P NMR Spectroscopy - An Experimentalists View On A Powerful Tool"

31P NMR spectroscopy
an experimentalists view on a powerful tool
Lecture for B.Sc. and M.Sc. students
Prof. R. Streubel
Institut fr Anorganische Chemie, Bonn, Germany
http://anorganik.chemie.uni-bonn.de/akstreubel/Streubel_Home.html
E-mail: [email protected]
Outline
1. Fundamental aspects
2. Phosphanes (phosphines)
3. Phosphane oxides and phosphate esters
4. Phosphane oxides vs. phosphoranes and phosphates
5. MLn and BH3 complexes
6. Phosphorus compounds in low coordination
7. Coupling of phosphorus to main group elements (H, C, F)
8. Coupling of phosphorus to transition metals (W)
9. Chemical shift range for phosphorus compounds
1. Fundamental aspects a short introduction
1
1. Fundamental aspects a comparison to hydrogen
Phosphorus contains just one isotope (31P: natural abundance 100%)

31P : 1H => 10.841 : 26.7519 = 40.480737 [MHz] (if 1H = 100 MHz)
Relative receptivity of 31P: 0.0665 => less sensitive than 1H (1.00) !
Standard for 31P NMR measurements: H3PO4 (concentration 85%)

Resonances are given in [ppm] relative to the standard, chemical shift
=> sign convention: + (= resonance at lower field; lowfield-shifted)
Chemical shift () is determined by

electronegativity ()
- -electron overlap (n)
bond angle ()
differences occur upon change in the bonding environment
(J. R. van Wazer):
2
Structural features (I): RmPHm-n

(33-P, PIII, pyramidal, between p3 and sp3 hybridisation)
Strong downfield-shift upon increasing degree of C substitution at P
3
Steric effects !?
4
Examples of phosphanes and their chloro derivatives of RmPClm-n

(33-P, PIII, pyramidal)
Strong downfield-shift upon increasing degree of Cl substitution at P

Electronegative elements such as chlorine lead to a deshielded P center
Introducing an increment system based on:

1) Electronegativity of directly bound atoms
2) Electronegativity of atoms bonded to the , , etc. atom
5
2. Estimating chemical shifts: increments systems
6
2. Phosphanes and chloro derivatives
Examples of phosphanes and their chloro derivatives of RmPClm-n

(33-P, PIII, pyramidal)
values: 1) PMe2Cl vs PMeCl2:: 98.8

2) P(t-Bu2)Cl vs P(t-Bu)Cl2: 53.3 (!?)
Attention:
In addition, the increment system has to take
steric and electronic effects into account !
7
3. Phosphane oxides vs. phosphate esters
Examples of phosphane oxides and their alkoxy derivatives RmP(O)ORm-n

(45-P, PV, tetrahedral; ~ sp3 hybridisation with some d-orbital
contribution)
Upfield-shift upon increasing degree of OR/OAr substitution at P
8
3. Phosphane oxides vs. sulfides and imines
Examples of phosphane oxides and their SR and NR derivatives RmP(E)

(45-P, PV, tetrahedral; ~ sp3 hybridisation with some d-orbital contrib
Note: OR and NR derivatives resonate upfield from respective SR deriv.

=> SR show weaker -backbonding
9
4. Phosphane oxides vs. phosphoranes vs. phosphates
1) 45-P, PV, tetrahedral; 2) 55-P, PV, trigonal bipyramidal;

3) 65-P, PV, octahedral; ~ sp3 hybridisation with some d-orbital contribution
10
5. MLn complexes of phosphanes and derivatives (I)
Coordination chemical shift values (): Cr > Mo > W (~ 20-30 ppm)

Why is their a shielding or deshielding effect in complexes?
Why are Cr complexes more deshielding than Mo or W complexes ?
11
5. MLn complexes of phosphanes and derivatives (II)
12
5. BH3 complexes of phosphanes and derivatives
Borane complexation has a deshielding effect unless -atoms can

deliever electron density !
13
Phosphaalkynes,
13-P, PIII, linear
sp hybridisation
14
Diphosphenes, 23-P, PIII, bent, ~ sp2 hybridisation
15
Phosphaalkenes, 23-P, PIII, bent, ~ sp2 hybridisation
15
6. Low-coordinated phosphorus compounds
Phosphenium salts, 22-P, PIII, planar, ~ sp2 hybridisation
In phosphenium compounds substituents have huge effects on the

chemical shift !?
Phosphenium compounds are charged species and therefore the

chemical shift is strongly dependend of c, T and solvent polarity !
16
7. Coupling of P to main group elements (H,C,F): 1H
General aspects of couplings of

P to H => nJ(P,H):
1J(P,H) is positiv;
=> the sign is then alternating (f(n))
The magnitude of nJ(P,H):

1J(P,H) > 3J(P,H) > 2J(P,H) > 4J(P,H)
1J(P,H)coupling constants:
Na[PH2] < CH2CH2PH < PH3 < PH4+< PH2F3
139.0 < 158.3 < 188.2 < 547 < 841 Hz
The magnitude of 2J(P,H)

in cyclic systems:
depends on the angle
17
7. Coupling of P to main group elements (H,C,F): 13C
General aspects of couplings of P to C => nJ(P,C)

1J(P,C) is negativ => the sign is depending on and increases with
increasing electronegativity, coordination number and bond angle sum
Within a series of
alkyl phosphanes
the magnitude of nJ(P,C)
1J(P,C) > 3J(P,C) > 2J(P,C) >
4J(P,C)
The magnitude of 2J(P,C)

in cyclic systems:
depends also on the angle
(Karplus curve)
18
7. Coupling of P to main group elements (H,C,F): 19F
General aspects of couplings of P to F => nJ(P,F)
1J(P,F) is negativ => the sign is depending on and increases with

increasing electronegativity and coordination number
Selected examples of 1J(P,F) coupling constants:

PF3 < P(O)F3 < PF5 < PF6- < H2P(NH2)F2
-1441 < -1080 < -938 < -706 < -598 Hz
Within a class of phosphorus compounds the magnitude of nJ(P,F):

1J(P,E) > 3J(P,E) > 2J(P,E) > 4J(P,E)
The magnitude of 1J(P,F) depends very much on the

s-character of the bond: sp > sp2 > sp3 > dsp2 > dsp3 > d2sp3
19
1J(W,P) coupling constant magnitudes [Hz]
In the case of W(CO)5PR3 complexes:

Strong correlation of the 1J(W,P) coupling constants from the
EN values (Pauling) of directly to P bonded atoms !
20
1J(W,P) coupling constant magnitudes [Hz]
21
9. Chemical shift range for phosphorus compounds
22
6. Low-coordinated phosphorus compounds

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31P NMR spectroscopy

an experimentalists view on a powerful tool

Lecture for B.Sc. and M.Sc. students

Institut fr Anorganische Chemie, Bonn, Germany

Phosphorus contains just one isotope (31P: natural abundance 100%)

Relative receptivity of 31P: 0.0665 => less sensitive than 1H (1.00) !

Standard for 31P NMR measurements: H3PO4 (concentration 85%)

Chemical shift () is determined by

Structural features (I): RmPHm-n

Strong downfield-shift upon increasing degree of C substitution at P

Examples of phosphanes and their chloro derivatives of RmPClm-n

Strong downfield-shift upon increasing degree of Cl substitution at P

Introducing an increment system based on:

Examples of phosphanes and their chloro derivatives of RmPClm-n

values: 1) PMe2Cl vs PMeCl2:: 98.8

Examples of phosphane oxides and their alkoxy derivatives RmP(O)ORm-n

Upfield-shift upon increasing degree of OR/OAr substitution at P

Examples of phosphane oxides and their SR and NR derivatives RmP(E)

Note: OR and NR derivatives resonate upfield from respective SR deriv.

1) 45-P, PV, tetrahedral; 2) 55-P, PV, trigonal bipyramidal;

Coordination chemical shift values (): Cr > Mo > W (~ 20-30 ppm)

Borane complexation has a deshielding effect unless -atoms can

Diphosphenes, 23-P, PIII, bent, ~ sp2 hybridisation

Phosphaalkenes, 23-P, PIII, bent, ~ sp2 hybridisation

Phosphenium salts, 22-P, PIII, planar, ~ sp2 hybridisation

In phosphenium compounds substituents have huge effects on the

Phosphenium compounds are charged species and therefore the

General aspects of couplings of

The magnitude of nJ(P,H):

The magnitude of 2J(P,H)

General aspects of couplings of P to C => nJ(P,C)

The magnitude of 2J(P,C)

General aspects of couplings of P to F => nJ(P,F)

1J(P,F) is negativ => the sign is depending on and increases with

Selected examples of 1J(P,F) coupling constants:

Within a class of phosphorus compounds the magnitude of nJ(P,F):

The magnitude of 1J(P,F) depends very much on the

In the case of W(CO)5PR3 complexes:

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