supporting information for the manuscriptsupporting information for the manuscript facile...

Supporting information for the manuscript

Facile N-functionalization and strong magnetic communication in a diuranium(V) bis-nitride complex

Luciano Barluzzia, Lucile Chatelaina, Farzaneh Fadaei-Tirania, Ivica Zivkovicb and Marinella

Mazzanti*a

aInstitut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland. bLaboratory for Quantum Magnetism, Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2019

Contents

A) NMR SPECTRA .......................................................................................................................... 3

B) IR SPECTRA ............................................................................................................................. 26

C) X-RAY CRYSTALLOGRAPHIC DATA .......................................................................................... 28

D) MAGNETIC DATA .................................................................................................................... 30

E) UV-VIS DATA .......................................................................................................................... 35

A) NMR spectra

Fig. S1: 1H-NMR (400 MHz) at 298 K in d8-thf of the crude reaction mixture between [U(OSi(OtBu)3)3]2, 1 and one equivalent of KN3 in thf after 4 days at -40°C leading to a mixture of complex [K{[U(OSi(OtBu)3)3]2(μ-N)}], 2 and complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3

Fig. S2: 1H-NMR (400 MHz) at 298 K in d8-thf of isolated [K{[U(OSi(OtBu)3)3]2(μ-N)}], 2

-8-7-6-5-4-3-2-1012345678f1(ppm)

-1.58

-0.68

1.73

2.60

3.58

thf[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3[K{[U(OSi(OtBu)3)3]2(μ-N)}], 2[U(OSi(OtBu)3)3]2, 1

-2.2-2.0-1.8-1.6-1.4-1.2-1.0-0.8-0.6-0.4-0.20.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.2f1(ppm)

-0.67

1.73

3.58

thf[K{[U(OSi(OtBu)3)3]2(μ-N)}], 2

Fig. S3: 1H-NMR (400 MHz) at 298 K in d8-thf of the reaction mixture between [U(OSi(OtBu)3)3]2, 1 and two equivalents of

KN3 in thf at -40°C for 5 days forming complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3

Fig. S4: 1H-NMR (400 MHz) at 298 K in d8-thf of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3

-5.5-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.0f1(ppm)

-1.58

thf[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3

-5.5-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)

-1.58

thf[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3

Fig. S5: 13C-NMR (400 MHz) at 298 K in d8-thf of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3

Fig. S6: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3 at room

temperature

-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)

tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4[U(OSi(OtBu)3)4][K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3

immediately

7h

24h

3d

5d

Fig. S7: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3 after 24h at 70°C affording

complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

Fig. S8: 1H-NMR (400 MHz) at 298 K in d8-tol of [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3, after 5 days at RT (top) and after

24h at 70°C (bottom).

-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)

-1.76

tol

[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)

tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4[U(OSi(OtBu)3)4][K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-N3)}], 3

after 5d at RT

after 24h at 70°C

Fig. S9: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

Fig. S10: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)

-1.76

-1.14

-0.86

1.40

1.63

2.09

7.02

7.10

tol

[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

Fig. S11: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture 6h after the addition of one equivalent of CS2 to

[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5

Fig. S12: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5

-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

0.39

0.60

0.720.98

1.06

2.08

6.97

7.01

7.12

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)

0.39

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5

Fig. S13: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}], 13C-5

Fig. S14: 13C-NMR (400MHz) at 298 K in d6-dmso of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}], 13C-5

Fig. S15: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-

N)2}], 4 and 10 equivalents of 13CS2 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}], 13C-5 and an unidentified precipitate

Fig. S16: 13C-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 10

equivalents of 13CS2

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

toluene[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-NCS)}], 5

immediately

24h

2030405060708090100110120130140150160170180190f1(ppm)

toluenesiloxide (C(CH3)3)

siloxide (C(CH3)3)NCS in complex 5unknown

CS2

Fig. S17: Quantitative 13C-NMR (600 MHz) at 298 K in d6-dmso of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 10 equivalents of 13CS2

Fig. S18: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of one equivalent of

CO2 to [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6

2030405060708090100110120130140150160170180f1(ppm)

1.38

1.00

d6-dmso

KNCS

toluene

CH313COONa

Fig. S19: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6

Fig. S20: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-N13CO)}], 13C-6

-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)

0.18

2.08

6.97

7.01

7.09

toluene[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6

Fig. S21: 13C-NMR (400 MHz) at 298 K in D2O using d6-dmso as a reference of isolated [K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-N13CO)}], 13C-6

Fig. S22: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 2 equivalents of CO2 to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

0.19

1.06

toluene[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-O)(µ-NCO)}], 6[U(OSi(OtBu)3)4]

Fig. S23: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 10 equivalents of

13CO2 to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

Fig. S24: 13C-NMR (400 MHz) at 298 K in d6-dmso of the reaction mixture after the addition of 10 eqvs of 13CO2 to complex

[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

-9-8-7-6-5-4-3-2-1012345678910f1(ppm)

0.45

0.741.06

1.56

2.08

6.97

7.09

toluene

Fig. S25: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 1 eqv of CO to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

Fig. S26: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 3 eqvs of CO to

complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7

-6-5-4-3-2-10123456789f1(ppm)

-1.76

0.78

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

0.78

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7

Fig. S27: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 1 atm of CO to complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 affording complex [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7

Fig. S28: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture immediately after the addition of 6 atm of CO to

complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

-6-5-4-3-2-10123456789f1(ppm)

0.78

toluene


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)

0.12

0.98

1.00

0.42

-0.52

0.26

0.78

1.06

1.34

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-CN)(µ-O)(µ-NCO)}], 7[U(OSi(OtBu)3)4]

Fig. S29: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7

Fig. S30: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(µ-13CN)(μ-O)(µ-N13CO)}], 13C-7

-7-6-5-4-3-2-101234567891011f1(ppm)

-0.64

0.77

2.08

3.10

6.80

6.97

7.01

7.09

toluene


-160-140-120-100-80-60-40-20020406080100120140160180200220f1(ppm)

-158.48

30.72

73.12

214.19

toluenesiloxide (C(CH3)3)

siloxide (C(CH3)3)

CN

NCO

oror

Fig. S31: Quantitative 13C-NMR (600 MHz) at 298 K in d6-dmso of isolated [K2{[U(OSi(OtBu)3)3]2(µ-13CN)(μ-O)(µ-N13CO)}],

13C-7

Fig. S32: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 1 atm

of H2 heated up at 60°C for 1h affording complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

3035404550556065707580859095100105110115120125130135140145150155160165170175f1(ppm)

0.96

1.00

d6-dmsoKNCOKCN

Fig. S33: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 1 atm of H2 affording complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

Fig. S34: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 1 atm of H2 after 16h at RT affording complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

toluene[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

2.41

1.00

-1.77

-0.86

-0.23

2.08

6.97

7.01

7.09

0.68

1.00

-1.78

-0.87

-0.23

2.08

6.97

7.01

7.09

-0.87

-0.22

2.086.97

7.017.09

[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

1.00 2.41

1.00 0.68

immediately

8h

16h

-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)

-0.87

-0.22

2.08

6.97

7.01

7.09


Fig. S35: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

Fig. S36: 1H-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8 on a broader spectral window

-11-10-9-8-7-6-5-4-3-2-10123456789101112f1(ppm)

-0.87

0.26

2.08

6.97

7.077.09


-30-20-100102030405060708090100110120130140150160170180190200f1(ppm)

162.00

1.69

-0.88

2.08

6.95

7.07

176.46

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

Fig. S37: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and D2 heated up at 60°C for 1h affording complex [K2{[U(OSi(OtBu)3)3]2(μ-ND)2}], 8

Fig. S38: 13C-NMR (400 MHz) at 298 K in d8-tol of isolated [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

-100102030405060708090100110120130140150160170180f1(ppm)

-0.85

2.08

6.97

7.01

7.09

toluene

[K2{[U(OSi(OtBu)3)3]2(μ-ND)2}], 8

Fig. S39: 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 5.5

atm of H2 after 3h at RT

Fig. S40: 1H-NMR (400 MHz) at 298 K in d6-dmso of the volatiles and the headspace of the reaction between complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 5.5 atm of H2 after 3h at RT collected in a frozen 2M solution of HCl in Et2O

-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)

0.80

1.01

1.171.201.241.32

1.35

1.571.62

1.65

2.04

2.08

2.11

toluene

-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1(ppm)

1.04

3.42

4.22

Et2O

dmso

Fig. S41: 1H-NMR (400 MHz) at 298 K in d6-dmso of the reaction mixture between solid complex 4 and an excess of a 2M

solution of HCl in Et2O


solution of HCl in Et2O

-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1(ppm)

23.07

6.24

2.99

7.33

NH4Cldimethylsulfonedmso

-5-4-3-2-1012345678910f1(ppm)

89.00

5.64



solution of HCl in Et2O in presence of excess KC8


N)2}], 4 and 1 eq of PyHOTf

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1(ppm)

16.93

4.00

3.00

7.187.26


-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

immediately

24h

3d

4d

5d

6d

7d

10d

Fig. S45: Evolution of the 1H-NMR (400 MHz) at 298 K in d8-tol of the reaction mixture between [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8 and 1 eq of PyHOTf

Fig. S46: 1H-NMR (400 MHz) at 298 K in d6-dmso of the volatiles and the headspace of the reaction mixture between between [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4 and 30 eq of H2O in thf collected in a frozen 2M solution of HCl in Et2O

-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1(ppm)

tol

[K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

immediately

12h

24h

36h

48h

60h

72h

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

12.10

0.19

7.03

7.167.29



N)2}], 4 and 1 eq of Si2Me6. The formation of an unidentified yellow precipitate is also observed.

B) IR spectra

Fig. S48: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-S)(µ-N)(μ-NCS)}], 5 in a Nujol suspension measured on

KBr windows.

-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)

tol[K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4Si2Me6

immediately

30 min

1h

2h

6h

12h

18h

1977

Fig. S49: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-N13CS)}], 5 in a Nujol suspension measured on KBr windows.

Fig. S50: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-NCO)}], 6 in a Nujol suspension measured on

KBr windows.

0

10

20

30

40

50

60

70

80

050010001500200025003000350040004500

%T

Wavenumber(cm-1 )

IRspectrumofcomplex[K2{[U(OSi(OtBu)3)3]2(μ-N)(µ-S)(µ-N13CS)}]

1931

Fig. S51: IR spectrum of isolated complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-N13CO)}], 13C-6 in a Nujol suspension measured on KBr windows.

C) X-Ray crystallographic data 2 3 5

Formula C72H162KNO24Si6U2 C72H162K2N4O24Si6U2 C73H162K2N2O24S2Si6U2Crystal size (mm3) 0.642x0.503x0.419 0.48×0.31×0.26 0.12×0.06×0.04

crystal system Monoclinic Monoclinic monoclinicspace group P21/c P21/n P21volume (Å3) 10803(2) 5538.4(16) 5619.3(4)

a (Å) 14.210(3) 14.382(2) 13.9065(4)b (Å) 28.1537(19) 17.661(3) 18.2338(7)c (Å) 27.910(3) 21.819(4) 22.1810(9)α (deg) 90 90 90β (deg) 104.632(8) 92.012(9) 92.450(4)γ (deg) 90 90 90

Z 4 2 2 formula weight

(g/mol) 2109.72 2190.85 2238.96

density (g cm-3) 1.297 1.314 1.323absorption

coefficient (mm-1) 3.156 3.118 10.139

F(000) 4320 2240 2288 temp (K) 100(2) 100(2) 139.99(10)

total no. reflections 115428 97679 38004unique reflections

[R(int)] 24309[0.1089] 19106 [0.0447] 13621[0.0881]

Final R indices [I > 2σ(I)]

R1=0.0686,wR2=0.1330

R1 = 0.0592, wR2 = 0.1241

R1 = 0.0772, wR2 = 0.1898

Largest diff. peak and hole (e.A-3) 2.689and-2.107 4.561and -2.717 3.583and-4.163

GOOF 1.111 1.135 1.074

6 7 8 Formula C73H162K2N2O26Si6U2 C81H170K2N2O26Si6U2 C79H172K2N2O24Si6U2

Crystal size (mm3) 0.10×0.06×0.04 0.19×0.09×0.08 0.76×0.42×0.35cryst syst Monoclinic Monoclinic Monoclinic

space group P21 P21 P21/nvolume (Å3) 5510.8(3) 5673.2(9) 5536.5(3)

a (Å) 13.9377(5) 13.9927(15) 14.4207(4)b (Å) 17.9175(5) 18.2874(12) 17.5321(5)c (Å) 22.0849(6) 22.208(2) 21.9098(6)α (deg) 90 90 90 β (deg) 92.306(3) 93.321(7) 91.840(3)γ (deg) 90 90 90

Z 2 2 2formula weight

(g/mol) 2206.84 2310.98 2256.98

density (g cm-3) 1.330 1.353 1.354absorption

coefficient (mm-1) 10.000 3.049 3.121

F(000) 2256 2368 2316 temp (K) 100.00(10) 120(2) 140.01(10)

total no. reflections 39631 67143 73741unique reflections

[R(int)] 17996 [0.0796] 20671 [0.0523] 19069 [0.0618]

Final R indices [I > 2σ(I)]

R1 = 0.0640, wR2 = 0.1592

R1 = 0.0511, wR2 = 0.1029

R1 = 0.0390, wR2 = 0.0824

Largest diff. peak and hole (e.A-3) 2.543and -3.689 1.503and -0.802 2.543and -1.684

GOOF 1.017 1.067 1.060

D) Magnetic data

Fig. S52: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-N)2}], 4

0 50 100 150 200 250 300Temperature (K)

0.6

0.7

0.8

0.9

1

1.1

1.2

1.3

1.4

1.5-

0 (e

mu/

mol

Oe)

10-3

Fig. S53: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-S)(µ-N)(μ-NCS)}], 5

Fig. S54: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-O)(µ-N)(μ-NCO)}], 6

0 50 100 150 200 250 300Temperature (K)

1

1.5

2

2.5

3

3.5

-0

(em

u/m

ol O

e)

10-3

0 50 100 150 200 250 300Temperature (K)

6

7

8

9

10

11

12

13

-0

(em

u/m

ol O

e)

10-4

Fig. S55: c vs T plot for complex [K{[U(OSi(OtBu)3)3]2(μ-N)}], 2

0 50 100 150 200 250 300Temperature (K)

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0.045

0.05

0.055

-0

(em

u/m

ol O

e)

Fig. S56: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3

Fig. S57: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7

0 50 100 150 200 250 300Temperature (K)

0.005

0.01

0.015

0.02

0.025

0.03

0.035

-0

(em

u/m

ol O

e)

0 50 100 150 200 250 300Temperature (K)

5.8

6

6.2

6.4

6.6

6.8

7

7.2

-0

(em

u/m

ol O

e)

10-3

Fig. S58: c vs T plot for complex [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

0 50 100 150 200 250 300Temperature (K)

0.005

0.01

0.015

0.02

0.025

0.03

-0

(em

u/m

ol O

e)

Fig. S59: Ortep diagram of the core showing the metrical parameters for the bridging atoms in complexes a) [K2{[U(OSi(OtBu)3)3]2(μ-N)(μ-N3)}], 3; b) [K2{[U(OSi(OtBu)3)3]2(µ-CN)(μ-O)(µ-NCO)}], 7; c) [K2{[U(OSi(OtBu)3)3]2(μ-NH)2}], 8

E) UV-Vis data

Fig. S60: UV-Vis absorption spectra in toluene solution of complexes 3-8.

U1 U1

N1

N2

N3

N4

3.6330(6) Å

124.6(7)°

91.5(4)°

U1 U1

N1

H1

3.5687(2) Å

106.10(12)°

U1 U2O2A

N1

C1A

O1A

90.7(6)°

N2

115.8(6)°

92.5(7)°

C2A

3.6358(7)Å

a) b)

c)

0

2000

4000

6000

8000

10000

250 750 1250 1750

ε(M

-1cm

-1)

wavelenght (nm)

345678

Fig. S61: NIR absorption spectra in toluene solution of complexes 3-8.

0

20

40

60

80

100

120

450 950 1450 1950

ε(M

-1cm

-1)

wavelenght (nm)

345678

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