PDF /NMRPz7 Yf[T/ YbWT/ - 名古屋大学

/ / NMR P Pz z7 7 Y Yf f[ [T T/ /_ _Y Yb bW WT T/ /

1 / NMR z

<R/@c96UgdNMRS

" K, 4L , " M& FQA*xG" # H ISBN: 9784782705681

(/c@Nbgh)0 '%(Z:%c,)

?!'%(¹³C/j8)

C?!'%

(;3eE(Y^¹³C/j8) R’ = I ( I+ 1)

( + 1) 2

1 2

1 ×

ν_13C ν₀

× α_13C α₀

3

R’ = I ( I+ 1) ( + 1) 21

21 ×

ν_13C ν₀ ³ S = I(I+1)ν₀³N I : /mrw

ν₀: O5+

N : /mrw:%

D$ (line width factor) LW= (2I + 3)Q²

I²(2I – 1)

I : /mrw

Q : /1uytwq

gW>XihI=1/2c/

2H (I = 1, 0.015%), ⁷Li (I = 3/2, 92.6%)

11B (I = 3/2, 81.2%), ¹⁴N (I = 1, 99.6%)

17O (I = 5/2, 0.037%)

15N (0.37%), ¹⁹F (100%), ²⁹Si (4.7%), ³¹P (100%)

77Se (7.58%), ¹¹¹Cd (12.75%), ¹¹⁹Sn (8.58%)

125Te (6.99%), ¹⁹⁵Pt (33.8%), ²⁰⁷Pb (22.6%) gW>XihI=1/2c/

c/_ckosvwlVgW>Xih/

103Rh (I = –1/2, 100%)

107Ag (I = –1/2, 51.82%), ¹⁰⁹Ag (I = –1/2, 48.18%)

/mrwf'%Q\i]ic/c8=Ia`cpynV+)J

-2.B 8 (2020/5/12)

NMR + +Y Y8 8G G9 9G GA A A A * * > > N NT TP P

2

*B5>@C;=-F

(AJSVLXΔE = hν>7F>

ν= γ·B₀ 2π

*A)- Zhigh frequency

*A- Z low frequency 'B)AI¹H@ 6=

I-H-H$7F4>1- (=¹⁹FABOUXRWMI¹H@7)

@!.KXPOUXRWMB 4A*I%7F

http://www.chem.wisc.edu/areas/reich/nmr/notes-7-multi.pdf

8G9GA@03F*(¹HI100 MHz>6:>2)

NTPB5>@?F

1

H ~ 15 ppm

13

C ~ 200 ppm

11

B ~ 210 ppm

31

P ~ 450 ppm

77

Se ~ 3000 ppm

195

Pt ~ 6700 ppm

59

Co ~ 18000 ppm

NTP A-B I/?1D

NMQVI#<3F"1,F (E&6@7F4>)

3

NMR & &D D 2 H NMR 7 7= =4 48 8@ @

2

H, 7;B I = 1, 0.015%, "' γ = 4.1066

?C>B8 = 2.8 + 10

^–3

, !$ = 1.45 + 10

^–6

D)*#-1.8/7=48@

J. Mol. Cat. B: Enzymatic 2011, 73,17.

1H NMR spectrum (C₆D₆)

2H NMR spectrum (C₆D₆)

5<80 Si(CD

3

)

4

= 0

Chem. Commun. 2002,66.

Dstyrene-d₈/MeReO₃2,.

% 6:9A35(

NMR * *K K 7 Li, 6 Li NMR : :C C8 8> >F F

4

7

Li, :@I I = 3/2, 92.6%, #+ γ = 10.396

EJDI> = –4 . 10

^–2

, "& = 1.54 . 10

³

9A>3 LiCl/D

2

O = 0

$ 3% –10~5 ppm

J. Am. Chem. Soc. 2007, 129, 3492.

7Li!KMe₃Si7;=GI2'BH>I6 RI(rapid injection)NMR0,-E?<J

6

Li, :@I I = 1, 7.4%, #+ γ = 3.937 EJDI> = –8 . 10

^–4

, "& = 3.58

6Li!K(Ph⁶Li)₂1(Ph⁶Li)₄2 (6Et₂O2⁶Li/54

13C NMR:C8>F0)

J. Am. Chem. Soc. 1998, 120, 7201.

Prof. Hans J. Reich@U Wisconsin

NMR 2 2X X 11 B NMR F FM MC CI IS S

5

11

B, FJT I = 3/2, &" 80.42%, ,#4" γ = 8.5847 PUOTI = 4.1 8 10

^–2

, +0 = 7.52 8 10

²

EKI%> BF

₃

·OEt

₂

= 0 ->. –120~90 ppm

X BBr

3

: 38.5 ppm, BBr

3

·pyridine: –7.1 ppm

=;=BHLRTD>V6YW6

http://u-of-o-nmr-facility.blogspot.jp/2008/04/11-b-cosy.html http://u-of-o-nmr-facility.blogspot.jp/2008/04/1-h-11-b-hmqc.html

(!<)=

¹¹

B @?' NA/CQFGU:>

¹¹

B NMR 9*

Nat. Chem. 2013, 5, 115.

Pt B

Et₃P Et₃P

B Dur

Dur 3

Science 2010, 328, 345.

Science 2006, 314, 113. Science 2011, 333, 610.

Science 2012, 336, 1420.

Energy Environ. Sci. 2009, 2,706.

¹¹

B NMR :

$/17=

@53

δB17 δB130

δB47 δB 12.5 δB39

NMR & &; ; 15 N NMR 1 15 5/ /2 28 8

6

15

N, 139 I = –1/2, 0.37%, ' γ = –2.716 7:692 = ,+ , % = 2.19 * 10

^–2

042. CH

₃

NO

₂

= 0

".# –600~600 ppm

1H-¹⁵N HSQC

(-;!$)-

Nat. Chem. 2011, 3, 120.

N N N

N N

N

Mo N

N N N

P N

P

N P

P Mo

δN–29.0

(dt, ¹J_NN&²J_PN = 6.1&2.4 Hz, terminal Nα) δN–16.5

(d, ¹J_NN= 6.1 Hz, terminal Nβ) δN8.5

(s, bridging N)

α

β P = PⁱPr2

NMR / /P P 19 F NMR ? ?F F= =B BM M

7

19

N, ?DN I = 1/2, $ 100%, (!0 γ = 25.1815 KOJNB = 75 , ', = 4.73 3 10

³

>EB#: CFCl

₃

= 0 ):* –300~900 ppm

%P EA+GLHO92. 19%PC@I9-&8

F-cytosine <"469;; F-uracil <

http://www.cerij.or.jp/

¹⁹

F NMR P

http://www.toray-research.co.jp/new_bunseki/index.html

−25

−20

−15

−10

−5 0

5 10

Chemical shift (ppm)

-2 -1 0 1 2 3 4 5

Chemical shift (ppm) 5-FC

5-FU

5-FC

A 5-FU

B

Brit. J. Cancer 2004, 89,1796.

NMR 0 0T T 29 Si NMR E EL LB BH HP P

8

)T

²⁹

Si NMR 8<=

Al,Si G@O?H9

29

Si, EJR I = –1/2, $! 4.7%, +"1! γ = –5.3190 NSMRH = 75 , *. = 4.95 4 10

^–1

DKH#: SiMe

₄

= 0 ,:- –200~100 ppm

Science 2004, 305, 1755.

Science 2011, 331, 1306.

δSi90

δSi –52, –50, 300, 308

29T& 7(9

²⁹

Si >;%

)TISF/3856 DQACR9'

Sci. Rep. 2012, 2, 564.

http://www.ube-ind.co.jp/usal/

documents/o224_145.htm

NMR 1 1 31 P NMR ' '+ +% %( (. .

9

31

P, ')/ I = 1/2, 100%, γ = 10.8394 -0,/( = #" , = 1.44 ! 10

²

&*($ 85%H

₃

PO

₄

= 0

$ –400~600 ppm

Fig. 4 ³¹P NMR traces for the time course of transesterification of p-nitrophenyl uridineH-phosphonate4awith EtOH (5 equiv.). Note the immediate consumption ofLP-4ain the first minute of the reaction.

Ar = 4-nitrophenyl

New J. Chem. 2010, 34,854.

PPM

40.0 30.0 20.0 10.0 0.0 -10.0 -20.0

Rh CO H

CO P P

two unidentified doublets δ_P19.2

1J_RhP= 122 Hz

free xantphos δ_P38.8

δ_P෥22.2

δ_P෥17.7

δ_P0.7, J= 148 Hz δP8.1, J= 135 Hz 10

10

7

O Ph₂P PPh2

Ru CO CO

Ph Ph

Ph Ph O

P P Ru

CO CO

Ph Ph

Ph Ph O

P P

(b) 1 + xantphos (1 eq), 120 °C, 15 min, in DMA, under H₂/CO (1/1, 0.1 MPa)

(c) Rh(acac)(CO)2 + xantphos (1 eq) + 1 (2.5 eq), 120 °C, 15 min, in DMA, under H2/CO (1/1, 0.1 MPa)

(d) Rh(acac)(CO)2 + xantphos (1 eq), 120 °C, 15 min, in DMA, under H2/CO (1/1, 0.1 MPa)

(e) Rh(acac)(CO)2 + xantphos (1 eq), 120 °C, 15 min, in DMA, under CO (0.1 MPa)

(f) Rh(acac)(CO)2 + xantphos (1 eq), 80 °C, 15 min, in C6D6, under H2/CO (1/1, 0.1 MPa)

(g) Rh(acac)(CO)2 + xantphos (1 eq), 120 °C, 15 min, in DMA, under Ar (0.1 MPa) (a) 1 + xantphos (1 eq), 80 °C, 15 min, in C6D6, under H2/CO (1/1, 0.1 MPa)

Rh CO O O

P P Rh

CO O O

P

P

11 11

11' Rh

CO O O

P P

12 Rh CO

P P O CO O

31

1

Angew. Chem. Int. Ed. 2010, 49,4488.