supporting information - wiley-vch.de file1 steric and polarity controlled reaction of tbuli with...

Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008

1

Steric and polarity controlled reaction of tBuLi with -P=CH-NR-heterocycles:

Novel heterocyclic P- and P,O-ligands and first tests in transition metal catalysis

Bhaskar Reddy Aluri,[a] Markus K. Kindermann,[a] Peter G. Jones,[b] Joachim W. Heinicke*[a]

[a] Institut für Chemie und Biochemie, Ernst-Moritz-Arndt-Universität Greifswald, D-17487 Greifswald, Germany,

[b] Institut für Anorganische und Analytische Chemie der Technischen Universität Braunschweig, 38023

Braunschweig, Germany

2

1. Procedures with supplementary NMR data.

2. 13C NMR Spectra

of metalation products (formed in THF, in THF/KOtBu, pentane)

of separated compounds (6b, 7b, 7c, 11b,12b)

3. Tables of crystal structure data

3

1. Procedures with supplementary NMR data.

Lithiation of 1b in THF.

tBuLi (0.23 mL, 1.5 M pentane solution, 0.34 mol) was added dropwise to 1b (64 mg, 0.31 mmol)

in THF (2 mL) at - 60°C. This mixture was warmed up slowly to - 40°C and stirred for 4h. The

solvent was removed in vacuum to give orange-yellow crystalline residue. 31P NMR spectra show

sharp signals for 2b (δ=104.3) and 4b (δ= - 9.1) and two small but broad signals in the phosphine

and phosphide reagion (δ=5.3, - 41.6), tentatively assigned to 3b and 5b; 1H integration of tBu

signals (of neopentyl group) ca. 40:28:17:15 (for equal intensity order).

2b: 1H NMR ([D8]THF): d=0.93 (s; CMe3), 6.73 (tm, 3J=7-8 Hz, 1H; H-5), 6.92 (td, 3J=7-8, 4J=1.6 Hz, 1H; H-6), 7.38 (d, 3J=8.2 Hz, 1H; H-7), 7.62 (dt, 3J=7.6, 4J˜ 3J(P,H)˜ 1.5 Hz, 1H; H-4); 13C{1H} (DEPT) NMR ([D8]THF): δ=29.66 (CMe3), 35.47 (CMe3), 65.10 (d, 3J=7.3 Hz; NCH2),

112.75 (d, 3J=1.3 Hz; CH-7), 116.15 (d, 3J=6.4 Hz; CH-5), 118.47 (CH-6), 126.39 (d, 2J=12.2 Hz,

CH-4), 149.44 (d, 2J=8.9 Hz; Cq-7a), 150.03 (d, 1J=60.5 Hz; Cq-3a), 253.11 (d, 1J=109.9 Hz; CLi-2).

These NMR data except of the different N-substituent are closely similar to those of pure 2a,

characterized unambiguously by X-ray crystallography as µ-CLi bridging dimer with two THF per

lithium.[6]

4b: 1H NMR ([D8]THF): d=0.89 (d, 3J(P,H)=11.9 Hz; PCMe3), 0. 97 (s; CMe3), 2.70 (d, 2J=14.6 Hz,

1H; NCHa), 3.15 (d, 2J=14.5 Hz, 1H; NCHb), 3.32 (dd, 2J(P,H)=22.5, 2J=13.2 Hz; PCHtrans to tBuN),

3.76 (dd, 2J=13, 2J(P,H)=3.6 Hz, 1H; PCHcisN), 6.47 (d br, 3J=8.2 Hz; H-7), 6.54 (ddd, 3J=7.3, 4J(P,H)=2.5, 4J=0.8 Hz, 1H; H-5), 7.06 (tm, 3J=7-8, 4J=1.4 Hz, 1H; H-6), 7.22 (ddd, 3J=7.1, 3J(P,H)=5.6, 4J=1.4 Hz, 1H; H-4); 13C{1H} (DEPT) NMR ([D8]THF): d=26.80 (d, 2J=14.9 Hz;

PCMe3), 28.63 (s; CMe3), 30.40 (d, 1J=19.7 Hz; PCMe3), 35.04 (s; CMe3), 53.54 (d, 1J=20.8 Hz,

PCH2N), 65.42 (s; NCH2), 108.89 (s; CH-7), 117.19 (d, 4J=7.8 Hz; CH-6), 124.14 (d, 1J=11.7 Hz;

Cq-3a), 130.87 (s; CH-5), 132.23 (d, 2J=22.4 Hz; CH-4), 157.75 (s; Cq-7a). The NMR data are in

good accordance with those of independently synthesized 4b recorded in C6D6 (see below).

Adducts, tentatively assigned to as 3b and 5b by 1H NMR: 0.79, 0.83, 0.96, 1.07 (s; tBu), 2.58 (d, 2JAB=14.7 Hz; NCH), 3.05 (d, 2JAB=15.0 Hz; NCH), 3.23 (d, 2JAB=14.6 Hz; NCH), 3.48 (d br,

J=14.0 Hz; NCH), 4.00 (td, J˜ 8, J=2.4 Hz; CH), 4.13 (s br; CH), 4.30-4.42 (m; CH), 5.86 (d, 3J=7.3 Hz; H-7), 6.05 (t br, 3J=7.2, 4J + 4J(P,H)=2.4 Hz; H-5), 6.19 (td, 3J=7.4, 4J=1.4 Hz; H-6), 6.26

(d, 3J=8.2 Hz; H-7), 6.34 (td, 3J=7.1, 4J=2.2 Hz; H-5), ca. 6.42 (unresolved ddd; H-4), 6.61 (t br, 3J=7-8 Hz; H-6), 6.66 (ddd, 3J=7.0, 3J(P,H)=4.0, 4J=1.2 Hz; H-4).

5

2. 13C NMR Spectra.

Reaction of tBuLi with 1b in THF (- 60 °C to 20 °C): 13C NMR Spectrum (aryl region) of crude products.

6

Reaction of tBuLi with 1b in THF (- 60 °C to 20 °C): 13C NMR Spectrum (alkyl region) of crude products.

7

Reaction of tBuLi with 1b in THF (- 60 °C to 20 °C): 31P NMR Spectrum of crude products (2b and 4b, contaminated by a trace of starting material 1b

and impurities I1 (phosphine region) and I2 (phosphide region).

9

Reaction of 1b with KOtBu and tBuLi in THF (- 78 °C to 20 °C) followed by reaction with ClSiMe3 and MeOH: 13C NMR Spectrum of 8b (δ 126.7) /

1b (δ 71.3) mixture (62:38 mol% by 1H NMR integration).

11

Reaction of 1b with KOtBu and tBuLi in THF (- 78 °C to 20 °C) followed by reaction with ClSiMe3 and MeOH: 13C NMR Spectrum (aryl region) of

the crude 8b (δ 126.7) / 1b (δ 71.3) mixture (62:38 mol% by 1H NMR integration).

12

Reaction of 1b with KOtBu and tBuLi in THF (- 78 °C to 20 °C) followed by reaction with ClSiMe3 and MeOH: 31P NMR Spectrum (aryl region) of

the crude 8b (δ 126.7) / 1b (δ 71.3) mixture (62:38 mol% by 1H NMR integration).

14

Reaction of 1b with tBuLi in pentane (- 30 to 20 °C, 20h), followed by methanolysis. 13C NMR- Spectrum (range δ 0-37 ppm) of the product (4b, 10b,

ca. 75:25 mol% by 1H NMR integration).

15

Reaction of 1b with tBuLi in pentane (- 30 to 20 °C, 20h), followed by methanolysis. 13C NMR- Spectrum (range δ 37-75 ppm) of the product (4b,

10b, ca. 75:25 mol% by 1H NMR integration).

16



18



20

13C NMR Spectrum of 6b (small impurity of 1b).

21

13C NMR Spectrum of 7b.

23

13C NMR Spectrum (alkyl region) of 7c.

24

13C NMR Spectrum (aryl region) of 7c.

26

13C NMR Spectrum of 11b (overview).

28

13C NMR Spectrum of 11b (alkyl region).

30

13C NMR Spectrum of 11b (alkyl region 2).

31

13C NMR Spectrum of 11b (olefin, CH-7 region).

33

2. Tables of crystal structure data

Table 1. Crystal data and structure refinement of 6b.

Identification code gwait

Empirical formula C13H16NO2P

Formula weight 249.24

Temperature 133(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P21/c

Unit cell dimensions a = 5.8021(4) Å α= 90°

b = 13.0437(8) Å β= 93.6140(10)°

c = 16.5657(10) Å γ = 90°

Volume 1251.21(14) Å3

Z 4

Density (calculated) 1.323 Mg/m3

Absorption coefficient 0.209 mm-1

F(000) 528

Crystal size 0.25 x 0.20 x 0.20 mm3

Theta range for data collection 1.99 to 30.51°

Index ranges -8<=h<=8, -18<=k<=18, -23<=l<=23

Reflections collected 19962

Independent reflections 3818 [R(int) = 0.0509]

Completeness to theta = 30.00° 100.0 %

Absorption correction None

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 3818 / 0 / 158

Goodness-of-fit on F2 1.023

Final R indices [I>2sigma(I)] R1 = 0.0366, wR2 = 0.0912

R indices (all data) R1 = 0.0600, wR2 = 0.1021

Largest diff. peak and hole 0.451 and -0.182 e.Å-3

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Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters

(Å2x 103) of 6b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

___________________________________________________________________________

x y z U(eq)

___________________________________________________________________________

N(1) 4681.0(17) 6657.1(7) 1692.3(6) 17.0(2)

C(2) 4460(2) 5719.1(9) 1310.3(7) 17.3(2)

P(3) 6641.9(6) 4851.0(3) 1548.8(2) 20.7(1)

C(3A) 7936(2) 5774.1(9) 2208.4(7) 19.0(2)

C(4) 9999(2) 5696.1(11) 2710.1(8) 24.2(3)

C(5) 10640(2) 6483.2(11) 3222.8(8) 28.0(3)

C(6) 9245(2) 7363.1(11) 3264.1(8) 27.7(3)

C(7) 7251(2) 7478.5(10) 2773.8(8) 23.2(3)

C(7A) 6618(2) 6681.7(9) 2228.6(7) 18.3(2)

C(8) 3157(2) 7548.8(9) 1533.7(7) 17.4(2)

C(9) 3937(2) 8298.2(9) 873.0(7) 18.2(2)

C(10) 5716(2) 9062.5(10) 1239.0(8) 26.3(3)

C(11) 1774(2) 8889.6(11) 567.0(9) 28.7(3)

C(12) 4985(2) 7747.1(10) 167.5(8) 25.1(3)

C(13) 2483(2) 5453.6(10) 740.7(7) 18.9(2)

O(1) 1015.9(16) 6045.5(7) 453.9(6) 24.2(2)

O(2) 2472.3(17) 4459.6(7) 572.2(6) 27.8(2)

___________________________________________________________________________

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Table 3. Bond lengths [Å] and angles [°] of 6b.

N(1)-C(2) 1.3798(15)

N(1)-C(7A) 1.3884(15)

N(1)-C(8) 1.4746(14)

C(2)-C(13) 1.4798(17)

C(2)-P(3) 1.7255(12)

P(3)-C(3A) 1.7619(13)

C(3A)-C(7A) 1.4107(17)

C(3A)-C(4) 1.4174(17)

C(4)-C(5) 1.3688(19)

C(5)-C(6) 1.409(2)

C(6)-C(7) 1.3793(18)

C(7)-C(7A) 1.4102(17)

C(8)-C(9) 1.5559(16)

C(9)-C(12) 1.5304(17)

C(9)-C(11) 1.5320(18)

C(9)-C(10) 1.5323(17)

C(13)-O(1) 1.2229(15)

C(13)-O(2) 1.3261(15)

C(2)-N(1)-C(7A) 111.22(10)

C(2)-N(1)-C(8) 125.48(10)

C(7A)-N(1)-C(8) 123.23(10)

N(1)-C(2)-C(13) 123.08(10)

N(1)-C(2)-P(3) 115.55(9)

C(13)-C(2)-P(3) 121.36(9)

C(2)-P(3)-C(3A) 88.35(6)

C(7A)-C(3A)-C(4) 119.03(12)

C(7A)-C(3A)-P(3) 112.20(9)

C(4)-C(3A)-P(3) 128.73(10)

C(5)-C(4)-C(3A) 119.75(12)

C(4)-C(5)-C(6) 120.45(12)

C(7)-C(6)-C(5) 121.58(13)

C(6)-C(7)-C(7A) 118.13(12)

N(1)-C(7A)-C(7) 126.46(11)

N(1)-C(7A)-C(3A) 112.55(10)

C(7)-C(7A)-C(3A) 120.94(11)

N(1)-C(8)-C(9) 115.03(9)

C(12)-C(9)-C(11) 109.91(11)

C(12)-C(9)-C(10) 108.52(10)

C(11)-C(9)-C(10) 108.70(11)

C(12)-C(9)-C(8) 112.91(10)

C(11)-C(9)-C(8) 106.29(10)

C(10)-C(9)-C(8) 110.43(10)

O(1)-C(13)-O(2) 122.78(11)

O(1)-C(13)-C(2) 126.35(11)

O(2)-C(13)-C(2) 110.87(11)

_____________________________

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Table 4. Torsion angles [°]of 6b.

________________________________________________________________

C(7A)-N(1)-C(2)-C(13) 176.47(11)

C(8)-N(1)-C(2)-C(13) -6.51(18)

C(7A)-N(1)-C(2)-P(3) -2.72(13)

C(8)-N(1)-C(2)-P(3) 174.29(9)

N(1)-C(2)-P(3)-C(3A) 0.71(10)

C(13)-C(2)-P(3)-C(3A) -178.50(10)

C(2)-P(3)-C(3A)-C(7A) 1.47(10)

C(2)-P(3)-C(3A)-C(4) 179.45(12)

C(7A)-C(3A)-C(4)-C(5) 2.15(19)

P(3)-C(3A)-C(4)-C(5) -175.71(10)

C(3A)-C(4)-C(5)-C(6) 1.0(2)

C(4)-C(5)-C(6)-C(7) -2.4(2)

C(5)-C(6)-C(7)-C(7A) 0.6(2)

C(2)-N(1)-C(7A)-C(7) -173.61(12)

C(8)-N(1)-C(7A)-C(7) 9.30(18)

C(2)-N(1)-C(7A)-C(3A) 3.78(14)

C(8)-N(1)-C(7A)-C(3A) -173.31(10)

C(6)-C(7)-C(7A)-N(1) 179.75(12)

C(6)-C(7)-C(7A)-C(3A) 2.56(18)

C(4)-C(3A)-C(7A)-N(1) 178.50(11)

P(3)-C(3A)-C(7A)-N(1) -3.31(13)

C(4)-C(3A)-C(7A)-C(7) -3.95(18)

P(3)-C(3A)-C(7A)-C(7) 174.25(10)

C(2)-N(1)-C(8)-C(9) -90.91(13)

C(7A)-N(1)-C(8)-C(9) 85.76(13)

N(1)-C(8)-C(9)-C(12) 37.53(14)

N(1)-C(8)-C(9)-C(11) 158.11(10)

N(1)-C(8)-C(9)-C(10) -84.16(12)

N(1)-C(2)-C(13)-O(1) 10.8(2)

P(3)-C(2)-C(13)-O(1) -170.06(10)

N(1)-C(2)-C(13)-O(2) -168.84(11)

P(3)-C(2)-C(13)-O(2) 10.30(15)

38

________________________________________________________________

39

Table 5. Hydrogen bonds [Å and °] in 6b.

___________________________________________________________________________

D-H...A d(D-H) d(H...A) d(D...A) <(DHA)

___________________________________________________________________________

O(2)-H(02)...O(1)#1 0.88(2) 1.76(2) 2.6430(13) 174.9(18)

___________________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 -x,-y+1,-z

41


Identification code groope

Empirical formula C32H50N2P2





Space group P21/n


b = 13.8134(3) Å β= 101.177(2)°

c = 16.9844(3) Å γ = 90°

Volume 3102.89(11) Å3

Z 4



F(000) 1144



Index ranges -18<=h<=18, -19<=k<=19, -23<=l<=23




Absorption correction Semi-empirical from equivalents

Max. and min. transmission 1.00000 and 0.98283







42

Table 7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters of

11b (Å2x 103). U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

___________________________________________________________________________

x y z U(eq)

___________________________________________________________________________

N(1) 6291.7(7) 5223.8(7) 2179.5(5) 14.4(2)

C(2) 5825.8(9) 4380.5(8) 1725.4(6) 13.2(2)

P(3) 5736.4(2) 3417.9(2) 2498.3(2) 14.5(1)

C(3A) 6674.7(9) 4071.5(8) 3212.8(7) 15.0(2)

C(4) 7221.8(9) 3741.3(9) 3943.7(7) 19.5(2)

C(5) 7945.0(10) 4334.3(10) 4407.0(7) 22.8(3)

C(6) 8121.3(10) 5249.3(10) 4123.6(7) 22.1(3)

C(7) 7591.2(9) 5594.5(9) 3393.7(7) 18.8(2)

C(7A) 6860.1(9) 5001.0(8) 2929.9(6) 14.4(2)

C(8) 6137.3(9) 6213.1(8) 1881.9(7) 15.4(2)

C(9) 5262.6(9) 6793.8(8) 2120.9(7) 14.5(2)

C(10) 4238.4(9) 6355.5(9) 1740.8(7) 18.4(2)

C(11) 5343.5(9) 6828.1(9) 3032.0(7) 18.0(2)

C(12) 5331.5(10) 7818.9(9) 1787.8(7) 20.3(3)

C(13) 6420.3(8) 3980.5(8) 1091.0(6) 13.1(2)

C(14) 5801.4(10) 3147.1(9) 642.1(7) 19.8(3)

C(15) 7464.4(9) 3615.6(9) 1502.3(7) 17.6(2)

C(16) 6567.6(9) 4757.9(9) 481.4(7) 17.6(2)

N(1') 3665.7(7) 2163.6(7) 3085.4(5) 13.8(2)

C(2') 4123.4(8) 2981.4(8) 3579.1(6) 12.5(2)

P(3') 4326.7(2) 3963.9(2) 2857.5(2) 13.5(1)

C(3A') 3455.4(9) 3345.0(8) 2068.0(6) 14.0(2)

C(4') 3052.8(9) 3679.4(10) 1299.2(7) 19.4(2)

C(5') 2417.9(10) 3088.3(10) 760.3(7) 23.4(3)

C(6') 2176.6(10) 2175.4(10) 999.1(7) 22.3(3)

C(7') 2564.6(9) 1824.2(9) 1765.6(7) 18.5(2)

C(7A') 3217.2(8) 2410.7(8) 2305.4(6) 13.8(2)

C(8') 3773.1(9) 1161.5(8) 3360.8(7) 15.3(2)

C(9') 4696.8(9) 584.5(9) 3202.1(7) 17.4(2)

43

C(10') 4571.9(11) -448.7(9) 3495.6(8) 26.5(3)

C(11') 4752.0(10) 569.0(10) 2310.6(8) 22.6(3)

C(12') 5679.0(10) 1009.7(10) 3681.0(9) 26.6(3)

C(13') 3480.8(9) 3388.0(8) 4178.2(6) 13.4(2)

C(14') 3233.3(10) 2598.9(9) 4741.7(7) 19.8(2)

C(15') 2490.0(9) 3834.7(9) 3734.7(7) 18.2(2)

C(16') 4115.2(10) 4159.0(9) 4691.6(7) 20.6(3)

___________________________________________________________________________

44


__________________________________________________________________________

N(1)-C(7A) 1.3885(14)

N(1)-C(8) 1.4580(14)

N(1)-C(2) 1.4691(14)

C(2)-C(13) 1.5631(15)

C(2)-P(3) 1.8886(11)

P(3)-C(3A) 1.8146(12)

P(3)-P(3') 2.2367(4)

C(3A)-C(4) 1.3923(16)

C(3A)-C(7A) 1.4100(16)

C(4)-C(5) 1.3941(18)

C(5)-C(6) 1.3892(19)

C(6)-C(7) 1.3899(17)

C(7)-C(7A) 1.4011(16)

C(8)-C(9) 1.5442(16)

C(9)-C(11) 1.5307(16)

C(9)-C(10) 1.5311(16)

C(9)-C(12) 1.5343(16)

C(13)-C(15) 1.5304(16)

C(13)-C(16) 1.5311(16)

C(13)-C(14) 1.5350(16)

N(1')-C(7A') 1.3880(14)

N(1')-C(8') 1.4594(14)

N(1')-C(2') 1.4694(14)

C(2')-C(13') 1.5631(15)

C(2')-P(3') 1.8838(11)

P(3')-C(3A') 1.8160(12)

C(3A')-C(4') 1.3922(15)

C(3A')-C(7A') 1.4077(16)

C(4')-C(5') 1.3905(18)

C(5')-C(6') 1.3826(19)

C(6')-C(7') 1.3927(17)

C(7')-C(7A') 1.3994(16)

C(8')-C(9') 1.5454(16)

C(9')-C(12') 1.5305(17)

C(9')-C(11') 1.5305(17)

C(9')-C(10') 1.5318(17)

C(13')-C(16') 1.5286(16)

C(13')-C(14') 1.5295(16)

C(13')-C(15') 1.5304(16)

C(7A)-N(1)-C(8) 122.84(9)

C(7A)-N(1)-C(2) 114.19(9)

C(8)-N(1)-C(2) 122.92(9)

N(1)-C(2)-C(13) 114.70(9)

N(1)-C(2)-P(3) 105.77(7)

C(13)-C(2)-P(3) 109.91(7)

C(3A)-P(3)-C(2) 89.10(5)

C(3A)-P(3)-P(3') 99.72(4)

C(2)-P(3)-P(3') 97.13(4)

C(4)-C(3A)-C(7A) 120.26(11)

C(4)-C(3A)-P(3) 127.83(9)

C(7A)-C(3A)-P(3) 111.83(8)

C(3A)-C(4)-C(5) 120.16(12)

C(6)-C(5)-C(4) 119.14(11)

C(5)-C(6)-C(7) 121.89(12)

C(6)-C(7)-C(7A) 118.99(11)

N(1)-C(7A)-C(7) 126.10(11)

N(1)-C(7A)-C(3A) 114.32(10)

C(7)-C(7A)-C(3A) 119.55(10)

N(1)-C(8)-C(9) 117.44(9)

C(11)-C(9)-C(10) 108.68(10)

C(11)-C(9)-C(12) 110.29(9)

45

C(10)-C(9)-C(12) 108.88(10)

C(11)-C(9)-C(8) 111.93(9)

C(10)-C(9)-C(8) 110.85(9)

C(12)-C(9)-C(8) 106.17(9)

C(15)-C(13)-C(16) 108.13(9)

C(15)-C(13)-C(14) 110.06(10)

C(16)-C(13)-C(14) 108.62(9)

C(15)-C(13)-C(2) 110.55(9)

C(16)-C(13)-C(2) 111.68(9)

C(14)-C(13)-C(2) 107.79(9)

C(7A')-N(1')-C(8') 122.48(9)

C(7A')-N(1')-C(2') 114.37(9)

C(8')-N(1')-C(2') 122.80(9)

N(1')-C(2')-C(13') 115.04(9)

N(1')-C(2')-P(3') 106.29(7)

C(13')-C(2')-P(3') 109.48(7)

C(3A')-P(3')-C(2') 89.22(5)

C(3A')-P(3')-P(3) 95.85(4)

C(2')-P(3')-P(3) 99.96(4)

C(4')-C(3A')-C(7A') 120.24(11)

C(4')-C(3A')-P(3') 127.97(9)

C(7A')-C(3A')-P(3') 111.77(8)

C(5')-C(4')-C(3A') 120.06(12)

C(6')-C(5')-C(4') 119.49(11)

C(5')-C(6')-C(7') 121.67(12)

C(6')-C(7')-C(7A') 119.02(12)

N(1')-C(7A')-C(7') 125.81(11)

N(1')-C(7A')-C(3A') 114.67(10)

C(7')-C(7A')-C(3A') 119.51(10)

N(1')-C(8')-C(9') 117.81(10)

C(12')-C(9')-C(11') 109.15(11)

C(12')-C(9')-C(10') 108.84(11)

C(11')-C(9')-C(10') 109.78(10)

C(12')-C(9')-C(8') 110.66(10)

C(11')-C(9')-C(8') 112.03(10)

C(10')-C(9')-C(8') 106.30(10)

C(16')-C(13')-C(14') 107.78(9)

C(16')-C(13')-C(15') 109.78(10)

C(14')-C(13')-C(15') 108.65(10)

C(16')-C(13')-C(2') 107.60(9)

C(14')-C(13')-C(2') 111.53(9)

C(15')-C(13')-C(2') 111.43(9)

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46

Table 9. Torsion angles [°] of 11b.

__________________________________________________________________________

C(7A)-N(1)-C(2)-C(13) -98.17(11)

C(8)-N(1)-C(2)-C(13) 84.21(13)

C(7A)-N(1)-C(2)-P(3) 23.12(11)

C(8)-N(1)-C(2)-P(3) -154.50(9)

N(1)-C(2)-P(3)-C(3A) -18.41(8)

C(13)-C(2)-P(3)-C(3A) 105.94(8)

N(1)-C(2)-P(3)-P(3') 81.27(7)

C(13)-C(2)-P(3)-P(3') -154.39(7)

C(2)-P(3)-C(3A)-C(4) -165.90(11)

P(3')-P(3)-C(3A)-C(4) 97.01(11)

C(2)-P(3)-C(3A)-C(7A) 10.89(9)

P(3')-P(3)-C(3A)-C(7A) -86.19(8)

C(7A)-C(3A)-C(4)-C(5) 1.07(18)

P(3)-C(3A)-C(4)-C(5) 177.63(9)

C(3A)-C(4)-C(5)-C(6) -0.99(19)

C(4)-C(5)-C(6)-C(7) 0.54(19)

C(5)-C(6)-C(7)-C(7A) -0.17(19)

C(8)-N(1)-C(7A)-C(7) -20.56(18)

C(2)-N(1)-C(7A)-C(7) 161.81(11)

C(8)-N(1)-C(7A)-C(3A) 161.35(10)

C(2)-N(1)-C(7A)-C(3A) -16.27(14)

C(6)-C(7)-C(7A)-N(1) -177.75(11)

C(6)-C(7)-C(7A)-C(3A) 0.25(17)

C(4)-C(3A)-C(7A)-N(1) 177.52(10)

P(3)-C(3A)-C(7A)-N(1) 0.46(13)

C(4)-C(3A)-C(7A)-C(7) -0.70(17)

P(3)-C(3A)-C(7A)-C(7) -177.77(9)

C(7A)-N(1)-C(8)-C(9) -85.20(13)

C(2)-N(1)-C(8)-C(9) 92.22(12)

N(1)-C(8)-C(9)-C(11) 55.11(13)

N(1)-C(8)-C(9)-C(10) -66.40(12)

N(1)-C(8)-C(9)-C(12) 175.50(9)

N(1)-C(2)-C(13)-C(15) 62.95(12)

P(3)-C(2)-C(13)-C(15) -56.05(11)

N(1)-C(2)-C(13)-C(16) -57.49(12)

P(3)-C(2)-C(13)-C(16) -176.49(8)

N(1)-C(2)-C(13)-C(14) -176.72(9)

P(3)-C(2)-C(13)-C(14) 64.28(10)

C(7A')-N(1')-C(2')-C(13') 101.49(11)

C(8')-N(1')-C(2')-C(13') -85.18(13)

C(7A')-N(1')-C(2')-P(3') -19.84(11)

C(8')-N(1')-C(2')-P(3') 153.49(9)

N(1')-C(2')-P(3')-C(3A') 16.68(8)

C(13')-C(2')-P(3')-C(3A') -108.15(8)

N(1')-C(2')-P(3')-P(3) -79.12(7)

C(13')-C(2')-P(3')-P(3) 156.04(7)

C(3A)-P(3)-P(3')-C(3A') 175.94(5)

C(2)-P(3)-P(3')-C(3A') 85.63(5)

C(3A)-P(3)-P(3')-C(2') -93.82(5)

C(2)-P(3)-P(3')-C(2') 175.87(5)

C(2')-P(3')-C(3A')-C(4') 170.75(11)

P(3)-P(3')-C(3A')-C(4') -89.32(11)

C(2')-P(3')-C(3A')-C(7A') -10.91(9)

P(3)-P(3')-C(3A')-C(7A') 89.02(8)

C(7A')-C(3A')-C(4')-C(5') -0.41(18)

P(3')-C(3A')-C(4')-C(5') 177.80(9)

C(3A')-C(4')-C(5')-C(6') 1.16(18)

C(4')-C(5')-C(6')-C(7') -0.87(19)

C(5')-C(6')-C(7')-C(7A') -0.18(19)

C(8')-N(1')-C(7A')-C(7') 20.03(17)

C(2')-N(1')-C(7A')-C(7') -166.62(11)

C(8')-N(1')-C(7A')-C(3A') -160.66(10)

C(2')-N(1')-C(7A')-C(3A') 12.69(14)

C(6')-C(7')-C(7A')-N(1') -179.79(11)

47

C(6')-C(7')-C(7A')-C(3A') 0.93(17)

C(4')-C(3A')-C(7A')-N(1') 180.00(10)

P(3')-C(3A')-C(7A')-N(1') 1.52(13)

C(4')-C(3A')-C(7A')-C(7') -0.64(17)

P(3')-C(3A')-C(7A')-C(7') -179.12(9)

C(7A')-N(1')-C(8')-C(9') 84.35(14)

C(2')-N(1')-C(8')-C(9') -88.44(13)

N(1')-C(8')-C(9')-C(12') 66.02(13)

N(1')-C(8')-C(9')-C(11') -56.04(14)

N(1')-C(8')-C(9')-C(10') -175.96(10)

N(1')-C(2')-C(13')-C(16') 174.55(9)

P(3')-C(2')-C(13')-C(16') -65.86(10)

N(1')-C(2')-C(13')-C(14') 56.55(12)

P(3')-C(2')-C(13')-C(14') 176.14(8)

N(1')-C(2')-C(13')-C(15') -65.07(12)

P(3')-C(2')-C(13')-C(15') 54.52(11)

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49


Identification code grobag

Empirical formula C29H50ClNO0.5PRhSi





Space group P21/n


b = 36.045(2) Å β= 109.623(4)°

c = 9.4470(6) Å γ = 90°

Volume 3020.7(3) Å3

Z 4



F(000) 1304



Index ranges -13<=h<=13, -51<=k<=51, -13<=l<=13




Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.8618 and 0.7192







50

Table 11. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters

(Å2x 103) of 12b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

___________________________________________________________________________

x y z U(eq)

___________________________________________________________________________

Rh 4062.7(2) 1011.5(1) 6299.8(2) 16.3(1)

Cl 3589.7(7) 1605.9(2) 7153.0(7) 26.6(1)

Si 2369.7(7) 1576.8(2) 2475.4(7) 22.1(1)

N(1) 5357(2) 1684.3(5) 2553(2) 16.6(4)

C(2) 4477(2) 1666.6(6) 3605(2) 15.6(4)

P(3) 5456.3(6) 1305.2(1) 4993.5(6) 13.8(1)

C(3A) 6082(2) 1087.3(6) 3570(2) 15.8(4)

C(4) 6790(3) 747.1(6) 3594(3) 20.9(4)

C(5) 7375(3) 655.9(6) 2469(3) 23.5(5)

C(6) 7250(3) 908.6(6) 1319(3) 22.1(5)

C(7) 6552(3) 1249.4(6) 1266(3) 20.8(4)

C(7A) 5978(2) 1346.7(6) 2413(2) 15.8(4)

C(8) 4973(2) 1960.5(6) 1342(2) 17.7(4)

C(9) 6070(2) 2287.0(6) 1547(2) 16.8(4)

C(10) 7638(3) 2158.2(7) 1605(3) 22.0(5)

C(11) 6179(3) 2504.7(6) 2967(3) 23.0(5)

C(12) 5421(3) 2539.1(7) 174(3) 26.6(5)

C(13) 7293(3) 1503.2(6) 6339(3) 20.4(4)

C(14) 8496(3) 1559.6(8) 5599(3) 27.4(5)

C(15) 7017(3) 1871.7(8) 6996(3) 36.7(7)

C(16) 7877(3) 1219.2(10) 7603(3) 45.9(9)

C(17) 1214(3) 1380.8(8) 3545(3) 32.0(6)

C(18) 1469(4) 2034.6(10) 1742(5) 57.2(11)

C(19) 2285(4) 1271.9(11) 878(4) 51.7(9)

C(21) 3414(3) 742.5(7) 8104(3) 24.0(5)

C(22) 2135(3) 796.2(7) 6875(3) 26.3(5)

C(23) 1348(3) 501.1(8) 5751(3) 33.9(6)

C(24) 2429(3) 275.7(8) 5197(3) 35.5(6)

C(25) 3812(3) 494.7(6) 5165(3) 25.5(5)

C(26) 5150(3) 494.2(6) 6385(3) 23.3(5)

51

C(27) 5407(3) 298.7(7) 7875(3) 27.5(5)

C(28) 4165(3) 370.0(7) 8555(3) 26.3(5)

O(91) -215(7) 55.6(14) 11538(6) 57.8(13)

C(92) -180(20) -285(4) 10717(14) 56(3)

C(93) -246(16) -160(3) 9223(13) 87(3)

C(94) 330(30) 219(4) 9399(16) 84(5)

C(95) 581(10) 327(2) 10980(11) 55(2)

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52


__________________________________________________________________________

Rh-C(26) 2.116(2)

Rh-C(25) 2.123(2)

Rh-C(22) 2.204(2)

Rh-C(21) 2.218(2)

Rh-P(3) 2.3354(5)

Rh-Cl 2.3832(6)

Si-C(19) 1.847(3)

Si-C(17) 1.856(3)

Si-C(18) 1.878(3)

Si-C(2) 1.939(2)

N(1)-C(7A) 1.376(3)

N(1)-C(8) 1.468(3)

N(1)-C(2) 1.494(3)

C(2)-P(3) 1.859(2)

P(3)-C(3A) 1.817(2)

P(3)-C(13) 1.908(2)

C(3A)-C(4) 1.393(3)

C(3A)-C(7A) 1.417(3)

C(4)-C(5) 1.391(3)

C(5)-C(6) 1.392(3)

C(6)-C(7) 1.386(3)

C(7)-C(7A) 1.407(3)

C(8)-C(9) 1.534(3)

C(9)-C(11) 1.527(3)

C(9)-C(10) 1.531(3)

C(9)-C(12) 1.533(3)

C(13)-C(15) 1.525(4)

C(13)-C(16) 1.528(3)

C(13)-C(14) 1.531(3)

C(21)-C(22) 1.377(4)

C(21)-C(28) 1.511(3)

C(22)-C(23) 1.510(4)

C(23)-C(24) 1.526(4)

C(24)-C(25) 1.532(4)

C(25)-C(26) 1.393(4)

C(26)-C(27) 1.519(3)

C(27)-C(28) 1.533(4)

C(26)-Rh-C(25) 38.37(10)

C(26)-Rh-C(22) 96.23(10)

C(25)-Rh-C(22) 81.65(10)

C(26)-Rh-C(21) 80.80(9)

C(25)-Rh-C(21) 89.54(9)

C(22)-Rh-C(21) 36.30(10)

C(26)-Rh-P(3) 93.95(6)

C(25)-Rh-P(3) 96.75(7)

C(22)-Rh-P(3) 161.03(7)

C(21)-Rh-P(3) 162.38(7)

C(26)-Rh-Cl 157.30(8)

C(25)-Rh-Cl 163.37(8)

C(22)-Rh-Cl 88.28(7)

C(21)-Rh-Cl 90.12(7)

P(3)-Rh-Cl 88.47(2)

C(19)-Si-C(17) 110.25(16)

C(19)-Si-C(18) 109.37(19)

C(17)-Si-C(18) 105.08(13)

C(19)-Si-C(2) 107.72(12)

C(17)-Si-C(2) 116.29(11)

C(18)-Si-C(2) 107.96(14)

C(7A)-N(1)-C(8) 121.78(18)

C(7A)-N(1)-C(2) 112.03(16)

C(8)-N(1)-C(2) 120.08(17)

N(1)-C(2)-P(3) 104.15(13)

N(1)-C(2)-Si 109.56(14)

53

P(3)-C(2)-Si 116.42(11)

C(3A)-P(3)-C(2) 89.32(9)

C(3A)-P(3)-C(13) 102.01(10)

C(2)-P(3)-C(13) 109.38(10)

C(3A)-P(3)-Rh 125.06(7)

C(2)-P(3)-Rh 117.17(7)

C(13)-P(3)-Rh 111.23(7)

C(4)-C(3A)-C(7A) 120.14(19)

C(4)-C(3A)-P(3) 129.85(17)

C(7A)-C(3A)-P(3) 109.30(15)

C(5)-C(4)-C(3A) 120.4(2)

C(4)-C(5)-C(6) 119.4(2)

C(7)-C(6)-C(5) 121.5(2)

C(6)-C(7)-C(7A) 119.5(2)

N(1)-C(7A)-C(7) 125.4(2)

N(1)-C(7A)-C(3A) 115.52(18)

C(7)-C(7A)-C(3A) 119.01(19)

N(1)-C(8)-C(9) 116.25(18)

C(11)-C(9)-C(10) 110.18(19)

C(11)-C(9)-C(12) 109.18(19)

C(10)-C(9)-C(12) 108.37(18)

C(11)-C(9)-C(8) 110.42(18)

C(10)-C(9)-C(8) 111.86(18)

C(12)-C(9)-C(8) 106.71(18)

C(15)-C(13)-C(16) 109.4(2)

C(15)-C(13)-C(14) 108.9(2)

C(16)-C(13)-C(14) 108.6(2)

C(15)-C(13)-P(3) 110.89(17)

C(16)-C(13)-P(3) 106.12(17)

C(14)-C(13)-P(3) 112.92(16)

C(22)-C(21)-C(28) 123.8(2)

C(22)-C(21)-Rh 71.31(13)

C(28)-C(21)-Rh 112.42(15)

C(21)-C(22)-C(23) 125.3(2)

C(21)-C(22)-Rh 72.39(14)

C(23)-C(22)-Rh 108.95(17)

C(22)-C(23)-C(24) 113.0(2)

C(23)-C(24)-C(25) 113.7(2)

C(26)-C(25)-C(24) 121.4(2)

C(26)-C(25)-Rh 70.54(13)

C(24)-C(25)-Rh 113.14(17)

C(25)-C(26)-C(27) 125.9(2)

C(25)-C(26)-Rh 71.09(14)

C(27)-C(26)-Rh 111.62(16)

C(26)-C(27)-C(28) 113.8(2)

C(21)-C(28)-C(27) 112.45(19)

C(95)-O(91)-C(92) 105.8(9)

O(91)-C(92)-C(93) 104.6(9)

C(94)-C(93)-C(92) 106.5(8)

C(93)-C(94)-C(95) 106.7(9)

O(91)-C(95)-C(94) 105.4(9)

54

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