title: Distinctive unimolecular gas-phase reactivity of [M(en)2]2+ (M = Ni, Cu) dications and their inclusion complexes with the macrocyclic cavitand cucurbit[8]uril.
abstract: Electrospray ionization mass spectrometry makes it possible to generate gas-phase bis-ethylenediamine nickel and copper dications, [M(en)(2)](2+) (M = Ni, 1; M = Cu, 2), as well as their {[M(en)(2)]@cuc[8]}(2+) inclusion complexes with the macrocyclic cavitand cucurbit[8]uril (cuc[8]). The unimolecular gas-phase reactivity of these species has been investigated by electrospray ionization tandem mass spectrometry with a quadrupole-time-of-flight configuration. Distinctive fragmentation pathways have been observed for the free and encapsulated [M(en)(2)](2+) (M = Ni, Cu) dications under collision-induced dissociation (CID) conditions. The dications [M(en)(2)](2+) (M = Ni, Cu) dissociate according to several competitive pathways that involve intra-complex hydrogen or electron-transfer processes. Most of these channels are suppressed after encapsulation inside the cucurbit[8]uril macrocycle and, as a consequence, a simplification of the {[M(en)(2)]@cuc[8]}(2+) fragmentation pattern is observed. The results obtained demonstrate that the encapsulation of a coordination complex inside a host molecule can be used to alter the nature of the product ions generated under CID conditions.
authors: A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russian Federation.
authors: Tatyana
authors: T
authors: Mitkina
authors: Vladimir
authors: V
authors: Fedin
authors: Rosa
authors: R
authors: Llusar
authors: Ivan
authors: I
authors: Sorribes
authors: Cristian
authors: C
authors: Vicent
references: Angew Chem Int Ed Engl. 2004 Mar 5;43(11):1329-31
references: 15368400
references: J Mass Spectrom. 2004 Jun;39(6):594-9
references: 15236296
references: J Am Chem Soc. 2005 Apr 27;127(16):6109-15
references: 15839712
references: Mass Spectrom Rev. 2001 Sep-Oct;20(5):253-309
references: 11948654
references: J Am Chem Soc. 2001 Oct 17;123(41):10071-5
references: 11592886
references: J Am Chem Soc. 2003 Aug 6;125(31):9284-5
references: 12889944
references: J Am Soc Mass Spectrom. 1993 Jan;4(1):11-5
references: 24234739
references: J Phys Chem A. 2006 Jul 13;110(27):8304-15
references: 16821814
references: J Am Chem Soc. 2001 Nov 14;123(45):11316-7
references: 11697985
references: J Mass Spectrom. 2006 Mar;41(3):312-22
references: 16421865
references: J Mass Spectrom. 2003 Mar;38(3):333-42
references: 12644996
references: Chemistry. 2004 Jun 21;10(12):2927-34
references: 15214074
references: J Am Soc Mass Spectrom. 1995 May;6(5):437-47
references: 24214225
references: Acc Chem Res. 2001 Aug;34(8):653-61
references: 11513573
references: Angew Chem Int Ed Engl. 2001 Jun 1;40(11):2119-2121
references: 11433463
references: Angew Chem Int Ed Engl. 2003 Apr 29;42(17):1896-9
references: 12730968
references: Angew Chem Int Ed Engl. 2005 Aug 5;44(31):4844-70
references: 16052668
references: Dalton Trans. 2006 Nov 14;(42):5051-61
references: 17060991
references: Inorg Chem. 2006 Aug 21;45(17):6950-5
references: 16903754
references: Rapid Commun Mass Spectrom. 2005;19(13):1797-805
references: 15945020
references: J Mass Spectrom. 2006 Feb;41(2):202-7
references: 16421860
references: Chem Soc Rev. 2007 Feb;36(2):267-79
references: 17264929
references: J Am Soc Mass Spectrom. 2001 Oct;12(10):1114-9
references: 11605973
references: Acc Chem Res. 2003 Aug;36(8):621-30
references: 12924959