plausible mechanism is discussed.