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Electrospray Mass Spectrometry Study on Polynuclear Pd(II) and Ni (II) Complexes of 3, 6, 9, 16, 19, 22‐Hexaazatricyclo [22. 2.2.2 11,14 ] triaconta‐11, 13, 24, 26 (1), 27, 29‐Hexaene
Author(s) -
He WeiJiang,
Liu Fang,
Ye ZhiFeng,
Mei YuHua,
Guo ZiJian,
Zhu LongGen
Publication year - 2001
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20010190809
Subject(s) - chemistry , electrospray ionization , palladium , dissociation (chemistry) , mass spectrometry , acetic acid , mass spectrum , methanol , medicinal chemistry , nuclear chemistry , stereochemistry , catalysis , chromatography , organic chemistry
Polynuclear Pd(II) and Ni(II) complexes of macrocyclic polyamine 3,6,9,16,19,22‐hexaazatricyclo[22.2.2.2 11,14 ]‐triaconta 11,13,24,26(l),27,29‐hexaene (L) in solution were investigated by electrospray ionization mass spectrometry (ESIMS). For methanol solution of complexes M 2 LX 4 (M = Pd(II) and Ni(II), X= Cl and I), two main clusters of peaks were observed which can be assigned to [M 2 LX 3 ] + and [M 2 LX 2 ] 2+ . When Pd 2 LCl 4 was treated with 2 or 4 mol of AgNO 3 , it gave rise formation of Pd 2 LCl 2 (NO 3 ) 2 · H 2 O and [Pd 2 L(H 2 O) m (NO 3 ) n ] (4‐n)+ , respectively. ESMS spectra show that the dissociation of the former in the ionization process gave peaks of [Pd 2 LCl 2 ] 2+ and [(Pd 2 LCl 2 )NO 3 ] + , while dissociation of the later gave the peaks of [Pd 2 L(CH 3 CO 2 ) 2 ] 2+ and [Pd 2 L(CH 3 CO 2 ) 2 ](NO 3 ) + in the presence of acetic acid. Similar species were observed for Pd 2 LI 4 when treated with 4 mol of AgNO 3 . When [Pd 2 L · (H 2 O) m (NO 3 ) n ] (4‐n)+ reacted with 2 mol of oxalate anions at 40°C, [Pd 4 L 2 (C 2 O 4 ) 2 (NO 3 ) 2 ] 2+ and [Pd 4 L 2 (C 2 O 4 ) 2 (NO 3 )] 3+ were detected. This implies the formation of square‐planar molecular box Pd 4 L 2 (C 2 O 4 ) 2 (NO 3 ) 4 in which C 2 O 4 − may act as bridging ligands as confirmed by crystal structure analysis. The dissociation form and the stability of complex cations in gaseous state are also discussed. This work provides an excellent example of the usefulness of ESIMS in the identification of metal complexes in solution.