Koordinációs kémai
Az NMR alapjai
2009. 03. 11.
The electromagnetic spectrum
Alapelvek
Alapelvek
2,35 T 100 MHz
8,46 T 360 MHz
9,40 400 MHz
11,747 500 MHz
22,316 950 MHz
FT NMR, suprevezető-mágnes
FT NMR
Felbontás
Információ források
Kémiai eltolódás
Kémiai eltolódás
2009.03.11.
Spin-spin csatolás: hetero S=1/2, 100%
Spin-spin csatolás: hetero, S=1/2
Tl(III)- CN-
Spin-spin csatolás: hetero, S=1/2, nem
100%
Spin-spin csatolás:
hetero, kvadrupol I= 9/2
nem 100%
Spin-spin csatolás:
hetero, kvadrupol I=1
100%Relaxáció!
T.I. esete a savas mintával…
Spin-spin csatolás: homo, S=1/2, nem
elsőrendű
Paramágneses minta
Integrál
2D technikák
2D NOESY , COSY
Dinamikus NMR
Időskálák
Jelalak analízis ill. jelszélesedés
Uranyl(VI)-carbonato complexes. Correlation between the kinetics and the binding mode of the ligand.
-500
-100
300
700
1100
1500
0.1 1 10 100 1000 1E4 1E5
10 parameters were fitted from the18 (4T1, 4M(0), 4M(∞) and 6 kobs)
kobs(FREE;MONO) = 109(12) s-1, kobs(FREE;TERM) = 2,6(0,4) s-1,
kobs(TERM;CENT) = 0,08(0,1) s-1, 1/T1(TERM) = 1,2(0,1) s-1, 1/T1(TERM) = 0,2(0,3) s-1 and
5 starting and final intensities
Color-code: yellow (FREE), red (MONO), black (TERM), grey (CENT)
Uranyl(VI)-carbonato com plexes. Correlation betw een the kineticsand the binding m ode of the ligand.
Summary of exchange reactions
(I–VI) in the uranyl(VI) – carbonate
equilibrium system
Uranyl(VI)-carbonato complexes. Correlation between the kineticsand the binding mode of the ligand.
CENT < TERM < MONO
-Water and proton catalysed carbonate exchange of MONO and TERM with FREE
-no exchange with CENT, the exchange between CENT and FREE is connected to the TRIN ⇔ MONO , i.e. the dissociation of the trinuclear complex
Equilibria in the Pt(CN)42− – Tl3+ – CN-– – H2O system
Recently, we have synthesised complexes with direct metal-metal bond:
mPt(CN)42– + Tl3+ + nCN– [Pt mTl(CN)4+n](n–1)–
Four binuclear (m=1, n=1-4), and a trinuclear complex (m=2, n=2) are formed in
aqueous solution.
2009. 03.25? Inkább majd az alkalmazásoknál…
Equilibria in the Pt(CN)42− – Tl3+ – CN-– – H2O system
Equilibria in the Pt(CN)42− – Tl3+ – CN-– – H2O system
Equilibria in the Pt(CN)42− – Tl3+ – CN-– – H2O system
Equilibria in the Pt(CN)42− – Tl3+ – CN-– – H2O system
(p p m )1 2 0 01 2 5 01 3 0 01 3 5 01 4 0 01 4 5 01 5 0 0
1 J T l– P t = 5 7 ,0 2 k H z
2 J T l– C ( A ) = 9 ,7 4 k H z 1 J T l– C (B ) = 2 ,4 5 k H z
2 J T l– C (C ) = 0 ,4 5 k H z
Structure of [(ACN)(CCN)4Pt-Tl(BCN)]–complex
EXAFS-structure
Figure 1a. 230.8 MHz 205Tl NMR spectrum of the [(ACN)(CCN)4Pt-Tl(BCN)]–-complex showing the spin-spin coupling schemes. The sample consists of 50 mM Tl3+, 50 mM Pt(13CN)4
2– and 150 mM Na13CN, pH = 1.04. b. Stuctural model based on Pt and Tl LIII EXAFS data.