az nmr alapjai - unideb.hu · alapelvek 2,35 t 100 mhz 8,46 t 360 mhz 9,40 400 mhz 11,747 500 mhz...

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.