M. Frøseth et al. / Journal of Organometallic Chemistry 690 (2005) 6125–6132
6131
3
1
H, H , DiPP), 7.20 (d, J = 2.2 Hz, 1H, NCHCHN, near
3.7. X-ray crystal structure determination of Ag and Pt
complexes 4 and 6
p
3
imine), 7.17 (d, J = 2.2 Hz, 1H, NCHCHN, near N-Me),
.09 (m, 2H, H , DiPP), 4.26 (s, 3 H, N-Me), 3.22 (sept.,
7
m
J = 6.8 Hz, 2H, CHMe ), 1.41 (d, J = 6.8 Hz, 6H,
X-ray quality crystals of 4 were obtained by crystalliza-
tion from chloroform/pentane, and of 6 from a dichloro-
methane/pentane mixture. Details of the data collection
and refinement for both compounds are summarized in
Table 1 and in the supplementary material.
2
1
3
CHMe ), 0.98 (d, J = 6.8 Hz, 6H, CHMe ).
C{H}
2
2
NMR (CD CN, 50 MHz) d 164.1 (NCN), 159.7 (C@N),
3
1
43.3 (C , DiPP), 140.4 (Cipso, DiPP), 134.0 (C , Ph),
o p
1
30.7 (C , Ph), 130.1 (C , Ph), 129.4 (C , DiPP), 126.8
o
m
p
(
Cipso, Ph), 126.1 (NCCN near N-Me), 124.7 (C , DiPP),
m
1
2
1
20.4 (NCCN near imine), 39.2 (N-Me), 29.7 (CHMe ),
4. Supplementary material
2
+
4.9 and 23.6 (CHMe ). MS-ESI: m/z 486 (M ꢁ Cl,
2
ꢁ
1
00%), IR
m
1609 cm
.
Anal. Calc. for
Crystallographic data (excluding structure factors) have
been deposited as cif files with the Cambridge Crystallo-
graphic Data Centre, CCDC no. 280291 for complex 4
and 280292 for complex 6. Copies of the data may be ob-
tained free of charge from The Director, CCDC, 12 Union
C@N
C H Cl N PdCH Cl : C, 47.43; H, 4.81; N, 6.91. Found:
C, 47.18; H, 4.98; N, 6.73.
2
3
27
2
3
2
2
i
3.6. Preparation of [3-Me-1-{C(C H )N(2,6- Pr C H )}-
6 5 2 6 3
C H N ]PtMe (6)
3
2
2
2
A cooled solution (ꢁ70 ꢁC) of the silver iminoyl carbene
(122 mg, 0.250 mmol) in CH Cl (5 mL) was slowly added
4
Acknowledgments
2
2
to a cooled solution (ꢁ70 ꢁC) of Pt Me (l-SMe ) (72 mg,
2
4
2 2
0
.125 mmol). The mixture was allowed to warm to room
We gratefully acknowledge the support from Borealis
AS and the Norwegian Research Council (stipends to
M.F.) and from the Department of Chemistry, University
of Oslo (stipend to K.A.N.)
temperature before removal of CH Cl under vacuum.
2
2
The crude product was dissolved in acetonitrile and filtered
to remove AgCl. The acetonitrile was removed in vacuo and
the product was recrystallized from CH Cl /CHCl /pen-
2
2
3
tane. Yield: 98 mg (69%). The atom numbering for the
References
NMR data that follow for compound 6 refers to the num-
1
bering scheme used in Fig. 2. H NMR (CDCl3,
[1] A.J. Arduengo Jr., R.L. Harlow, M. Kline, J. Am. Chem. Soc. 113
(
1991) 361.
5
00 MHz) d 7.39 (tt, J = 7.5, 1.2 Hz, 1H, H , Ph), 7.28 (t,
p
[
[
2] A.J. Arduengo Jr., Acc. Chem. Res. 32 (1999) 913.
3] T. Weskamp, V.P.W. B o¨ hm, W.A. Herrmann, J. Organomet. Chem.
6
J = 7.9 Hz, 2H, H , Ph), 7.19 (d, J = 8.3 Hz, 2H, H , Ph),
7
m
o
.06–7.11 (m, 1H, H , DiPP), 7.03–7.11 (m, 2H, H , DiPP),
p m
00 (2000) 12.
3
6
.95 (d, J = 2.2 Hz, 1H, NCHCHN near imine), 6.71 (d,
[
4] W.A. Herrmann, Angew. Chem. Int. Ed. 41 (2002) 1290.
3
J = 2.2 Hz, 1H, NCHCHN near N-Me), 3.86 (s, 3H, N-
[5] E. Peris, R.H. Crabtree, Coord. Chem. Rev. 248 (2004) 2239.
6] N.M. Scott, S.P. Nolan, Eur. J. Inorg. Chem. (2005) 1815.
[7] M. Frøseth, A. Dhindsa, H. Røise, M. Tilset, Dalton Trans. (2003)
516.
2
[
Me), 3.05 (sept., J = 6.8 Hz, 2H, CHMe ), 1.50 (s,
J
2
1
95
(
Pt–H) = 92.0 Hz, 3H, Pt–Me cis to carbene), 1.21 (d,
4
J = 6.7 Hz, 6H, CHMe2 H16 and H18), 0.84 (d,
J = 6.9 Hz, 6H, CHMe H15 and H19), 0.21 (s, J( Pt–
H) = 63.1 Hz, 3H, Pt–Me trans to carbene).
NMR (CDCl , 75 MHz) d 190.7 ( J( Pt–C) = 837 Hz,
[
8] M. Frøseth, K.A. Netland, K.W. T o¨ rnroos, A. Dhindsa, M. Tilset,
Dalton Trans. (2005) 1664.
2
195
2
1
3
C{H}
[9] H.M.J. Wang, I.J.B. Lin, Organometallics 17 (1998) 972.
10] G. Steiner, H. Kopacka, K.-H. Ongania, K. Wurst, P. Preishuber-
Pfl u¨ gl, B. Bildstein, Eur. J. Inorg. Chem. (2005) 1325.
11] J.C.C. Chen, I.J.B. Lin, Organometallics 19 (2000) 5113.
12] E. Peris, J. Mata, J.A. Loch, R.H. Crabtree, Chem. Commun. (2001)
201.
[13] A.A.D. Tulloch, A.A. Danopoulos, G.J. Tizzard, S.J. Coles, M.B.
Hursthouse, R.S. Hay-Motherwell, W.B. Motherwell, Chem. Com-
mun. (2001) 1270.
1
195
[
3
C(carbene)), 158.9 (imine-C@N), 140.9 (C , DiPP), 139.6
o
[
[
(
Cipso, DiPP), 130.9 (C , Ph), 128.6 (Cipso, Ph), 128.5 (Cm,
p
Ph), 128.1 (C , Ph), 126.6 (C , DiPP), 123.2 (NCCN near
N-Me), 123.0 (C , DiPP), 117.7 ( J( Pt–C) = 15.7 Hz,
NCCN near imine), 37.4 (N-Me), 27.6 (CHMe ), 24.4
o
p
3
195
m
2
(
(
(
CHMe C16 and C18), 23.0 (CHMe C15 and C19), 5.6
2
2
[
14] A.A.D. Tulloch, S. Winston, A.A. Danopoulos, G. Eastham, M.B.
1
195
J( Pt–C) = 618 Hz, Pt–Me trans to carbene), ꢁ22.7
Hursthouse, Dalton Trans. (2003) 699.
[15] M. Poyatos, J.A. Mata, E. Falomir, R.H. Crabtree, E. Peris,
Organometallics 22 (2003) 1110.
16] M. Poyatos, E. Mas-Marz a´ , J.A. Mata, M. Sana u´ , E. Peris, Eur. J.
Inorg. Chem. (2003) 1215.
17] A.A. Danopoulos, J.A. Wright, W.B. Motherwell, S. Ellwood,
Organometallics 23 (2004) 4807.
1
195
J( Pt–C) = 799 Hz, Pt–Me cis to carbene). IR (CH Cl )
2
2
ꢁ
1
195
+
mC@N 1614 cm
.
MS-ESI: m/z 596 ([M( Pt)] +
1
94
+
[
MeCN ꢁ Me, 100%), 595 ([M( Pt)] + MeCN ꢁ Me,
1
94
7
(
6%).
HRMS-ESI:
Calc.
for
C H N
Pt([M
2
6
33
4
[
1
94
+
Pt)] + MeCN ꢁ Me), 595.2326. Found: 595.2350.
Anal. Calc. for C H N Pt: C, 52.62; H, 5.83; N, 7.36.
Found: C, 52.56; H, 6.01; N, 7.19.
2
5
33
3
[18] A.A. Danopoulos, J.A. Wright, W.B. Motherwell, Chem. Commun.
(2005) 784.