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Interaction between Dioxoruthenium( VI ) Porphyrins and Hydroxylamines: Coordination of N ‐Substituted Hydroxylamine to Ruthenium and X‐ray Crystal Structures of Ruthenium Complexes with a Unidentate Nitrosoarene Ligand
Author(s) -
Liang JiangLin,
Huang JieSheng,
Zhou ZhongYuan,
Cheung KungKai,
Che ChiMing
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010601)7:11<2306::aid-chem23060>3.0.co;2-5
Subject(s) - ruthenium , chemistry , nitrosobenzene , denticity , hydroxylamine , ligand (biochemistry) , porphyrin , medicinal chemistry , photochemistry , moiety , nuclear magnetic resonance spectroscopy , coordination complex , stereochemistry , crystal structure , crystallography , catalysis , organic chemistry , biochemistry , receptor , metal
The interactions between dioxoruthenium( VI ) porphyrins 1 with N ‐phenylhydroxylamine or unsubstituted hydroxylamine are described. Reaction of complexes 1 with excess PhNHOH leads to isolation of bis(nitrosobenzene)ruthenium( II ) porphyrins 3 and mono(nitrosobenzene)ruthenium( II ) porphyrins 4 . Both the types of ruthenium complexes are characterized by 1 H NMR, IR, and UV/Vis spectroscopy, and mass spectrometry. The X‐ray structure determinations on [Ru II (TPP)(PhNO) 2 ] ( 3 a ), [Ru II (2,6‐Cl‐TPP)(PhNO) 2 ] ( 3 e ), and [Ru II (4‐MeO‐TPP)(PhNO)(PhNH 2 )] ( 4 d ) (TPP=tetraarylporphyrin) disclose a unidentate nitrosoarene coordination in all these complexes, with Ru−N(PhNO) bond lengths of 2.003(3) ( 3 a , average), 1.991(3) ( 3 e , average), and 2.042(2) Å ( 4 d ). In the case of 4 d , the Ru−N(PhNH 2 ) bond length is found to be 2.075(3) Å. Mechanistic investigations reveal the formation of intermediates [Ru II (Por)(PhNO)(PhNHOH)] ( 5 ; Por=porphyrin), a ruthenium complex with N ‐substituted hydroxylamine ligand, in the “ 1 + PhNHOH” system. The Ru−NH(OH)Ph moiety in 5 undergoes no rapid exchange with free PhNHOH in solution at room temperature, as revealed by 1 H NMR spectroscopy. Unlike the interaction between complexes 1 and PhNHOH, reaction of such complexes with NH 2 OH affords nitrosylruthenium( II ) porphyrins [Ru II (Por)(NO)(OH)] ( 6 ).