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The Construction of (Salophen)ruthenium(II) Assemblies Using Axial Coordination
Author(s) -
Chichak Kelly,
Jacquemard Ulrich,
Branda Neil R.
Publication year - 2002
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 - 10.1002/1099-0682(20022)2002:2<357::aid-ejic357>3.0.co;2-t
Subject(s) - chemistry , synthon , bimetallic strip , ruthenium , supramolecular chemistry , chromophore , adduct , metal , schiff base , diastereomer , electrochemistry , coordination complex , ligand (biochemistry) , stereochemistry , linker , crystallography , lewis acids and bases , crystal structure , photochemistry , catalysis , organic chemistry , electrode , biochemistry , receptor , operating system , computer science
Mononuclear and binuclear carbonylruthenium(II) complexes with N 2 O 2 Schiff base ligands based on 3,5‐di‐ tert ‐butylsalicylaldehyde and three different ortho ‐diamines have been prepared. The mononuclear Ru(BSP)(CO) [BSP = N , N′ ‐bis(3,5‐di‐ tert ‐butylsalicylidene)‐1,2‐phenylenediamine] complex 4 acts as a versatile supramolecular synthon, as illustrated by the fact that it spontaneously forms linear and three‐dimensional assemblies through axial coordination with pyridyl Lewis bases. Using this motif, neutral and charged assemblies 6 , 9 , and 12 were prepared. The versatility of the salophen ligand was highlighted by the preparation of bimetallic carbonylruthenium(II) compounds 14−17 from 1,2,4,5‐tetraaminobenzene and 2,3,7,8‐tetraaminodibenzo[1,4]dioxin. The bimetallic complexes were isolated as a mixture of cis and trans diastereomers with respect to the spatial relationship between the two axially bound carbon monoxide ligands. The electronic spectral and electrochemical properties of the pyridyl adducts 5 , 15 , and 17 were compared. The properties of 17 closely resembled 5 due to the insulating effect of the extended central tetraamino fragment, while 15 behaved as a single, novel chromophore. The electrochemical studies revealed that the central tetraamino linker regulates the communication between the two metal centers of 15 and 17 . It was found that the two metal atoms of 15 sense each other to a larger extent than those of 17 .