PMID- 25068385
OWN - NLM
STAT- MEDLINE
DCOM- 20150511
LR  - 20140818
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 53
IP  - 16
DP  - 2014 Aug 18
TI  - Mono- and binuclear copper(I) complexes of thionucleotide analogues and their 
      catalytic activity on the synthesis of dihydrofurans.
PG  - 8322-33
LID - 10.1021/ic500727z [doi]
AB  - The reaction of copper(I) halides with 2-thiouracil (TUC), 6-methyl-2-thiouacil 
      (MTUC), and 4-methyl-2-mercaptopyrimidine (MPMTH) in the presence of 
      triphenylphosphine (tpp) in a 1:1:2 molar ratio results in a mixed-ligand 
      copper(I) complex with the formulas [Cu2(tpp)4(TUC)Cl] (1), [Cu2(tpp)4(MTUC)Cl] 
      (2), [Cu(tpp)2(MPMTH)Cl].(1)/2CH3OH (3), [Cu(tpp)2(MTUC)Br] (4), and 
      [Cu(tpp)2(MTUC)I].(1)/2CH3CN (5). The complexes have been characterized by FT-IR, 
      (1)H NMR, and UV-vis spectroscopic techniques and single-crystal X-ray 
      crystallography. Complexes 1 and 2 are binuclear copper(I) complexes. Two 
      phosphorus atoms from tpp ligands are coordinated to the copper(I) ions, forming 
      two units that are linked to each other by a deprotonated TUC or MTUC chelating 
      ligand through a sulfur bridge. A linear Cu-S-Cu moiety is formed. The 
      tetrahedral geometry around the metal centers is completed by the nitrogen-donor 
      atom from the TUC or MTUC ligand for the one unit, while for the other one, it is 
      completed by the chloride anion. Two phosphorus atoms from two tpp ligands, one 
      sulfur atom from MPMTH or MTUC ligand, and one halide anion (Cl, Br, and I) form 
      a tetrahedron around the copper ion in 3-5 and two polymorphic forms of 4 (4a and 
      4b). In all of the complexes, either mono- or binuclear intramolecular O-H...X 
      hydrogen bonds enhance the stability of the structures. On the other hand, in 
      almost all cases of mononuclear complexes (with the exception of a 
      symmetry-independent molecule in 4a), intermolecular NH...O hydrogen-bonding 
      interactions lead to dimerization. Complexes 1-5 were studied for their catalytic 
      activity for the intermolecular cycloaddition of iodonium ylides toward 
      dihydrofuran formation by HPLC, (1)H NMR, and LC-HRMS spectroscopic techniques. 
      The results show that the geometry and halogen and ligand types have a strong 
      effect on the catalytic properties of the complexes. The highest yield of 
      dihydrofurans was obtained when "linear" complexes 1 and 2 were used as the 
      catalysts. The activity of the metal complexes on the copper(I)-catalyzed and 
      uncatalyzed intramolecular cycloaddition of iodonium ylide is rationalized 
      through electronic structure calculation methods, and the results are compared 
      with the experimental ones.
FAU - Charalampou, D C
AU  - Charalampou DC
AD  - Section of Inorganic and Analytical Chemistry, Department of Chemistry, double daggerMedical 
      Physics Laboratory, Medical School,  section signSection of Organic Chemistry, Department of 
      Chemistry, and  perpendicularX-ray Unit, Department of Chemistry, University of Ioannina , 
      45110 Ioannina, Greece.
FAU - Kourkoumelis, N
AU  - Kourkoumelis N
FAU - Karanestora, S
AU  - Karanestora S
FAU - Hadjiarapoglou, L P
AU  - Hadjiarapoglou LP
FAU - Dokorou, V
AU  - Dokorou V
FAU - Skoulika, S
AU  - Skoulika S
FAU - Owczarzak, A
AU  - Owczarzak A
FAU - Kubicki, M
AU  - Kubicki M
FAU - Hadjikakou, S K
AU  - Hadjikakou SK
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20140728
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
RN  - 0 (Furans)
RN  - 0 (Organometallic Compounds)
RN  - 0 (Thionucleotides)
RN  - 1191-99-7 (2,3-dihydrofuran)
RN  - 789U1901C5 (Copper)
SB  - IM
MH  - Catalysis
MH  - Copper/*chemistry
MH  - Furans/*chemical synthesis/chemistry
MH  - Models, Molecular
MH  - Molecular Structure
MH  - Organometallic Compounds/chemical synthesis/*chemistry
MH  - Thionucleotides/*chemistry
EDAT- 2014/07/30 06:00
MHDA- 2015/05/12 06:00
CRDT- 2014/07/29 06:00
PHST- 2014/07/29 06:00 [entrez]
PHST- 2014/07/30 06:00 [pubmed]
PHST- 2015/05/12 06:00 [medline]
AID - 10.1021/ic500727z [doi]
PST - ppublish
SO  - Inorg Chem. 2014 Aug 18;53(16):8322-33. doi: 10.1021/ic500727z. Epub 2014 Jul 28.