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Self‐Assembly of Oxamidato‐Chelated Re I ‐ and Mn I ‐Based Flexible Dinuclear Horse‐Stirrup‐Like Metallacycles
Author(s) -
Ramakrishna Buthanapalli,
Divya D.,
Monisha P. V.,
Manimaran Bala.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500962
Subject(s) - oxamide , chemistry , denticity , rhenium , ligand (biochemistry) , chelation , crystallography , metal , stereochemistry , nuclear magnetic resonance spectroscopy , medicinal chemistry , polymer chemistry , crystal structure , inorganic chemistry , organic chemistry , biochemistry , receptor
The self‐assembly of M 2 (CO) 10 (M = Mn, Re), oxamide ligands [H 2 L = N , N′ ‐dibutyloxamide (dbo), N , N′ ‐dibenzyloxamide (dbno)], and flexible bidentate linkers [L′ = 1,2‐bis(4‐pyridyl)ethane (bpe), 1,3‐bis(4‐pyridyl)propane (bpp)] afforded Mn I ‐ and Re I ‐based dinuclear metallacycles [(CO) 3 M(μ‐η 4 ‐L)(μ‐L′)M(CO) 3 ] ( 1 – 6 ). The oxidative addition of oxamide ligands to the equatorial sites and the addition of flexible dipyridyl ligands to the axial sites of facial metal tricarbonyl cores resulted in the formation of dinuclear metallacycles under one‐pot reaction conditions. Metallacycles 1 – 6 were characterized through elemental analysis, IR, UV/Vis, and NMR spectroscopy. The formation of dinuclear compounds 1 and 4 was ascertained by ESI mass spectrometry. The molecular structures of 2 , 3 , 5 , and 6 were elucidated by single‐crystal X‐ray crystallographic methods, which revealed horse‐stirrup‐like dinuclear frameworks in which the metal centers are orthogonally connected by a bridging oxamide ligand through ON∩NO bis(chelation) and a flexible bidentate ligand through M–N coordination. The first one‐step syntheses of self‐assembled neutral Mn I ‐based dinuclear metallastirrups containing bis(chelating) oxamide ligands and their rhenium analogues are reported herein.