Inorg. Chem.

2008, 47, 4442-4444

T-Shaped Cationic CuI Complexes with Hemilabile PNP-Type Ligands

Jarl Ivar van der Vlugt,*,† Evgeny A. Pidko,† Dieter Vogt,† Martin Lutz,‡ Anthony L. Spek,‡
and Auke Meetsma§

Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Department of Chemistry and

Chemical Engineering, EindhoVen UniVersity of Technology, P.O. Box 513, 5600 MB EindhoVen,
The Netherlands, Department of Crystal and Structural Chemistry, Utrecht UniVersity,
Padualaan 8, 3584 CH Utrecht, The Netherlands, and Department of Chemical Physics, Zernike
Institute for AdVanced Materials, UniVersity of Groningen, Nijenborgh 4,
9747 AG Groningen, The Netherlands

Received February 15, 2008

The versatile coordination behavior of the PNP ligands 1A (2,6- Scheme 1. Synthesis of Complexes 2-4 with Ligands 1A/1B as Well
as Reactivity of 3B toward Additional Donor Ligands
bis[(di-tert-butylphosphino)methyl]pyridine) and 1B (2,6-bis[(diphe-
nylphosphino)methyl]pyridine) to CuI is described, whereby a
hemilabile interaction of the pyridine N-donor atom to the copper
center resulted in a rare T-shaped complex with 1A, while with
1B also a tetracoordinated species could be isolated. Theoretical
calculations support the weak interaction of the pyridine N donor
in 1A with the Cu center.

The formation of so-called T-shaped (late) transition metal

complexes has been reported for a growing number of ligand therefore set out to explore the coordination of the neutral
systems and metal centers, and these inherently electron- ligands PNPtBu (1A)6 and PNPPh (1B)2a with CuI, anticipating
deficient complexes often display interesting reactivity.1 the formation of T-shaped complexes.
Pincer ligands based on 2,6-bis(methylene-E)benzene Reaction of an equimolar amount of 1 with CuBr(SMe2)
(monoanionic upon coordination) or -pyridine (neutral), in diethyl ether yielded a bright (A) or intense yellow (B)
denoted as ECE and ENE, wherein E is a (hetero)donor atom, solid after workup (Scheme 1). Complex 2A displayed a
have become a common structural motif for the synthesis singlet at δ 46.2 (acetone-d6) in the 31P NMR spectrum (δ
of a variety of transition metal complexes. It is therefore -3.0 for 2B). Notably, the IR spectrum indicated that the
surprising that complexes with a strict trigonal T-shaped
arrangement, wherein no additional ligand is present to stabilize (2) For the PPh2-based PNP-ligand, see: (a) Dahlhoff, W. V.; Nelson,
the metal center, are very rare and, to the best of our knowledge, S. M. J. Chem. Soc. A 1971, 218, 4–2190. (b) Sacco, A.; Vasapollo,
G.; Nobile, C. F.; Piergiovanni, A.; Pellinghelli, M. A.; Lanfranchi,
have not been reported for E ) phosphorus at all. M. J. Organomet. Chem. 1988, 356, 397–409. (c) Hahn, C.; Cucciolito,
Recently, the 2,6-bis(phosphinomethyl)pyridine skeleton M.; Vitagliano, A. J. Am. Chem. Soc. 2002, 124, 9038–9039. (d)
Cochran, B. M.; Michael, F. E. J. Am. Chem. Soc. 2008, 130, 2786–
has attracted attention within the family of neutral pincer 2792.
ligands.2,3 However, to date, no single report on the chemistry (3) For PR2-based PNP-ligands, see: (a) Trovitch, R. J.; Lobkovsky, E.;
of such neutral PNP ligands with copper(I) exists.4,5 We Chirik, P. J. Inorg. Chem. 2006, 45, 7252–7260. (b) Kloek, S. M.;
Heinekey, D. M.; Goldberg, K. I. Angew. Chem., Int. Ed. 2007, 46,
4736–4738. (c) Feller, M.; Ben-Ari, E.; Gupta, T.; Shimon, L. J. W.;
* Author to whom correspondence should be addressed. E-mail: Leitus, G.; Diskin-Posner, Y.; Weiner, L.; Milstein, D. Inorg. Chem.
j.i.v.d.vlugt@tue.nl. Tel.: +31 40 2475028. Fax: +31 40 2455054. 2007, 46, 10479–10490.
†
Eindhoven University of Technology. (4) One previous report mentions the intended formation of a CuI complex
‡
Utrecht University. with a PNP ligand, but phosphine and metal oxidation occurred and
§
University of Groningen. a CuII-oxide complex was obtained: Lang, H.-F.; Fanwick, P. E.;
(1) (a) Ingleson, M.; Fan, H.; Pink, M.; Tomaszewski, J.; Caulton, K. G. Walton, R. A. Inorg. Chim. Acta 2002, 329, 9–12.
J. Am. Chem. Soc. 2006, 128, 1804–1805. (b) Eckert, N. A.; Dinescu, (5) Tetrahedral coordination of CuI to a supermesityl substituted
A.; Cundari, T. R.; Holland, P. L. Inorg. Chem. 2005, 44, 7702–7704. bis(phosphaethenyl)pyridine ligand was recently reported, see: Hayashi,
(c) Braunschweig, H.; Radacki, K.; Rais, D.; Scheschkewitz, D. Angew. A.; Okazaki, M.; Ozawa, F.; Tanaka, R. Organometallics 2007, 26,
Chem., Int. Ed. 2005, 44, 5351–5354. (d) Yamashita, M.; Hartwig, 5246–5249.
J. F. J. Am. Chem. Soc. 2004, 126, 5344–5345. (e) Stambuli, J. P.; (6) (a) Kawatsura, M.; Hartwig, J. F. Organometallics 2001, 20, 1960–
Incarvito, C. D.; Bühl, M.; Hartwig, J. F. J. Am. Chem. Soc. 2004, 1964. (b) Hermann, D.; Gandelman, M.; Rozenberg, H.; Shimon,
126, 1184–1194. L. J. W.; Milstein, D. Organometallics 2002, 21, 812–818.

4442 Inorganic Chemistry, Vol. 47, No. 11, 2008 10.1021/ic800298a CCC: $40.75  2008 American Chemical Society
Published on Web 04/29/2008
 COMMUNICATION

Figure 2. Displacement ellipsoid plots (50% probability level) of the

cationic part of complex 3A, [Cu(1A)]SbF6. The noncoordinated SbF6
Figure 1. Displacement ellipsoid plots (50% probability level) of complex counterion and hydrogen atoms are omitted for clarity. Selected atom
2A, Cu(1A)Br. Hydrogen atoms are omitted for clarity. Selected distances distances (Å) and angles (deg): Cu1-P1, 2.2211(8); Cu1-P2, 2.2215(8);
(Å) and angles (deg): Cu-P1, 2.3150(5); Cu-P2, 2.3104(5); Cu · · · N, Cu1-N1, 2.091(2); P1-C6, 1.858(3); P2-C15, 1.865(3); Cu1 · · · Sb1, 5.4520(5);
2.8938(17); Cu-Br, 2.4376(3); P1-Cu-P2, 140.75(2); P1-Cu-Br, Cu1 · · · F3, 4.400(3); P1-Cu1-P2, 172.44(3); N1-Cu1-P1, 87.22(7);
106.555(16); P2-Cu-Br, 112.658(16); P1-Cu · · · N, 70.43(5); P2-Cu · · · N, N1-Cu1-P2, 87.49(7); Cu1-P1-C6, 98.47(10); Cu1-P2-C15, 98.69(10);
70.37(5); Br-Cu · · · N, 174.03(4); Cu-P1-C6, 114.56(7); Cu-P2-C15, Cu1 · · · N1 · · · C3, 161.13(15).
115.42(7); Cu · · · N · · · C3, 133.34(8).
additional solvent molecule. Recrystallization of complex 3A
pyridine nitrogen showed variable coordination behavior from THF/pentane furnished suitable single crystals that were
toward CuI, depending on the ligand environment. For 2A, analyzed by X-ray diffraction (Figure 2). Complex 3A was
bands were observed at ν 1584 (shoulder) and 1576 cm-1 shown to crystallize in the triclinic space group P1j.
that are assigned to an uncoordinated pyridine fragment,7 Coordination of the pyridine N atom is evident from the
similar as seen for ligand 1, while for 2B, the well-separated Cu-N bond length of 2.091(2) Å, which results in a large
bands at ν 1587 and 1567 cm-1 are indicative of a true Cu-N P1-Cu-P2 angle of 172.44(3)° and N-Cu-P angles of
bonding interaction (see the Supporting Information for the 87.22(7) and 87.49(2)°. The closest Cu contact to the SbF6
molecular structure of 2B, with an intramolecular Cu-N counterion is with fluorine-atom F3, but the distance of 4.400(3)
distance of 2.160(3) Å, confirming this statement). Å is clearly outside of the bonding range. The CuI environment
Recrystallization from Et2O at -20 °C yielded yellow block- in complex 3A has approximate local C2V symmetry with a
shaped single crystals suitable for X-ray diffraction (Figure 1) T-shaped geometry around copper, somewhat related to the CuI
for complex 2A, which crystallized in the monoclinic space complex reported by Halcrow et al. featuring a bis(pyra-
group P21/c, and with Cu-P atom distances of 2.3104(5) and zolyl)pyridine ligand.9 To the best of our knowledge, this kind
2.3150(5) Å. The P1-Cu-P2 angle was found to be 140.75(2)°, of trigonal, T-shaped arrangement is unprecedented for copper(I)
leading to a distorted equilateral triangular geometry for the complexes with a P-N-P donor set, judging from a search of
copper ion. The nitrogen atom of the pyridine ring is well the Cambridge Crystal Structure Database.10
outside the bonding distance at ∼2.89 Å. Furthermore, the From the side view of complex 3A, shown in Figure 2, the
pyridine ring is tilted out of the P-Cu-P plane, as deduced nonplanar arrangement of the pyridine ring with the CuI center
from the angle Cu · · · N1 · · · C3 of 133.34(8)°. is evident, which leads to an out-of-plane distortion of ∼19°.
We wondered whether the pyridine ring might be included Arguably, this conformation may lead to unusual reactivity, due
in the coordination environment of the CuI ion in the absence to weaker (i.e., hemilabile) binding of the pyridine N atom with
of the strongly σ-donating halide coligand. This would open the Cu ion, as the π orbital of the nitrogen donor does not
up a new coordination mode if additional exogenous ligation overlap perfectly with the dxz orbital of the copper center. Niecke
could be repressed. The reaction of AgSbF6 with complex 2 et al. reported a diphosphine macrocycle incorporating two
in THF yielded complex 3 as a bright green (3A) or light- pyridine rings that showed a distorted tetrahedral or “seesaw”
yellow solid (3B) after solvent removal. Surprisingly, these geometry upon coordination to CuI.11 Ligand 1A appears to be
compounds are not very susceptible to decomposition by air.8 unable to enforce a similar stable tetracoordinate geometry; the
The 31P NMR spectrum showed signals at δ 42.6 (3A) and addition of tBuNC to a solution of 3A in THF did not induce
δ 0.5 (3B) in acetone-d6, while IR spectroscopy revealed stable coordination of the neutral coligand in the solid state.11
that the pyridine ring is coordinated to the CuI ion, with bands This most likely relates to the steric hindrance induced by the
at 1591 and 1566 cm-1 (3A) or 1596 and 1567 cm-1 (3B). phosphine groups and the resulting unfavorable crystal packing,
The 1H NMR spectrum did not indicate ligation of any
(9) Foster, C. L.; Kilner, C. A.; Thornton-Pett, M.; Halcrow, M. A.
(7) (a) Hahn, C.; Vitagliano, A.; Giordano, F.; Taube, R. Organometallics Polyhedron 2002, 21, 1031–1041.
1998, 17, 2060–2066. (b) Müller, G.; Klinga, M.; Leskelä, M.; Rieger, (10) Cambridge Crystallographic Database, February 2008.
B. Z. Anorg. Allg. Chem. 2002, 628, 2839–2846, and references (11) Ekici, S.; Nieger, M.; Glaum, R.; Niecke, E. Angew. Chem., Int. Ed.
therein. 2003, 42, 435–438.
(8) Solid samples of complexes 2 and 3 appear to be stable in air. A full (12) Coordination of tBuNC was indicated by NMR and IR spectroscopy,
investigation of the electrochemical properties of these and related but recrystallization of the green solid led to reorganization, as
compounds will be reported elsewhere. indicated by NMR spectroscopy (see the Supporting Information).

Inorganic Chemistry, Vol. 47, No. 11, 2008 4443

COMMUNICATION

Figure 4. Displacement ellipsoid plots (50% probability level) of the

cationic part of complex 5. The noncoordinated SbF6 counterion and
hydrogen atoms are omitted for clarity. Selected atom distances (Å) and
angles (deg): Cu-P1, 2.2765(8); Cu-P2, 2.2792(7); Cu-P3, 2.2391(9),
Cu-N, 2.157(2); P1-C25, 1.853(3); P2-C31, 1.853(3); P1-Cu-P2, 133.64(3);
P1-Cu-P3, 110.46(3); P2-Cu-P3, 115.84(3); N-Cu-P1, 80.99(6);
N-Cu-P2, 82.63(6); N-Cu-P3, 114.13(6), Cu-P1-C25, 97.35(8);
Figure 3. Frontier orbital plots for the (a) HOMO and (b) LUMO of Cu-P2-C31, 95.44(8); Cu-N · · · C28, 166.30(12).
complex 2A and the (c) HOMO and (d) LUMO for complex 3A, based on
DFT calculations.

as indicated also by the results of DFT B3LYP/6-31G(d)

calculations.13
The observed out-of-plane tilting of the pyridine ring is
reproduced in the calculations. There is significant σ-bonding
character of the Cu-Br bond in 2A, and the Cu-N σ Figure 5. Structural correlation of T-shaped complex 3A and distorted
interaction is nonbonding. The highest occupied molecular trigonal-pyramidal species 5 with relevant literature precedents.5,9
orbital (HOMO) for both complex 2A and 3A (Figure 3)
shows strongly bonding Cu-P interactions, whereas anti- pyramidal CuI center. The assumed T-shaped geometry
bonding character for the Cu-N interaction is observed for present in 3B clearly shows flexible behavior, but a true
the cationic fragment in 3A. The LUMO for 3A indicates a “seesaw” arrangement was not observed. Figure 5 sum-
strongly bonding interaction between Cu and N. This marizes some notable structural comparisons of complexes
indicates the hemilabile character of the Cu-N bond. 3A and 5 with CuI species based on bis(carbene)pyridine5
With strongly donating anionic ligands, the above T- and bis(phosphaalkenyl)pyridine.9
shaped geometry is not retained. Thus, the addition of 1 equiv In summary, ligand class 1 exhibits hemilabile coordina-
of KSCN to a light-green solution of 3A in THF resulted in tion of the pyridine nitrogen donor toward CuI. The selective
the rapid formation of a deep-green solution. Characterization formation of T-shaped complexes 3 is demonstrated. The
of the corresponding green solid showed that the hemilabile addition of thiocyanate disrupts the Cu-NPy bond and
Cu-NPy bond is disrupted, indicated by the diagnostic IR band regenerates a trigonal planar geometry for the CuI ion. The
for the free pyridine fragment (ν 1574 cm-1) and a bound coordination of neutral donor ligands is governed by steric
thiocyanate ligand (ν 2067 cm-1) in the solid state. The product factors; only in the case of 3B was stable coordination of
was formulated as Cu(κ2-P,P-1)(NCS), complex 4.14 PMe3 and tBuNC observed, also in the solid state. The built-
As we were unable to crystallographically characterize a in hemilabile coordinationsswitch of the PNPsligand will
tetracoordinated CuI complex supported by ligand 1A, we prove useful for catalytic applications of these CuI complexes,
turned our attention to the diphenylphosphino analogue 1B. and initial screening studies are ongoing.
Instantaneous fading of the yellow color to leave a colorless Acknowledgment. This research has been made possible
solution was evident upon the addition of 1 equiv of PMe3 by an Innovation grant (VENI) from the Dutch Research
(5) or tBuNC (6) to a solution of 3B in THF (Scheme 1), as CouncilsChemical Sciences (NWO-CW) to J.I.v.d.V. and
deduced from the respective 1H NMR spectra. Complex 6 support from Eindhoven University of Technology.
showed an IR band at ν 2177 cm-1. Furthermore, the Supporting Information Available: Experimental details for
coordination around the CuI center in complex 5 (Figure 4) complexes 2-6, molecular structures of complexes 2B and 4,
was elucidated by an X-ray crystal structure determination. computational calculations (including full citation of ref 13),
Complex 5 crystallized in the monoclinic space group P21/n crystallographic details and CIF files for compounds 2A, 2B, 3A,
with four formula units per unit cell. 4, and 5. This material is available free of charge via the Internet
The N-Cu-P1 and P1-Cu-P2 angles of 80.99(6)° and at http://pubs.acs.org.
133.64(3)°, respectively, and the observed dihedral angle IC800298A
P1-P2-Cu-P3 of 176.69(6)° give rise to a distorted trigonal-
(14) We confirmed this by an independent synthesis of 4 starting from 1A
(13) Calculations were performed at B3LYP/6-31G(d) level: Frisch, M. J.; and commercially available Cu(SCN). This complex shows distorted
et al. Gaussian 03, revision B.05; Gaussian, Inc.: Pittsburgh PA, 2003 trigonal planar geometry around the CuI, analogous to complex 2. See
(see Supporting Information for full details). Figure S2 in the Supporting Information.

4444 Inorganic Chemistry, Vol. 47, No. 11, 2008