para-Functionalized NCN-Pincer Palladium() Complexes
FULL PAPER
formed with PLATON[27] (routine DELABS, µ ϭ 3.64 mmϪ1
,
van Klink, M. Lutz, A. L. Spek, A. J. Canty, G. van Koten,
Organometallics 2001, 20, 3159Ϫ3168.
0.49Ϫ0.72 transmission). 17563 measured reflections, 3671 unique
reflections (Rint ϭ 0.0508), 2999 observed reflections [I Ͼ 2σ(I)].
178 refined parameters, 0 restraints. R (obsd. refl.): R1 ϭ 0.0254,
wR2 ϭ 0.0517. R (all data): R1 ϭ 0.0387, wR2 ϭ 0.0549. S ϭ
1.039. CCDC-187019 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
[5]
L. A. van de Kuil, H. Luitjes, D. M. Grove, J. W. Zwikker, J.
G. M. van der Linden, A. M. Roelofsen, L. W. Jenneskens, W.
Drenth, G. van Koten, Organometallics 1994, 13, 468Ϫ477.
[6] [6a]
J. W. J. Knapen, A. W. van der Made, J. C. de Wilde, P. W.
N. M. van Leeuwen, P. Wijkens, D. M. Grove, G. van Koten,
Nature 1994, 372, 659Ϫ663. [6b] A. W. Kleij, R. A. Gossage, R.
J. M. Klein Gebbink, E. J. Reyerse, N. Brinkmann, U. Kragl,
M. Lutz, A. L. Spek, G. van Koten, J. Am. Chem. Soc. 2000,
[6c]
122, 12112Ϫ12124.
M. Albrecht, N. J. Hovestad, J.
CB2 1EZ, UK; Fax: (internat.)
deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033; E-mail:
Boersma, G. van Koten, Chem. Eur. J. 2001, 7, 1289Ϫ1294. [6d]
P. J. Davies, D. M. Grove, G. van Koten, Organometallics 1997,
[6e]
16, 800Ϫ802.
M. Albrecht, R. A. Gossage, M. Lutz, A. L.
Compound 1d: C14H21BrN2OPd, M ϭ 419.64, yellow plate, 0.12 ϫ
Spek, G. van Koten, Chem. Eur. J. 2000, 6, 1431Ϫ1445. [6f] M.
˚
0.12 ϫ 0.05 mm, monoclinic, P21/c (no. 14), a ϭ 17.1168(3) A, b ϭ
D. Meijer, N. Ronde, D. Vogt, G. P. M. van Klink, G. van
Koten, Organometallics 2001, 20, 3993Ϫ4000.
˚
˚
˚
15.1078(3) A, c ϭ 12.4777(3) A, β ϭ 107.1925(12)°, V ϭ
[6g]
L. A. van de
3
-3
3082.52(11) A , Z ϭ 8, ρ ϭ 1.808 g cm . The absorption correction
was performed with PLATON[27] (routine MULABS, µ ϭ 3.79
mmϪ1, 0.68Ϫ0.82 transmission). 26887 measured reflections, 7047
unique reflections (Rint ϭ 0.0729), 5091 observed reflections [I Ͼ
2σ(I)]. 353 refined parameters, 0 restraints. R (obsd. refl.): R1 ϭ
0.0456, wR2 ϭ 0.0931. R (all data): R1 ϭ 0.0748, wR2 ϭ 0.1034.
S ϭ 1.012. CCDC-187020 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
Kuil, D. M. Grove, J. W. Zwikker, L. W. Jenneskens, W. Drenth,
G. van Koten, Chem. Mater. 1994, 6, 1675Ϫ1683. [6h] C. Patma-
manoharan, P. Wijkens, D. M. Grove, A. P. Philipse, Langmuir
1996, 12, 4372Ϫ4377.
[7] [7a]
H. P. Dijkstra, P. Steenwinkel, D. M. Grove, M. Lutz, A.
L. Spek, G. van Koten, Angew. Chem. Int. Ed. 1999, 38,
[7b]
2186Ϫ2188; Angew. Chem. 1999, 111, 2321Ϫ2324.
H. P.
Dijkstra, C. A. Kruithof, N. Ronde, R. van de Coevering, D.
J. Ramon, D. Vogt, G. P. M. van Klink, G. van Koten, J. Org.
´
Chem., in press, manuscript available on the world wide web:
[7c]
H. P. Dijkstra, M. Al-
brecht, G. van Koten, Chem. Commun. 2002, 126Ϫ127.
For an overview on homogeneous catalyst recycling using ul-
tra- and nanofiltration membranes see: H. P. Dijkstra, G. P. M.
van Klink, G. van Koten, Acc. Chem. Res. 2002, 35, 798Ϫ810.
See ref.[7b] SelRo-nanofiltration membranes (MPF-60:
MWCO ϭ 400 Dalton; MPF-50: MWCO ϭ 700 Dalton) were
purchased from Koch Membrane Systems Inc., Düsseldorf,
Germany; further product information can be found at http://
www.kochmembrane.com.
[8]
[9]
Acknowledgments
This work was supported by the Council for Chemical Sciences of
the Netherlands Organization for Scientific Research (CW/NWO)
and the Dutch Technology Foundation (STW).
[10]
P. L. Alsters, P. J. Baesjou, M. D. Janssen, H. Kooijman, A.
Sicherer-Roetman, A. L. Spek, G. van Koten, Organometallics
1992, 11, 4124Ϫ4135.
[1]
[1a]
For representative examples see:
M. Gupta, C. Hagen, R.
[11] [11a]
J. Flesher, W. C. Kaska, C. M. Jensen, Chem. Commun. 1996,
M. Q. Slagt, R. J. M. Klein Gebbink, G. van Koten, J.
2083Ϫ2084. [1b] P. Dani, T. Karlen, R. A. Gossage, S. Gladiali,
[11b]
Chem. Soc., Dalton Trans. 2002, 2591Ϫ2592.
G. Rodrıguez, R. J. M. Klein Gebbink, W. Klopper, M. Lutz,
A. L. Spek, G. van Koten, submitted.
M. Q. Slagt,
G. van Koten, Angew. Chem. Int. Ed. 2000, 39, 743Ϫ745; An-
´
[1c]
gew. Chem. 2000, 112, 759Ϫ761.
M. Ohff, A. Ohff, M. E.
[12]
van der Boom, D. Milstein, J. Am. Chem. Soc. 1997, 119,
A. W. Kleij, H. Kleijn, J. T. B. H. Jastrzebski, A. L. Spek, G.
van Koten, Organometallics 1999, 18, 277Ϫ285.
11687Ϫ11688. [1d] L. A. van de Kuil, D. M. Grove, R. A. Goss-
For the synthesis of 2 and 3d, see ref.[1d] and ref.[5], respectively.
[13]
[14]
age, J. W. Zwikker, L. W. Jenneskens, W. Drenth, G. van Koten,
[1e]
Organometallics 1997, 16, 4985Ϫ4994.
D. E. Bergbreiter, P.
´
G. Rodrıguez, M. Albrecht, J. Schoenmaker, A. Ford, M. Lutz,
L. Osburn, Y.-S. Liu, J. Am. Chem. Soc. 1999, 121, 9531Ϫ9538.
A. L. Spek, G. van Koten, J. Am. Chem. Soc. 2002, 124,
5127Ϫ5138.
[1f]
A. S. Gruber, D. Zim, G. Ebeling, A. L. Monteiro, J. Du-
[1g]
[15]
[16]
pont, Org. Lett. 2000, 2, 1287Ϫ1290.
C. Granel, Ph. Du-
P. Steenwinkel, S. L. James, D. M. Grove, N. Veldman, A. L.
Spek, G. van Koten, Chem. Eur. J. 1996, 2, 1440Ϫ1445.
D. M. Grove, G. van Koten, J. N. Louwen, J. G. Noltes, A. L.
Spek, H. J. C. J. Ubbels, J. Am. Chem. Soc. 1982, 104,
6609Ϫ6616.
This information can be obtained from the Cambridge Struc-
tural Database: F. H. Allen, O. Kennard, Chem. Des. Autom.
News 1993, 8, 1 and 31.
The DFT-B3LYP/LANL2DZ method uses density functional
theory combined with effective core potentials. The basis set
used for palladium is the Los Alamos National Laboratory set
(LANL) for effective core potentials (ECP) of double ζ type,
consisting of a small core ECP with 3s and 3p orbitals in the
valence space. The functional form used is the B3LYP, and the
relativistic correlations for heavy atoms are considered in the
ECP.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M.
A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgom-
ery Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Mil-
lam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J.
Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Po-
´ ˆ
´
bois, R. Jerome, Ph. Teyssie, Macromolecules 1996, 29,
8576Ϫ8582.
For a review about pincerϪmetal(d8) chemistry see; M. Al-
brecht, G. van Koten, Angew. Chem. Int. Ed. 2001, 40,
3750Ϫ3781; Angew. Chem. 2001, 113, 3866Ϫ3898.
[2]
[17]
[18]
[3] [3a]
F. Gorla, A. Togni, L. M. Venanzi, A. Albinati, F. Lianza,
[3b]
Organometallics 1994, 13, 1607Ϫ1616.
J. M. Longmire, X.
[3c]
Zhang, M. Shang, Organometallics 1998, 17, 4374Ϫ4379.
M. A. Stark, G. Jones, C. J. Richards, Organometallics 2000,
[3d]
19, 1282Ϫ1291.
Y. Motoyama, H. Narusawa, H. Nishi-
[3e]
yama, Chem. Commun. 1999, 131Ϫ132.
S. E. Denmark, R.
A. Stavenger, A.-M. Faucher, J. P. Edwards, J. Org. Chem. 1997,
[3f]
62, 3375Ϫ3385.
L. A. van de Kuil, Y. S. J. Veldhuizen, D.
M. Grove, J. W. Zwikker, L. W. Jenneskens, W. Drenth, W. J. J.
Smeets, A. L. Spek, G. van Koten, Recl. Trav. Chim. Pays-Bas
1994, 113, 267Ϫ277. [3g] M. Albrecht, B. M. Kocks, A. L. Spek,
G. van Koten, J. Organomet. Chem. 2001, 624, 271Ϫ286. [3h] B.
S. Williams, P. Dani, M. Lutz, A. L. Spek, G. van Koten, Helv.
Chim. Acta 2001, 84, 3519Ϫ3530.
[19]
[4]
H. P. Dijkstra, M. D. Meijer, J. Patel, R. Kreiter, G. P. M.
Eur. J. Inorg. Chem. 2003, 830Ϫ838
837