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Mass spectrometry of transition metal π‐complexes. 40 —(η 4 ‐Norbornadiene)‐(η 5 ‐cyclopentadienyl)rhodium derivatives
Author(s) -
Zagorevskii D. V.,
Chen Hongwen,
Holmes J. L.,
Nekrasov Yu. S.,
Chizhevski I. T.,
Rastova N. V.,
Kolobova N. E.
Publication year - 1993
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210280434
Subject(s) - norbornadiene , substituent , chemistry , cyclopentadienyl complex , ligand (biochemistry) , moiety , diene , stereochemistry , photochemistry , medicinal chemistry , crystallography , organic chemistry , biochemistry , natural rubber , receptor , catalysis
Electron impact mass spectra of substituted norbornadienecyclopentadienylrhodium complexes have been studied. The decompositions of molecular ions are (i) metal–ligand bond rupture, (ii) norbornadiene skeleton destruction, (iii) substituent or hydrogen atom elimination from the norbornadiene moiety and (iv) radical or neutral molecule elimination from the substituent(s) on the diene ligand. Norbornadiene ligand loss occurs more easily than loss of the cyclopentadienyl ring. Elimination of C 2 H 2 R and C 2 H 3 from the diene ligand leads to the formation of rhodocenium or its corresponding substituted derivatives. It is proposed that bridging CC bond rupture followed by migration of the endo ‐H atom around the six‐membered ring precedes the loss of the substituent. Some decomposition pathways of the norbornadiene ligand are explained in terms of specific interaction between the metal atom and substituent.