Supporting Information

 Wiley-VCH 2011
69451 Weinheim, Germany

A Dimer of Silaisonitrile with Two-Coordinate Silicon Atoms**

Rajendra S. Ghadwal, Herbert W. Roesky,* Kevin Prpper, Birger Dittrich, Susanne Klein, and
Gernot Frenking*

anie_201101320_sm_miscellaneous_information.pdf

Supporting Information
For

A Dimer of Silaisonitrile with Two-Coordinate Silicon Atoms

Rajendra S. Ghadwal, Herbert W. Roesky,* Kevin Prpper, Birger Dittrich, Susanne Klein,
and Gernot Frenking*
Institut fr Anorganische Chemie, Georg-August-Universitt Gttingen, Tammannstrasse 4, 37077
Gttingen (Germany) and Fachbereich Chemie, Philipps-Universitt Marburg, Hans-MeerweinStrae, 35032 Marburg (Germany)

*To whom correspondence should be addressed. Fax: (+49) 551-393-373; (+49) 6421-282-5566
E-mail: hroesky@gwdg.de; frenking@chemie.uni-marburg.de

Contents:
(1) Experimental details and physical data
(2) X-ray crystallography
(3) Tables T1, T2 and T3
(4) Theoretical details
(5) References

(1) Experimental details and physical data

All syntheses and manipulations were carried out under an inert atmosphere of dry nitrogen
gas using glove-box or Schlenk-line techniques. The starting materials IPrCl2Si=NAr (1)[S1]
(Ar = 2,6-bis(2,4,6-triisopropylphenyl)phenyl) and IPrSiCl2[S2]

(IPr = 1,3-bis(2,6-

diisopropylphenyl)imidazol-2-ylidene) were prepared according to the reported methods.

Me3SiN3 (Aldrich) was used as received. C6D6 and THF-d8 were dried over Na or K metal
and distilled under dry nitrogen prior to use. All other solvents were dried and purified by a
MBRAUN solvent purification system (MB SPS 800). 1H,

13

C, and

29

Si NMR spectra were

recorded using a Bruker Avance DPX 200 or a Bruker Avance DRX 500 spectrometer. The
chemical shifts are given relative to SiMe4. EI-MS spectrum of 3 was obtained using a
Finnigan MAT 8230 instrument. Elemental analyses were performed by the Institut fr
Anorganische Chemie, Universitt Gttingen.
Synthesis of (ArNSi:)2 (3): To a Schlenk-flask containing IPrCl2Si=NAr (1) (9.90 g,10.06
mmol) (Ar = 2,6-bis(2,4,6-triisopropylphenyl)phenyl)and KC8 (3.45 g, 25.52 mmol) was
added pre-cooled (78 C) toluene (100 mL). The reaction mixture was allowed to warm to
room temperature and continued to stir overnight. Removal of the volatiles under vacuum
afforded a brown solid. Silaisonitrile (ArNSi:)2 (3) was obtained as yellow crystalline blocks
in 21 % (1.11 g) yield on storage of a saturated toluene solution at 30 C for 7 days.
Suitable single crystals for X-ray crystallographic studies were grown from a C6D6 solution
in a NMR tube at room temperature. Elemental analysis (%) calcd for C72H98N2Si2: C 82.54,
H 9.43, N 2.67; found: C 82.61, H 9.51, N 2.52. 1H NMR (200 MHz, C6D6, 25 C): 1.09 (d,
24H, J = 6.60 Hz, CHMe2); 1.24 (d, 24H, J = 6.80 Hz, CHMe2); 1.36 (d, 24H, J = 6.80 Hz,
CHMe2); 2.76 (m, 8H, CHMe2); 2.91 (m, 4H, CHMe2); 6.60-7.24 (m, 14H, C6H3, C6H2) ppm.
13

C NMR (125 MHz, C6D6, 25 C): 23.60, 24.37, 25.71(CHMe2); 31.57, 34.66 (CHMe2);

120.60, 122.00, 123.65, 131.39, 132.93, 139.85, 141.90, 146.64, 148.36( C6H3, C6H2) ppm.
29

Si NMR ( 99 MHz, C6D6, 25C): 183.29 ppm. EI-MS: m/z (%):1046 [(M)+] (90), 1003

[(M C3H7)+] (100).

Synthesis of bis-silaimine (ArNSi=NSiMe3)2 (4): To a 20 mL yellow toluene solution of 3
(0.35 g,0.33 mmol) was added a 20 mL toluene solution of Me3SiN3 (0.1 mL, 0.75 mmol).
The resulting yellow solution was stirred at room temperature, which turned to a colorless
solution after 2h. Removal of all the volatiles under reduced pressure gave a white solid,
2

which was re-dissolved in toluene (5 mL) and stored in a freezer at 4 C for 10 days.
Compound 4 was isolated as colorless crystals in 62% (0.25 g) yield. Elemental analysis (%)
calcd for C78H116N4Si2: C 76.66, H 9.57, N 4.58; found: C 76.54, H 9.44, N 4.47. 1H NMR
(200 MHz, C6D6, 25 C): 0.07 (s, 18H, SiMe3); 1.05 (d, 24H, J = 6.60 Hz, CHMe2); 1.28 (d,
24H, J = 6.80 Hz, CHMe2); 1.35 (d, 24H, J = 6.80 Hz, CHMe2); 2.80-3.11 (m, 12H, CHMe2);
6.55-7.10 (m, 14H, C6H3, C6H2) ppm.

13

C NMR (125 MHz, C6D6, 25 C): 1.36 (SiMe3);

23.98, 24.56, 25.47(CHMe2); 30.91, 34.80 (CHMe2); 117.70, 121.45, 125.64, 129.65, 133.80,
137.82, 142.90, 148.01, 148.80 ( C6H3, C6H2) ppm.

29

Si NMR ( 99 MHz, C6D6, 25C):

2.76 (SiMe3), 56.83 (NSi=N) ppm.

(2) X-ray crystallography
Crystal data are summarized in Tables T1 and T2. For compounds 3 and 4 single crystals
were measured on a Bruker three-circle diffractometer equipped with a SMART 6000 CCD
area detector and a CuK rotation anode. Integrations were performed with SAINT.[S3]
Intensity data for compounds 3 and 4 were corrected for absorption and scaled with
SADABS[S4]. Both structures were solved by direct methods and subsequently refined on F2
by full-matrix least-squares methods with the program SHELXL-97,[S5] utilizing anisotropic
displacement parameters for non-hydrogen atoms. Hydrogen atoms were included in the
model by constraints via a riding model after they have been located in difference Fourier
maps. The asymmetric unit of 4 contains half a molecule and crystallizes in space group P.
After initial independent atom model (IAM) refinement with SHELXL-97, parameter
values of compound 3 were used to initiate an Invariom refinement.[S6] The scattering-factor
model used in Invariom refinement is based on the Hansen and Coppens multipole
formalism.[S7] Rather than adjusting the respective multipole parameters to the experimental
data, which requires Bragg-data to high resolution, multipole parameters are predicted from
theory in Invariom refinement. This procedure also yields most benefits of a conventional
charge density refinement. These are an improved parameter precision, better Figures of
merit, ADPs de-convoluted from electron density, and an interpretable electron-density
model.

Reflections with [I> 3 (I)] were included in Invariom refinement, which was
performed with the program XDLSM as included in the XD package.[S8] Prior to XDLSM
refinement, input files were processed with the program InvariomTool,[S9] and full details of
the general Invariom modeling procedure can be found in the reference for this program.
Only positional and displacement parameters of non-hydrogen atoms were adjusted in
Invariom refinement, so that the number of parameters was not increased in comparison the
IAM. Bond distances to H-atoms were set to values of model compounds of the Invariom
database.[S10] Like compound 4 the asymmetric unit of 3 contains only half a molecule. 3
crystallizes in the space group C2/c. For the silaisonitrile core, two different conformations
have been modeled (Figure F1) in order to describe the N1SiN2 rotation around the
C1N1 and C20N2 single bonds. The dynamic rotational motion becomes apparent also
through the elongated atomic displacement parameters (ADPs). According to the occupancy
of the split positions the contribution of the main component Si(1) and Si(2) has been refined
to be 0.837(3), i.e. 84 % for the main and 16 % for the minor component.

Figure F1. Molecular structure of 3; anisotropic displacement parameters depicted at 50% probability.
Isopropyl groups and benzene molecules are omitted and residual groups are shown as wires for
clarity. The picture illustrates the silicon rotation of the Si2N2 core. The anisotropic displacement
parameters also emphasize the movement around the N1, N2 axis.

Figure F2. Side view of the molecular structure of 3; atoms in the silaisonitrile core are mapped as spheres.
Isopropyl groups and benzene molecules are omitted and residual groups are shown as wires for clarity. The
Si2N2 motive forms a planar layer in between the phenyl rings. The dihedral angles for the Si2N2 plane and the
phenyl rings are 56.162 and 26.905. The phenyl rings on the amino nitrogen atoms are almost perpendicular to
each other as indicated by a dihedral angle of 83.067.

Figure F3. Molecular structure of 4; anisotropic displacement parameters depicted at 50% probability.
Isopropyl groups and benzene molecules are omitted and residual groups are shown as wires for
clarity. The Si2N2 core with the attached TMS groups builds a straight line and perpendicular to the
phenyl rings. The dihedral angles for the Si2N2 plane and the phenyl ring are 91.22 and 93.49.

Figure F4. Deformation density plot of 3; the deformation electron density shows the difference
between total electron density (as modeled by the Invariom approach) and the independent atom
3
model. Contour level steps are 0.1 e/ with isosurface values as indicated in the legend.

(3) Tables T1 and T2

Table T1: Crystal data and structure refinement for 3 3 benzene
Identification code

3 3 benzene

Empirical formula

C90 H116 N2 Si2

Formula weight

1282.03

Temperature

100(2) K

Wavelength

1.54178

Crystal system

monoclinic

Space group

C 2/c

Unit cell dimensions

a = 18.5170(3)

= 90.

b = 18.0955(2)

= 109.724(1)

c = 24.6686(4)

= 90.

Volume

7780.9(2)

Density (calculated)

1.094 mg/m3

Absorption coefficient

0.743 mm-1

F(000)

2792

Crystal size

0.02 x 0.01 x 0.01 mm3

Theta range for data collection

3.52 to 72.52

Index ranges

-19<=h<=21,
-22<=k<=22, -30<=l<=30

Reflections collected

86369

Independent reflections

7740 [R(int) = 0.0328]

Completeness to = 72.52

97.7 %

Absorption correction

semi-empirical from
equivalents

Max. and min. transmission

0.4697 and 0.3916

Refinement method

Full-matrix least-squares on
F2

Data / restraints / parameters

5672 / 24 / 436

Goodness-of-fit on F

3.27

Final R indices [I >3(I)]

R1(F) = 0.0480, wR2(F) =

0.047

R indices (all data)

R1(F) = 0.071, wR2(F) =

0.094

Largest diff. peak and hole

0.774 and -0.561 e.-3

Table T2: Crystal data and structure refinement for 42 toluene.

Identification code

4 2 toluene

Empirical formula

C92 H132 N4 Si4

Formula weight

1406.38

Temperature

100(2) K

Wavelength

1.54178

Crystal system

triclinic

Space group

Unit cell dimensions

a = 12.7393(2)

= 88.000(1)

b = 13.6693(2)

= 75.83

c = 13.9072(2)

= 64.075(1)

Volume

2104.57(5)

Density (calculated)

1.110 mg/m3

Absorption coefficient

0.994 mm-1

000)

768

Crystal size

0.02 x 0.02 x 0.02 mm

Theta range for data collection

3.29 to 72.15

Index ranges

-15<=h<=14, -16<=k<=16, -

17<=l<=17
Reflections collected

94965

Independent reflections

8049 [R(int) = 0.0333]

Completeness to = 72.15

96.9 %

Absorption correction

semi-empirical from
equivalents

Max. and min. transmission

0.4696 and 0.3743

Refinement method

Full-matrix least-squares on
F2

Data / restraints / parameters

Goodness-of-fit on F

8049 / 1957 / 592

1.060

Final R indices [I >2(I)]

R1 = 0.0649, wR2 = 0.1770

R indices (all data)

R1 = 0.0707, wR2 = 0.1856

Largest diff. peak and hole

1.085 and -0.377 e.-3

Table T3: Energies (in a.u.) and coordinates (in ) of the calculated molecules

2M
22
E= -802.2457576 a.u.
N
3.667956 -0.653630
C
2.353472 -0.398864
N
2.264652 0.848474
C
3.498024 1.394835
C
4.402452 0.437771
Si
0.643755 -1.407455
N
-0.208564 -0.075773
C
-1.583382 0.034285
C
-2.378869 -0.899151
C
-3.754632 -0.753517
C
-4.384007 0.325122
C
-3.609472 1.262557
C
-2.235207 1.126625
H
3.641530 2.392700
H
5.473372 0.443431
H
1.308247 1.203866
H
4.046554 -1.530538
H
-1.634206 1.855458
H
-4.081814 2.110546
H
-5.455242 0.438129
H
-4.338531 -1.489695
H
-1.891059 -1.731010

-0.194643
-0.138839
0.306952
0.537005
0.217734
-0.566240
-0.081149
-0.008071
0.672213
0.741106
0.138201
-0.533569
-0.599601
0.899786
0.249300
0.405675
-0.501155
-1.122330
-1.007271
0.195161
1.273630
1.159371

3M
26
E = -1152.0227603
a.u.
C
1.180203
C
0.000000
C
-1.180280
C
-1.178497
C
0.000000
C
1.178568
N
-0.000191
Si
1.187262
N
-0.000191
C
0.000001
C
-1.180279

3.284382
2.574933
3.284598
4.669327
5.370291
4.669111
1.176632
0.000000
-1.176632
-2.574933
-3.284598

0.216627
-0.000214
-0.216780
-0.207231
0.000379
0.207685
-0.000565
-0.559551
-0.000565
-0.000214
-0.216780

C
C
C
C
Si
H
H
H
H
H
H
H
H
H
H

-1.178496
0.000001
1.178569
1.180204
-1.187100
-2.095074
-2.102051
0.000137
2.102177
2.094948
-2.095075
-2.102052
0.000136
2.102176
2.094947

-0.207231
0.000379
0.207685
0.216627
0.559588
-0.405419
-0.373947
0.000620
0.374633
0.405015
-0.405419
-0.373947
0.000620
0.374633
0.405015

-4.669327
-5.370291
-4.669111
-3.284382
0.000000
-2.742205
-5.201948
-6.448635
-5.201566
-2.741813
2.742205
5.201948
6.448635
5.201566
2.741814

4M
36
E = -1844.2532845
a.u.
C
5.341396
C
4.795583
C
3.422048
C
2.584541
C
3.124625
C
4.499812
N
1.183068
Si
-0.158348
N
-0.316225
Si
-0.975976
H
-0.616765
Si
0.158374
N
0.316313
Si
0.975850
H
0.617624
N
-1.183044
C
-2.584516
C
-3.422026
C
-4.795560
C
-5.341363
C
-4.499773

-0.672075
0.601925
0.779108
-0.329807
-1.609891
-1.773570
-0.154616
-1.230938
-2.774648
-4.336151
-5.044995
1.230905
2.774603
4.336196
5.044808
0.154583
0.329790
-0.779117
-0.601914
0.672098
1.773586

-0.000219
-0.036761
-0.038034
-0.001019
0.035943
0.035867
-0.001141
-0.003034
-0.005386
-0.018654
-1.266916
0.002769
0.005349
0.018228
1.266904
0.000769
0.001003
0.038098
0.037186
0.000909
-0.035277

C
H
H
H
H
H
H
H
H
H
H
H
H
H
H

-3.124590
2.457902
0.470119
-2.458110
-0.471352
2.998947
2.466600
-2.998933
-2.466558
-5.439178
-4.912681
-6.411321
5.439193
4.912724
6.411355

1.609885
4.311536
5.128371
-4.311299
-5.128208
1.772712
-2.466046
-1.772730
2.466033
-1.467409
2.769767
0.805741
1.467429
-2.769743
-0.805705

-0.035709
-0.073739
-1.12477
0.071988
1.124911
-0.067947
0.064063
0.06778
-0.063906
0.065748
-0.063795
0.000786
-0.065259
0.064583
0.000182

C6H5NSi
13
E = -575.9715026
a.u.
C
-0.560395
C
0.149222
C
-0.560419
C
-1.943948
C
-2.643604
C
-1.943926
N
1.520024
Si
3.076685
H
-0.007991
H
-2.478619
H
-3.722186
H
-2.478579
H
-0.007951

1.203289
-0.000010
-1.203298
-1.198336
0.000015
1.198350
-0.000028
0.000008
-2.129687
-2.135767
0.000025
2.135792
2.129668

-0.000147
-0.000695
-0.00019
0.000182
0.000164
0.000128
-0.000199
0.000264
-0.000114
0.000404
0.000433
0.000384
-0.000056

(4) Theoretical details

Geometry optimizations with and without symmetry constraints were carried out with
GAUSSIAN03[S11] at M05-2x/def2-TZVPP[S12],[S13] level of theory. Stationary points were characterized
by calculating the Hessian matrix analytically at this level of theory.
The Nuclei Independant Chemical Shifts (NICS) were calculated with the GIAO method at
[S14]

M05-2x/def2-TZVPP. The NBO

analyses were carried out with the internal module of

GAUSSIAN 03 at this level of theory. We also analyzed the electronic charge distribution with
the Atoms-in-Molecules (AIM) method[S15] which was performed at the M05-2x/def2-TZVPP
level of theory with a locally modified version of the AIMPAC program package.[S16]

(5) References
[S1]

R. S. Ghadwal, H. W. Roesky, C. Schulzke, M. Granitzka, Organometallics, 2010, 29,

6329-6333.

[S2]

R. S. Ghadwal, H. W. Roesky, S. Merkel, J. Henn, D. Stalke, Angew. Chem., Int. Ed.

2009, 48, 5683-5686; Angew. Chem. 2009, 121, 5793-5796.

[S3]

Bruker. APEX2, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin,
USA, 2009.

[S4]

G. M. Sheldrick, SADABS. University of Gttingen, Germany, 2009.

[S5]

G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112122.

[S6]

a) B. Dittrich, T. Koritsnszky, P. Luger, Angew. Chem. Int. Ed. 2004, 43, 27182721; Angew. Chem. 2004, 116, 2773-2776; b) B. Dittrich, C. B. Hbschle, M.
Messerschmidt, R. Kalinowski, D. Girnt, P. Luger, Acta Cryst. 2005, A61, 314- 320.

[S7]

N. K. Hansen, P. Coppens, Acta Cryst. 1978, A34, 909-921.

[S8]

T. Koritsnszky, T. Richter, P. Macchi, A. Volkov, C. Gatti, S. Howard, P. R.

Mallinson, L. Farrugia, Z. W. Su,N. K. Hansen, Freie Universitt Berlin, Berlin, 2003.

[S9]

C. B. Hbschle, P. Luger, B. Dittrich, J. Appl. Cryst. 2007, 40, 623-627.

[S10] B. Dittrich, C. B. Hbschle, P. Luger, M. A. Spackman, Acta Cryst. 2006, D65,

1325-1335.
[S11] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, R.J. Cheeseman,
J.A. Montgomery, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.

Hasegawa,

M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,

H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo,

R. Gomperts, R.E.

Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala,
K. Morokuma, G. A. Voth, P. Salvador, J.J. Dannenberg,

V.G.

Zakrzewski,

S.

Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick,

A.D. Rabuck, K.

Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul,

S.

Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,

I. Komaromi, R.L.

Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng,

Nanayakkara,

A.

Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M.W. Wong,

Clifford,

J.

M.

C. Gonzalez, J.A.

Pople, Gaussian 03, RevisionD.01; Gaussian Inc.: Wallingford CT, 2004.

[S12] (a) Y. Zhao, N. E. Schultz, D. G. Truhlar, J. Chem. Theory Comput. 2006, 2, 364-382;
(b) Y. Zhao, D. G. Truhlar, Acc. Chem. Res. 2008, 41, 157-167.
[S13] F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297-3305.
[S14] A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899-926.
[S15] R. F. W. Bader, Atoms in Molecules: A Quantum Theory, Oxford University
Press, Oxford, 1990.
[S16] a) AIMPAC, http://www.chemistry.mcmaster.ca/aimpac; b) A. Krapp, unpublished
results.