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Efficient Synthetic Approaches To Access Ruthenium(II) Complexes with 2‐(Trimethylsilyl)ethyl‐ or Acetyl‐Protected Terpyridine–Thiols
Author(s) -
Wen HuiMin,
Zhang DaoBin,
Zhang LiYi,
Shi LinXi,
Chen ZhongNing
Publication year - 2011
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.201001249
Subject(s) - chemistry , ruthenium , terpyridine , trimethylsilyl , ligand (biochemistry) , intramolecular force , proton nmr , chelation , chloride , nuclear magnetic resonance spectroscopy , medicinal chemistry , polymer chemistry , stereochemistry , inorganic chemistry , organic chemistry , metal , catalysis , biochemistry , receptor
Abstract A series of thiol‐functionalized terpyridines (tpy) with protective groups, such as acetyl (Ac), 2‐(trimethylsilyl)ethyl (TMSE), and tert ‐butyl ( t Bu), and the corresponding ruthenium(II) complexes were synthesized in high yields. The TMSE‐protected thiol‐functionalized Ru II (tpy) complexes can be readily converted into the corresponding ruthenium(II) complexes with an acetyl group by using AgClO 4 /acetyl chloride or TBAF/acetyl chloride. Based on this convenient synthetic approach under mild conditions, the ruthenium(II) complex [(AcSCH 2 C 6 H 4 tpy)(PPh 3 ) 2 Ru(C≡CC 6 H 4 C≡CC 6 H 5 )](ClO 4 ) {[ 12 ](ClO 4 )} with acetylthio–tpy was successfully obtained by a three‐step synthetic procedure. By utilizing 4′‐{4‐[(acetylsulfanyl)methyl]phenyl}‐2,2′:6′,2″‐terpyridine as a chelating ligand, a dinuclear dicyanamido‐linked ruthenium complex was prepared, characterized, and immobilized onto gold electrode surfaces to form self‐assembled monolayers (SAMs). The compounds were characterized by mass spectrometry, IR, 1 H NMR and 13 C NMR or 31 P NMR spectroscopy, and elemental analysis. The solid‐state structure of complex [ 14 ](PF 6 ) 3 was determined by X‐ray crystallography, in which the intramolecular S ⋅⋅⋅ S distance was found to be 31.194(2) Å.