Stephen T. Astley

Stephen T. Astley
1
8 June 2012
Stephen T. Astley
2
8 June 2012
the carboxylate group
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The carboxylate group as a bridging ligandcommon bonding modes
Syn-Syn
Syn-Anti
Monoatomic
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Syn-Syn bridging mode
Cu(II) paddlewheel complexes
possessing fluorinated
carboxylate ligands. A. Wein, J.F.
Eichler,*
J. Fluor. Chem. 2009, 130, 197.
5
Monoatomic bridging mode
Bond Lengths (Angstroms)
C6-O1 1.238 (3)
C6-O2 1.271 (3)
C7-O4 1.269 (3)
C7-O3 1.238 (3)
O4-Mn1 2.467 (2)
O2-Mn1 2.313 (2)
Bis(pyridine-2,6-dicarboxylato)
bis[triaquamanganese(II)]
N. Okabe and N. Ova
Acta Cryst. (2000). C56, 1416-1417
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Syn-anti bridging mode
Bond Lengths
(Amstrongs)
Copper(II) complexes derived from 6-(4,5-dihydro-1Himidazol-5-on-2-yl)pyridine-2-carboxylic acid.
P. Drabina et. al. Polyhedron 34, 2012, 31-40
C6-O2: 1.263 (5)
C6-O1: 1.229 (6)
Cu1-O2: 2.004 (3)
Cu1a-O1: 2.269 (3)
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Syn-Anti bridging mode
A Copper(II) Complex
with Single Syn−Anti
Carboxylate Bridges:
S. K. Dey et. al.,
Inorg. Chem., 2003, 42
(13), pp 4029–4035
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1D helical chain complex
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Stephen T. Astley
10
8 June 2012
Non-planar bonding in a dinickel complex:
L2Ni2(H2O)5.H2O
1
torsion angles
Ni1–O2–C1–C2
20.0(5) o
C2
1
Ni2–O3–C1–C2
111.0(4) o
A hydrogen-bonded anti-skew carboxylate bridge
N. Korkmaz, A. G. Gökçe et.al. Inorg. Chem. Commun. 12, 2009, 1204
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skewed nails….
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Anti-skew bonding in L2Ni2(H2O)5.H2O
Bond lengths
(Angstroms)
C2
Ni1–O2 2.051(3)
Ni2–O3 2.221(4),
C1-O2 1.260 (6)
C1-O3 1.252 (7)
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Out-of-plane bonding in a copper complex
A double out-of-plane
carboxylato-bridged
Cu(II) compound with
pyridine-2-carboxylate
B. Żurowska et al.
Polyhedron 26, 2007,
3379
Bond lengths
(Angstroms)
Cu-O (in plane):
1.975 (3)
Cu-O (out of plane):
2.737 (4)
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1D Chain
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IR Spectrum of L2Ni2(H2O)5.H2O
IR (KBr disc)
C=O:asym: 1627, 1531(s)
:sym: 1445 (w), 1384 (m)
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Bridging vs. non-bridging
solid state spectra
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Solution spectra
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Hydrogen Bonding
C2
Hydrogen Bonds
(Angstroms)
O2---H-O5w 2.66
(160o)
O4---H-O3w 2.72
(171o)
O6w---H-O4w 2.64
(152o)
A hydrogen-bonded anti-skew carboxylate bridge
N. Kormaz et. al. Inorg. Chem. Commun. 12, 2009, 1204
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2D-supramolecular structure
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TGA
Ni2L2(H2O)5.H2O
50 – 75 oC
-10% (4H2O)
165 – 195 oC
- 5% (2H2O)
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OH
Hydrogen-bonded antiparallel chains
N
N
N
O
1,2,4-triazole
carboxylate
nanostructures
A.D.Naik et.al
Cryst.Growth
Des. 10 (2010)
1798
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1,2,4-triazole carboxylate as a ligand:
[Cu3(μ3-O)(L)3(H2O)3]BF4.H2O
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Nanoball cavity
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Porous framework material
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Rigid carboxylate ligands for the preparation
of framework materials
Cu(NO3)2
+

3,3’,5,5’- biphenyltetracarboxylic acid
B. Chen et.al.
Angew. Chem. Int. Ed.
2005, 44, 4745 –4749
Pore diameter: 1.01nm
2.5 wt% H2 uptake
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Metal-Organic Frameworks for catalysis
L2(pdtc)Cu3.(H2O)3
A metal-organic
framework for
the catalytic
Henry reaction.
L.-Xu Shi, C.-D. Wu
Chem Commun.
2011, 47, 2928-2930
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Syn-anti bonding mode
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Conclusions
• The carboxylate group is a highly versatile
ligand.
• It can adopt a variety of bonding modes
for the preparation of novel structures.
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Acknowledgements
• Ege Ü.: N. Korkmaz
• DEÜ.: A. G. Gökçe
M. Aygün
• 19 Mayis Ü.: O. Büyükgüngör
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Elemental Analysis
Calculated (%)
Found (%)
C
48,75
48.57
N
7,58
6.30
H
4,77
5.00
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30 – 100
oC
-4%
(1.5 H2O)
250 –
290 oC
-28%
(L)
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IR Spectrum of L2Ni2(H2O)5.H2O
(R = 2-butyl)
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IR spectrum of a related non-bridging complex
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Supramolecular structure
C2
A hydrogen-bonded anti-skew carboxylate bridge
N. Kormaz et. al. Inorg. Chem. Commun. 12, 2009, 1204
39
Stephen T. Astley
Carboxylate-containing ligands
for the preparation of novel
dinuclear complexes,
supramolecular structures and
metal-organic frameworks.
40
Acknowledgements
•
•
Neslihan Korkmaz
Prof.Dr. Demet Koyuncu
•
•
•
D.E.Ü
Yrd.Doç.Dr. Muhittin Aygün
Yrd.Doç.Dr. Aytaç Gökçe
•
•
•
•
Diploma Öğrenciler
M. Zeliha Yiğit
E. Aslı Koç
Selda Bakal
•
•
•
TGA
Erhan Öztürk
Dr. Yeliz Yıldırım
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Carboxylate-containing
ligands for the preparation of
novel dinuclear complexes,
supramolecular structures and
metal-organic frameworks.
42