Conformational changes and anion-cation interactions in palladium-cyclometalated BINAP and chiraphos cationic complexes. A structural study via NMR and X-ray methods

Article abstract of DOI:10.1021/om700299b

The cyclometalated Pd complexes [Pd{(A or B)C₆H ₃CH=N(p-CH₃C₆H₄)}(BINAP)](X) (8-13; X = PF₆-, BArF, CF₃SO₃-, A, B = meta or para ring substituent), [Pd{(C₆H₄CH(CH₃)N(CH ₃)₂)}{(S)- or (R)-BINAP))KCF₃SO₃) (14a,b), and [Pd{(C₆H₄CH(CH₃)N(CH ₃)₂)}{(S,S)- or (R,R)-Chiraphos)}](CF₃SO ₃) (15a,b) have been prepared, and five of these have been studied by X-ray diffraction. NMR Overhauser measurements reveal that the chiral cyclometalated amine chelate senses the change in the chirality, for both the BINAP and the Chiraphos auxiliaries, and responds by a conformational adjustment of the ring. ¹H, ¹⁹F-HOESY data for both 14 and 15 suggest differences between the diastereomers 14a,b (and 15a,b). PGSE diffusion data for these salts are reported.

Full text of DOI:10.1021/om700299b

4942
Organometallics 2007, 26, 4942-4954
Conformational Changes and Anion-Cation Interactions in
Palladium-Cyclometalated BINAP and Chiraphos Cationic
Complexes. A Structural Study via NMR and X-ray Methods
Devendrababu Nama, Pietro Butti, and Paul S. Pregosin*
Laboratory of Inorganic Chemistry, ETH Zurich, Zu¨rich CH-8093, Switzerland
ReceiVed March 28, 2007
The cyclometalated Pd complexes [Pd{(A or B)C6H3CHdN(p-CH3C6H4)}(BINAP)](X) (8-13; X )
PF6 , BArF-, CF3SO3 , A, B ) meta or para ring substituent), [Pd{(C6H4CH(CH3)N(CH3)2)}{(S)- or
(R)-BINAP)}](CF3SO3) (14a,b), and [Pd{(C6H4CH(CH3)N(CH3)2)}{(S,S)- or (R,R)-Chiraphos)}](CF3-
SO3) (15a,b) have been prepared, and five of these have been studied by X-ray diffraction. NMR
Overhauser measurements reveal that the chiral cyclometalated amine chelate senses the change in the
chirality, for both the BINAP and the Chiraphos auxiliaries, and responds by a conformational adjustment
of the ring. 1H,19F-HOESY data for both 14 and 15 suggest differences between the diastereomers 14a,b
(and 15a,b). PGSE diffusion data for these salts are reported.
-
-
anion may (a) be a complexed ligand, (b) simply sit in an area
through which a reagent must pass in order to reach the metal
center,5b,14 or (c) simply slow the deactivation of a complex
via steric effects (e.g. steric hindrance to cluster formation).15
There are not many ways of monitoring how anions such as
CF3SO3-, PF6,- and BF4- interact with metals. However, several
groups have settled on a combination of NMR diffusion and
1H,19F-HOESY measurements as the methods of choice.16-20
The former allows one to estimate the extent of ion pairing,
whereas the latter permits a qualitative placement of the anion
in three-dimensional space. In contrast to the case for conductiv-
ity measurements, there is no solvent polarity limitation using
this NMR approach. Further, as long as the pertinent NMR
resonances are well resolved, one can obtain results for mixtures
containing a number of species.
Introduction
An increasing number of homogeneous catalysts contain
cationic transition-metal salts, e.g., in Pd-1,2 or Ru-catalyzed3
allylic alkylation, Pd-catalyzed copolymerization,4 Ru-catalyzed
Diels-Alder chemistry,5 or Ir-catalyzed hydrogenation.6 Oc-
casionally, one finds reports of an anion effect on the reaction
rate, the nature of the product, or both.7-12 Normally, there is
either a vague or no explanation for this type of anion effect.
Recently, Marks and Macchioni13 have studied how boron
reagents generate and activate Ti and Zr polymerization catalysts
by investigating the nature of the ion pairs formed. Their
explanation involves, partially, inner sphere vs outer sphere ion
pairs. However, generally speaking, it is also possible that an
(1) Helmchen, G.; Pfaltz, A. Acc. Chem. Res. 2000, 33, 336-345.
(2) Helmchen, G. J. Organomet. Chem. 1999, 576, 203-214.
(3) Trost, B. M.; Fraisse, P. L.; Ball, Z. T. A. Angew. Chem., Int. Ed.
2003, 41, 1059-1061. Trost, B. M.; Fraisse, P. L.; Ball, Z. T. Angew. Chem.,
Int. Ed. 2002, 41, 1059-1061. Hermatschweiler, R.; Fernandez, I.; Breher,
F.; Pregosin, P. S.; Veiros, L. F.; Calhorda, M. J. Angew. Chem., Int. Ed.
2005, 44, 4397-4400.
Although the anions do not usually markedly affect the ee’s
in enantioselective catalytic reactions,5,6 it would be useful to
know if (and how) the nature of a chiral pocket changes the
cation/anion interaction. To this end, we have prepared a number
of cyclometalated monocationic palladium complexes containing
(4) Gsponer, A.; Consiglio, G. HelV. Chim. Acta 2003, 86, 2170-2172.
Sirbu, D.; Consiglio, G.; Milani, B.; Kumar, P. G. A.; Pregosin, P. S.;
Gischig, S. J. Organomet. Chem. 2005, 690, 2254-2262.
(5) (a) Kundig, E. P.; Saudan, C. M.; Bernardinelli, G. H. Angew. Chem.
1999, 111, 1298-1301. (b) Kumar, P. G. A.; Pregosin, P. S.; Vallet, M.;
Bernardinelli, G.; Jazzar, R. F.; Viton, F.; Kundig, E. P. Organometallics
2004, 23, 5410-5418.
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2004, 10, 4685-4693. Mazet, C.; Smiidt, S. P.; Meuwly, M.; Pfaltz, A. J.
Am. Chem. Soc. 2004, 126, 14176-14181. McIntyre, S.; Hormann, E.;
Menges, F.; Smidt, S. P.; Pfaltz, A. AdV. Synth. Catal. 2005, 347, 282-
288.
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14884-14892.
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(9) Krossing, I.; Raabe, I. Angew. Chem., Int. Ed. 2004, 43, 2066-2090.
(10) Lancaster, N. L.; Welton, T. J. Org. Chem. 2004, 69, 5986-5992.
(11) Faller, J. W.; Fontaine, P. P. Organometallics 2005, 24, 4132-
4138.
(14) Kumar, P. G. A.; Pregosin, P. S.; Schmid, T. M.; Consiglio, G.
Magn. Reson. Chem. 2004, 42, 795-800.
(15) Martinez-Viviente, E.; Pregosin, P. S. Inorg. Chem. 2003, 42, 2209-
2214.
(16) (a) Pregosin, P. S. Prog. Nucl. Magn. Reson. Spectrosc. 2006, 49,
261-288. (b) Pregosin, P. S.; Kumar, P. G. A.; Fernandez, I. Chem. ReV.
2005, 105, 2977-2998. (c) Pregosin, P. S.; Martinez-Viviente, E.; Kumar,
P. G. A. Dalton Trans. 2003, 4007-4014.
(17) (a) Pettinari, C.; Pettinari, R.; Marchetti, F.; Macchioni, A.;
Zuccaccia, D.; Skelton, B. W.; White, A. H. Inorg. Chem. 2007, 46, 896-
906. (b) Ciancaleoni, G.; Di Maio, I.; Zuccaccia, D.; Macchioni, A.
Organometallics 2007, 26, 489-496. (c) Zuccaccia, D.; Busetto, L.; Cassani,
M. C.; Macchioni, A.; Mazzoni, R. Organometallics 2006, 25, 2201-2208.
(d) Zuccaccia, D.; Bellachioma, G.; Cardaci, G.; Zuccaccia, C.; Macchioni,
A. Dalton Trans. 2006, 1963-1971. (e) Zuccaccia, C.; Bellachioma, G.;
Cardaci, G.; Macchioni, A.; Binotti, B.; Carfagna, C. HelV. Chim. Acta
2006, 89, 1524-1546. (f) Macchioni, A. Chem. ReV. 2005, 105, 2039-
2073. (g) Zuccaccia, C.; Macchioni, A.; Orabona, I.; Ruffo, F. Organome-
tallics 1999, 18, 4367-4372 and references therein.
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10229.
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Soc. 2003, 125, 5256-5257. Zuccaccia, C.; Stahl, N. G.; Macchioni, A.;
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10.1021/om700299b CCC: $37.00 © 2007 American Chemical Society
Publication on Web 08/29/2007

Pd-Cyclometalated BINAP and Chiraphos Complexes
Organometallics, Vol. 26, No. 20, 2007 4943
Scheme 1
(primarily) various BINAP enantiomers and, to a lesser extent,
the two commercially available optically pure 2,3-bis(diphen-
ylphosphino)butane (Chiraphos) ligands (see Scheme 1). We
have chosen two different, but well-known, types of cyclo-
metalated C,N-chelates and show these precursors as I and II.
30 years,21-23 can be modified to P,C-analogues,24,25 and have
been used in a variety of applications: e.g., for chiral recogni-
tion,26 as a template,27 or in asymmetric synthesis.28
We report here aspects of the solid-state structures (for five
of these salts), NMR diffusion characteristics, and most
important, the solution structures, via 1H,1H-NOESY and 1H,19F-
HOESY data, for several CF3SO3- (triflate) salts. The observed
selective Overhauser results on the diastereomeric triflate salts
(21) Dehand, J.; Pfeffer, M. Cyclometallated Compounds. Coord. Chem.
ReV. 1976, 18, 327-352. Pfeffer, M.; Fischer, J.; Mitschler, A.; Ricard, L.
J. Am. Chem. Soc. 1980, 102, 6338. Pfeffer, M. Recl. TraV. Chim. Pays-
Bas 1990, 109, 567 and references therein.
(22) Ryabov, A. D. Chem. ReV. 1990, 90, 403.
(23) Espinet, P.; Esteruelas, M. A.; Oro, L. A.; Serrano, J. L.; Sola, E.
Coord. Chem. ReV. 1992, 15, 215 and references therein.
(24) Li, Y.; Tan, G.-K.; Koh, L. L.; Vittal, J. J.; Leung, P. H. Inorg.
Chem. 2005, 44, 9874-9886.
(25) Albinati, A.; Affolter, S.; Pregosin, P. S. Organometallics 1990, 9,
379-387.
Set I was chosen as a general model for II and because the
substituents A and B could be varied. Precursor II was selected
because of its asymmetric nature and the commercial availability
of, for example, the enantiopure R configuration. The reaction
of II with an enantiopure P chelate (R or S of the bidentate
phosphine) will afford cationic diastereomers that might differ
in their interactions with the anions. N,C-cyclopalladated
compounds of various types have been known for more than
(26) (a) Miyashita, A.; Takaya, H.; Souchi, T.; Noyori, R. Tetrahedron
1984, 40, 1245-1253. (b) Lopez, C.; Bosque, R.; Sainz, D.; Solans, X.;
Font-Bardia, M. Organometallics 1997, 16, 3261-3266. (c) Roberts, N.
K.; Wild, S. B. J. Am. Chem. Soc. 1979, 101, 6254.
(27) Qin. Y.; Lang, H.; Vittal, J. J.; Tan, G.-K.; Selvaratnam, S.; White,
A. J. P.; Williams, D. J.; Leung, P.-H. Organometallics 2003, 22, 3944-
3950.
(28) Kirsch, S. F.; Overman, L. E. J. Am. Chem. Soc. 2005, 127, 2866-
2867. Overman, L. E.; Remarchuk,. T. P. J. Am. Chem. Soc. 2002, 124,
12-13.

4944 Organometallics, Vol. 26, No. 20, 2007
Nama et al.
Table 1. 13C NMR Data for the Bound C Atom C1 in
clearly demonstrate that the anion recognizes, and adjusts to,
the chiral pocket.
Complexes 8a-15ab
Results and Discussion
The new complexes were prepared by reaction of the
appropriate bidentate phosphine with the known cyclometalated
chloro-bridged Pd(II) species, in the presence of AgX, as
indicated in Scheme 1. These salts were characterized via NMR,
X-ray, mass spectrometric, and microanalytical methods.
The 31P NMR spectra for the new salts showed AX spin
systems with two very different phosphorus chemical shifts:
e.g., for 12a, P1 at 40.8 ppm and P2 at 13.3 ppm (2JPP ) 47.8
Hz). The lower frequency resonance, P2, can be assigned to
1
the P atom trans to the σ-bound carbon donor. The H spectra
for the Schiff base complexes showed the imine proton at
relatively high frequency, e.g., for 12a, H7 at 8.05 ppm, whereas
the diastereomeric dimethylamino salts revealed three well-
resolved methyl signals in addition to the aliphatic methine CH
absorption.
a 125.8 MHz. b Conditions unless other stated: CD2Cl2, 100 MHz, 298
K.
Table 2. Bond Lengths (Å) and Bond Angles (deg) for 8a,
10a, and 14b,c
Complex 8a
Pd(1)-C(1)
Pd(1)-N(1)
2.065(4)
2.124(3)
Pd(1)-P(1)
Pd(1)-P(2)
2.2601(10)
2.3876(10)
C(1)-Pd(1)-N(1)
C(1)-Pd(1)-P(1)
N(1)-Pd(1)-P(1)
80.11(14)
92.16(11)
166.94(9)
C(1)-Pd(1)-P(2)
N(1)-Pd(1)-P(2)
P(1)-Pd(1)-P(2)
160.27(11)
98.50(9)
92.31(3)
Complex 10a
Pd(1)-C(1)
Pd(1)-N(1)
2.069(2)
2.134(2)
Pd(1)-P(2)
Pd(1)-P(1)
2.2670(6)
2.3643(6)
C(1)-Pd(1)-N(1)
C(1)-Pd(1)-P(2)
N(1)-Pd(1)-P(2)
80.39(9)
92.96(7)
167.86(6)
C(1)-Pd(1)-P(1)
N(1)-Pd(1)-P(1)
P(2)-Pd(1)-P(1)
166.13(7)
96.97(6)
91.86(2)
As expected, the 13C chemical shifts for the imine complexes
8-15 show that the Pd-bound carbon atom appears at relatively
high frequency29-31 and senses the presence of the A substituent,
in that this resonance is shifted markedly to high frequency30-32
with A ) NO2 and to lower frequency with A ) MeO (see
Table 1). Interestingly, 2J(P,C) is not markedly affected by the
A or B groups.
Complex 14b
2.026(3)
2.192(2)
Pd(1)-C(1)
Pd(1)-N(1)
Pd(1)-P(2)
Pd(1)-P(3)
2.2616(6)
2.4182(7)
C(1)-Pd(1)-N(1)
C(1)-Pd(1)-P(2)
N(1)-Pd(1)-P(2)
78.74(10)
90.39(8)
162.77(7)
C(1)-Pd(1)-P(3)
N(1)-Pd(1)-P(3)
P(2)-Pd(1)-P(3)
171.30(9)
101.46(7)
91.31(2)
Complex (R,S)-14c
2.043(4)
2.181(4)
Solid-State Structures. Table 2 gives selected bond lengths
Pd(1)-C(1)
Pd(1)-N(1)
Pd(1)-P(2)
Pd(1)-P(1)
2.2653(11)
2.4100(11)
-
(Å) and bond angles (deg) for the Pd(rac-BINAP) CF3SO3
salts of the imine derivatives 8a and 10a, as well as for the
Pd(R-cyclometalated amine)((R)-BINAP) diastereomer 14b and
the R, rac combination 14c. The first descriptor refers to the
amine (and is always R) and the second to the phosphine.
Figures 1-4 show ORTEP views of these salts. The X-ray data
for a fifth salt, 15a, afforded a clear result for the cation (see
Figure 5); however, a suitable solution for the disorder in the
anion could not be found.
The four cations 8a, 10a, and 14b,c reveal a local distorted-
square-planar geometry about the palladium atom. Within each
cation, the two Pd-P separations are quite different. The Pd-P
distance trans to the carbon is seen to be ca. 0.10-0.15 Å, longer
than that found for the Pd-P distance trans to the nitrogen atom.
We note that for 14b the Pd-P separation of ca. 2.42 Å lies at
C(1)-Pd(1)-N(1)
C(1)-Pd(1)-P(2)
N(1)-Pd(1)-P(2)
79.38(16)
92.82(13)
164.42(12)
C(1)-Pd(1)-P(1)
N(1)-Pd(1)-P(1)
P(2)-Pd(1)-P(1)
170.72(11)
97.97(10)
91.75(4)
Complex (R,R)-14c
2.035(4)
2.187(3)
Pd(2)-C(55)
Pd(2)-N(2)
Pd(2)-P(4)
Pd(2)-P(3)
2.2531(10)
2.3968(10)
C(55)-Pd(2)-N(2)
C(55)-Pd(2)-P(4)
N(2)-Pd(2)-P(4)
78.69(14)
91.36(11)
159.46(10)
C(55)-Pd(2)-P(3)
N(2)-Pd(2)-P(3)
P(4)-Pd(2)-P(3)
170.27(11)
100.29(9)
92.48(3)
the upper end of the range for this type of bond. Moreover, this
value is significantly larger than the analogous distance found
in 10a, ca. 2.36 Å, suggesting a stronger trans influence for the
aliphatic carbon donor. The Pd-N and Pd-C bond lengths are
consistent with the literature values.33 As expected, the N-Pd-C
angle from the five-membered ring is relatively small, ca. 79-
80°, whereas the P-Pd-P angles are all slightly larger than
90°. This latter angle is typical for the BINAP chelate.34 Figures
(29) Mann, B. E.; Taylor, B. F. 13C NMR Data for Organometallic
Compounds; Academic Press: London, 1981.
(30) Tschoerner, M.; Kunz, R. W.; Pregosin, P. S. Magn. Reson. Chem.
1999, 37, 91-97.
(31) Tschoerner, M.; Pregosin, P. S. Inorg. Chim. Acta 1999, 290, 95-
99.
(32) Martinez-Viviente, E.; Pregosin, P. S.; Tschoerner, M. Magn. Reson.
Chem. 2000, 38, 23-28.
(33) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson, D.
G.; Taylor, R. J. Chem. Soc., Dalton Trans. 1989, S1-S83.

Pd-Cyclometalated BINAP and Chiraphos Complexes
Organometallics, Vol. 26, No. 20, 2007 4945
the model Pd(rac-BINAP)(MeO-Schiff base) salts 11a-c, which
contain CF3SO3-, BArF-, and PF6- as anions, respectively. For
1
all three salts there are numerous H,19F contacts, and indeed
these three differ, but not dramatically. The strongest contacts
stem from a number of PPh2 BINAP protons, as previously
described.36 In addition, the relatively small PF6 anion (right
-
trace) “sees” the MeO group, the Schiff base ring protons H5,
H9, and H10 and the imine proton H7. There is no contact to
the aromatic methyl group. This suggests that this anion is trying
to position itself close to the partial positive charges on the imine
N, Pd, and P atoms. For the slightly larger CF3SO3- anion (left
trace) we find contacts to the MeO group, the Schiff base ring
protons H2, H3, H5, H9, and H10 and the imine proton H7,
plus a number of interactions with the PPh2 BINAP protons.
As before, there is no contact to the aromatic methyl group;
however, as the triflate is slightly larger and the F atoms
somewhat remote from the O atoms bearing the negative charge,
we now have contacts to H2 and H3 (see arrow in the figure).
These results are consistent with the same type of approach as
Figure 1. ORTEP view of the cation of 8a with thermal ellipsoids
drawn at the 30% probability level (the solvent molecules are
omitted for clarity).
for the PF6 anion. For the even larger BArF- anion (center
-
trace), we find contacts to the MeO group, the para methyl
group, the Schiff base ring protons H2, H3, H5, H9, and H10,
and the usual PPh2 BINAP protons; however, the contact to
the imine proton H7 is absent. The larger BArF anion, with its
meta CF3 groups, stretches far enough to approach the para
methyl group but is now slightly further from the imine proton
H7. We conclude that in solution, for 8a and 10a, the anions
prefer to be localized close to the partially positive coordinated
imine, Pd, and P moieties. These observations do not reflect
directly on the amount of ion pairing (see the diffusion
discussion below) but rather on the fact that these anions can
approach the cation in a similar way.
(b) Cyclometalated Amine Salts. For the chiral amine salts
14a,b and 15a,b, the interpretation of the 1H,19F-HOESY results
rests on the assignment of the three methyl resonances. The
Figure 2. ORTEP view of the cation of 10a with thermal ellipsoids
drawn at the 30% probability level (the solvent molecules are
omitted for clarity).
3-5 give views of several of the five-membered N,C-chelate
rings. As expected, this ring is not planar, and this subject will
be extended in the solution discussion.
We note further that the coordinated BINAP ligands dem-
onstrate the usual34,35 pseudo-axial and pseudo-equatorial P-
phenyl rings and that both rings for the Schiff base do not lie
in the same plane. Figures 1-4 suggest that the CF3SO3- anion
is localized near the nitrogen chelate, and we shall address this
point via the HOESY results that follow.
correct assignment of the two N-methyl groups CH3′ (somewhat
closer to the aliphatic methyl) and CH3 (proximate to the
methine CH) is crucial, since we expect that the anion may
approach the cation via the amine moiety, in analogy to the
results described above. The assignment of the aliphatic methyl
signal is trivial, as it is spin-spin coupled to the adjacent
methine CH and appears as a sharp doublet. The differentiation
between NCH3′ and NCH3 was not straightforward and was
made primarily using 1H,1H Overhauser measurements, together
with 31P spin coupling data. The two N-methyl groups reveal
very different and characteristic line shapes. 31P,1H correlations
(see Figure 7) reveal that the broad “triplet” shape associated
with an N-methyl group stems from long-range 31P spin-spin
coupling to two P atoms, and this was interesting but deceptive.37
Figure 8 shows NOE results for the (R,S)- and (R,R)-BINAP
diastereomers 14a,b. The selectivity shown from these NOE
data (note the absences indicated by the circles) suggests that
the conformation of the five-membered metallacycle ring
changes with the chirality of the BINAP. For the R,S diastere-
Overhauser Spectroscopy. (a) Cyclometalated Imine Salts.
1
Figure 6. shows H,19F-HOESY results in CDCl3 solution for
(34) (a) Ohta, T. H. T.; Noyori, R. Inorg. Chem. 1988, 27, 566-569.
(b) Mashima, K.; Kusano, K.; Ohta, T.; Noyori, R.; Takaya, H. J. Chem.
Soc., Chem. Commun. 1989, 1208. (c) Pathak, D. D.; Adams, H.; Bailey,
N. A.; King, P. J.; White, C. J. Organomet. Chem. 1994, 479, 237. (d)
Zhang, X.; Mashima, K.; Koyano, K.; Sayo, N.; Kumobayashi, H.;
Akutagawa, S.; Takaya, H. J. Chem. Soc., Perkin Trans. 1994, 2309-2322.
(e) Brown, J. M.; Torrente, J. J. P. Organometallics 1995, 14, 1195-1203.
(f) Wiles, J. A.; Lee, C. E.; McDonald, R.; Bergens, S., H. Organometallics
1996, 15, 3782-3784.
(35) Ruegger, H.; Kunz, R. W.; Ammann, C. J.; Pregosin, P. S. Magn.
Reson. Chem. 1991, 29, 197-203. Ammann, C. J.; Pregosin, P. S.; Ruegger,
H.; Albinati, A.; Lianza, F.; Kunz, R. W. J. Organomet. Chem. 1992, 423,
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J. Organometallics 2006, 25, 4596-4604.

4946 Organometallics, Vol. 26, No. 20, 2007
Nama et al.
Figure 3. (left) ORTEP view of the cation of 14b with thermal ellipsoids drawn at the 30% probability level and (right) a section showing
the five-membered cyclometalated ring.
Figure 4. (top) ORTEP views of the cations of 14c with thermal ellipsoids drawn at the 30% probability level and (bottom) sections
showing the five-membered cyclometalated rings for the two cations (the anions are not shown for clarity).
Chart 1. Structural Fragment of 16a
omer, the N atom is placed slightly above the plane defined by
the Pd and the three carbon atoms, see the sketch in Chart 1).
This places the C-Me group in a pseudo-trans position relative
to the NCH3 (and thus one finds no NOE between these two
groups) but proximate to NCH3′, and the arrow in the sketch
indicates this NOE contact. For the R,R diastereomer, the N
atom is placed slightly below the plane defined by the Pd and
the three carbon atoms (see the sketch in Chart 2). This places
the C-Me group roughly equidistant from both the NCH3 and
the NCH3′ moieties, with the result that two fairly strong
a The bold line in the right-hand sketch represents the plane defined
by the Pd and the three carbon atoms.
interactions (see arrows) are observed. In line with this proposal
are the selective NOE’s from the methine CH proton: one each
to the NCH3 and the NCH3′ groups in 16 and only one to the
NCH3 in 17. Exactly these two specific ring conformations are
found in the solid-state structures, and we show these in Figures
3-5. It is interesting that both amine ring conformations are
found for the two diastereomers of the racemic BINAP of 14c
(37) The difference in the line shape stems from the dependence of
4J(P,H) on the relative position of the NMe and NMe′ groups. However,
since the change from, for example, (R)-BINAP to (S)-BINAP changes the
amine ring conformation and consequently the relative positions of these
two NMe groups, in one diastereomer the NMe appears as a triplet whereas
in the other diastereomer the NMe′ is now the triplet.

Pd-Cyclometalated BINAP and Chiraphos Complexes
Organometallics, Vol. 26, No. 20, 2007 4947
Figure 5. ORTEP view of the cation of 15a with thermal ellipsoids drawn at the 30% probability level and section showing the five-
membered cyclometalated ring.
Figure 6. 1H,19F HOESY NMR spectra for the complexes 11a (left), 11b (middle), and 11c (right) in CDCl3. The spectra show selective
strong contacts primarily to the P-phenyl ring protons as well as contacts to the cyclometalated ligand. In complex 11b, one finds a contact
to the para methyl group and not to the imine (H7) proton (400 MHz, 298 K).
(see Figure 4). Moreover, the solid-state data showsif one
defines a plane made up of the metal, the two C atoms of the
metalated ring C1 and C6, and the methine CH atom C7sthat
in one diastereomer the N1 atom lies 0.75 Å below this plane,
whereas in the second diastereomer, the N2 atom lies 0.87 Å
above this plane.
Figure 8): e.g., for the R,R diastereomer two of these are found
at lower frequency. Possibly, this change in amine ring
conformation, as a function of the shape of the chiral pocket,
relieves unfavorable steric interactions between the PPh2 groups
from P2 (trans to the C donor) and the two proximate N-methyl
groups.
Furthermore, the changes in ring conformation are ac-
companied by selective anisotropic effects from the P-phenyl
array on the chemical shifts of the three methyl groups (see
The shapes and relative positions of the chiral arrays
containing the four P-phenyl groups of complexed (S)- and (R)-
BINAP are shown in 18 and 19, respectively, and these have
been defined by both NMR and X-ray measurements a number
of times.34-36,38,39
Figure 9 gives the 1H,19F-HOESY results in CDCl3 solution
for the BINAP salts 14a-c. The strongest contacts arise from
the protons of the P-phenyl groups; however, there is a great
Chart 2. Structural Fragment of 17

4948 Organometallics, Vol. 26, No. 20, 2007
Nama et al.
Figure 7. Sections of 31P,1H COSY spectra for the complexes (top)
14a (CD2Cl2, 500 MHz, 298 K) and (bottom) 15b (CDCl3, 300
MHz, 298 K), each showing two 31P contacts to the methyl 8-CH3′
and 8-CH3 respectively, thereby explaining the observed triplet
multiplicity.
deal of selectivity. The contacts for (R,R)-14b are not as
numerous and are ca. twice as strong as for (R,S)-14a. In 14b,
there are six fairly strong interactions stemming from the
methine CH and five aromatic protons of the BINAP and several
weaker contacts from the cyclometalated ring.40 In 14a, the
contact to the methine CH bond in is now Very weak (and easily
missed). For the R,rac BINAP mixture (far right trace), only
-
the cross-peaks from the CF3SO3 anion to those of the R,R
diastereomer CH and the Me protons are readily observed. This
is partly because the strong signals from 14b mask the weaker
ones from 14a. In any case, the measurement of the racemic
mixture, alone, would not have afforded a clear picture of how
the triflate anion interacts with the two diastereomeric cations.
In summary, these two diastereomers do not show identical
1H,19F-HOESY contacts.
Figure 8. Sections of the 1H,1H NOESY spectra for the complexes
(top) 14a (CD2Cl2, 500 MHz) and (bottom) 14b (CDCl3, 400 MHz),
showing selective NOE contacts in both cases. Blank circles indicate
no contact and suggest a specific conformation.
1
The H,19F-HOESY results for the Chiraphos salts 15a,b in
For the Chiraphos diastereomeric pair 15a,b, the 1H,1H NOE’s
(see the Supporting Information) indicate that, for these salts
as well, the nature of the five-membered metallacycle ring
changes with the chirality of the Chiraphos ligand. The salt 15a
(R,2S,3S) shows the conformation 16; however, for the salt 15b
(R,2R,3R) the situation is somewhat different but is in line with
the literature.41 For 15b, in contrast to 14b, one finds a somewhat
more flexible five-membered-ring conformation on the basis
of the observed NOE’s.41 This is interesting and suggests that
each enantiomer of BINAP can induce a more decisive
conformational change, whereas this is not completely true for
both forms of Chiraphos.
CDCl3 solution (Figure 10) are simpler relative to the BINAP
analogues. In the R,S,S salt (left trace), one finds major contacts
to a P-phenyl set and modest cross-peaks42 arising from the
NCH3′ and NCH3 groups. As in 15a, we do not observe a
contact to the methine CH signal. In the R,R,R salt 15b (right
trace) the contacts are more numerous. One finds several strong
contacts from the P-phenyl groups42 plus interactions with the
three methyl groups and the methine CH group. Once again,
we observe differences between the diastereomers.
1
Summarizing this section, we note that the observed H,19F
HOESY contacts are (a) different for the two Binap-based
diastereomers 14a,b, (b) also different for the Chiraphos
diastereomeric pair 15a,b, and (c) somewhat similar for 14a
and 15a (as well as 14b and 15b). The source of the difference
might involve a different position of the anion, relative to the
cation; however, the exact structures are not proven. There are
several literature examples in which the anion can be shown to
take up specific positions.16,17e-g
(38) Wiles, J. A.; Bergens, S. H. Organometallics 1999, 18, 3709-3714.
(39) Drago, D.; Pregosin, P. S.; Tschoerner, M.; Albinati, A. J. Chem.
Soc., Dalton Trans. 1999, 2279-2280.
(40) Despite a significant spectroscopic effort, it was not possible to
assign each BINAP proton unambiguously. Considerable overlap led to an
element of uncertainty with respect to the HOESY contacts.
(41) McFarlane and co-workers (McFarlane, W.; Swarbrick, J. D.;
Bookham, J. L. J. Chem. Soc. Dalton 1998, 3233-3238) report (almost)
an average of the two conformations for this diastereomer. Our proton
spectra and observed NOE results are in agreement with their data. See
also Jiang, O.; Ru¨egger, H.; Venanzi, L. M. J. Organomet. Chem. 1995,
488, 233-240, for related findings.
Diffusion Data. Tables 3 and 4 give PGSE diffusion data
(D values) for the cations and anions of the complexes 8-13
(42) There is a very weak contact to the Chiraphos methyl groups. The
chiral array does not show marked axial or equatorial P-phenyl groups.

Pd-Cyclometalated BINAP and Chiraphos Complexes
Organometallics, Vol. 26, No. 20, 2007 4949
Figure 9. 1H,19F HOESY spectra for the complexes 14a (left), 14b (middle), and 14c (right, with rac-BINAP) in CDCl3, all showing
selective strong contacts primarily to the BINAP P-phenyl ring protons. One finds medium to weak contacts to the chiral amine cyclometalated
ligand protons H7 and H8 in 14a,b and selective contacts in 14c (400 MHz, 298 K). The stars and crosses in the spectrum of 14c indicate
the signals from the individual diastereomers.
The calculated hydrodynamic radii,44 rH, are in good agree-
ment with the rX-ray values estimated from the solid-state
measurements. From Table 3, one finds that the D values for
the CF3SO3- and PF6- anions are similar, and from Table 4, as
expected, it is clear that complexes 14 are somewhat larger than
complexes 15. If we assume an rH value of ca. 5.9 Å for the
solvated BArF anion,16a then the ca. rH value of 6.5 Å for the
BArF- anion in 8-13 in CD2Cl2 solution, given in Table 3, is
suggestive of ca. 10% ion pairing: i.e., very modest but not
zero ion pairing for this anion. This estimation, in conjunction
with the NOE data, serves as a reminder that the observation
of strong HOESY contacts does not imply strong ion pairing
but, rather, that the anion can approach the cation.
Conclusions
We find that the chiral organometallic amine chelate recog-
nizes the change in the sense of the chirality, for both the BINAP
and the Chiraphos auxiliaries, and responds by a conformational
adjustment. Associated with this is a change in the approach of
the CF3SO3- anion toward the positively charged centers. The
Figure 10. 1H,19F HOESY spectra for complexes 15a (left) and
conformational change of the amine ring was easily detected
15b (right) in CDCl3, both showing selective strong contacts
via intramolecular proton-proton NOE data. It was not possible
primarily to the Chiraphos ortho P-phenyl ring protons. One finds
selective medium to weak contacts to the chiral amine cyclometa-
lated ligand protons H7 and H8 in 15a,b (400 MHz, 298 K).
(43) This assumes (a) that other interactions are absent, e.g., hydrogen
bonding, anion encapsulation, etc., which would result in restricted
translation of the anion, and (b) that the two ions are markedly different in
size.
and 14 and 15, respectively, in CD2Cl2 and CDCl3 solutions.
As in previous studies, we assign ca. 100% ion pairing to a salt
when the individual D values for the cation and anion are
identical, within experimental error.43 In all cases there is much
more ion pairing in CDCl3 solution. Further, for 8-13, in CD2-
Cl2 solution, the ion pairing seems to be more or less
independent of the substituents A and B. For 14 and 15, we do
not find a dependence of the D values on the sense of the
chirality.
(44) From the diffusion coefficients it is possible to obtain the so-called
hydrodynamic radius, rH, via the Stokes-Einstein equation rH ) kT/6πηD,
which, in turn, allows one to estimate the molecular volume. This equation
is useful, as it allows one to correct for the solvent viscosity, η; however,
the equation has been criticized, and the literature suggests that the value
“6” should be corrected to some smaller value which takes into consideration
the volume of the solvent. For a few cases we have made this correction,
and these rH values are given in parenthesis under the values calculated
using “6”. These “corrected” larger values are likely to be more realistic
and are often in better agreement with rX-ray
.

4950 Organometallics, Vol. 26, No. 20, 2007
Table 3. Diffusion Constantsa and Radiib for Complexes 8-13
Nama et al.
-
-
CF3SO3
BArF-
PF6
cation (1H)
H (rH)
anion (19F)
cation (1H)
rH (rH)
In CD2Cl2
anion (19F)
cation (1H)
anion (19F)
compd
D
r
rX-ray
D
r
H (rH)
D
D
rH
D
r
H (rH)
D
rH (rH)
8
9
10
11
12
13
7.83
7.74
7.73
7.69
7.94
7.75
6.8 (7.2)
6.8
6.8 (7.3)
6.9
6.7
6.8
7.0
7.1
12.91
12.72
12.46
12.84
12.98
12.30
4.1 (5.0)
4.2
4.2 (5.2)
4.1
4.1
4.3
7.54
7.42
7.48
7.41
7.61
7.69
7.0
7.1
7.1 (7.5)
7.1
7.0
8.14
8.12
8.20
8.10
8.20
8.23
6.5
6.5
6.5 (7.0)
6.5
6.5
7.66
7.71
6.9 (7.4)
6.9
12.65
14.19
4.2 (5.1)
4.0
6.9
6.4
In CDCl3
10
11
5.49
5.62
7.5 (8.0)
7.3
5.78
6.06
7.1 (7.6)
6.8
4.85
4.95
8.5 (8.9)
8.3
5.00
5.21
8.2 (8.6)
7.9
5.66
5.68
7.2 (7.8)
7.2
5.95
6.15
6.9 (7.4)
6.7
a Conditions: 400 MHz, 2 mM. D values are given in 10-10 m2 s-1 b rH values are given in Å; “c” corrected rH values are given in parentheses. rvdw
. )
2.49 Å (CD2Cl2), rvdw) 2.60 Å (CDCl3), η(CH2Cl2) ) 0.414 × 10-3 kg m-1 s-1, η(CHCl3) ) 0.534 × 10-3 kg m-1 s-1 at 299 K.
Table 4. Diffusion Constantsa and Radiib for Complexes 14 and 15 in CD2Cl2 and in CDCl3.
CD2Cl2
CDCl3
cation (1H)
H (rH)
anion (19F)
cation (1H)
rH (rH)
anion (19F)
rH (rH)
compd
confignc
a (R,S)
b (R,R)
c (R,rac)
D
r
rX-ray
D
r
H (rH)
D
D
14
8.24
8.16
8.11
8.18
8.86
8.86
6.4
6.5 (7.0)
6.5
6.5
6.0 (6.5)
6.0
13.04
12.58
13.04
4.1
4.2 (5.1)
4.1
5.86
5.97
5.97
5.88
6.30
6.30
7.0
6.9 (7.4)
6.9
7.0
6.5 (7.1)
6.5
6.27
6.17
6.24
6.5
6.6 (7.2)
6.6
6.9
15
a (R,2S,3S)
b (R,2R,3R)
12.70
12.65
4.2 (5.1)
4.2
6.68
6.53
6.1 (6.8)
6.2
a Conditions: 400 MHz, 2 mM. D values are given in 10-10 m2 s-1 b rH values are given in Å; “c” corrected rH values are given in parentheses. rvdw
. )
2.49 Å (CD2Cl2), rvdw ) 2.60 Å (CDCl3), η(CH2Cl2) ) 0.414 × 10-3 kg m-1 s-1, η(CHCl3) ) 0.534 × 10-3 kg m-1 s-1 at 299 K. c The first configuration
refers to the asymmetric carbon in the cyclometalated ring, and the second configuration refers to the BINAP ring.
were recorded with Bruker DPX-250, 300, 400, 500, and 700 MHz
spectrometers at room temperature unless otherwise noted. Elemen-
tal analysis and mass spectra were performed at the ETH Zu¨rich.
to unambiguously define the interplay between the anion and
cation, although some interesting selectivity exists.
We believe that the NOE observations will eventually prove
helpful in understanding how chiral auxiliaries affect structural
changes and thus influence the outcome of enantioselective
reactions. It is now well documented that a prochiral substrate,
e.g., an olefin capable of forming a chelate ring, may complex
either the re or si face and that the chiral pocket assists in this
selection process. However, it is not obvious that the chiral
pocket might be able to induce a change in the conformation
of such a chelate ring. Further, from this and earlier studies, it
is now becoming clear that noncoordinating anions (a) can be
selective in their approach to a metal center and (b) do not all
demonstrate the same degree of ion pairingsand this is
especially true for the commonly used BArF- anion.
Diffusion Measurements. All of the PGSE measurements were
carried out using the stimulated echo pulse sequence and performed
on a 400 MHz Bruker Avance spectrometer, equipped with a
microprocessor-controlled gradient unit and a multinuclear inverse
probe with an actively shielded Z-gradient coil. The shape of the
gradient pulse was rectangular, and its length was 1.75 ms. The
gradient strength was incremented in 4% steps from 4% to 60%,
so that 12-15 points could be used for regression analysis. The
time between midpoints of the gradients was 167.75 ms, and the
gradient recovery time was set at 100 µs for all experiments. All
1
of the diffusion H spectra were acquired using 16K points, 16
transients, a 5 s relaxation delay, and a 1.5 s acquisition time. All
of the 19F spectra were acquired using 16K points, 16 or 8 transients,
a relaxation delay of 5T1 (approximately 15-20 s), and a 4 s
acquisition time. Spin-lattice relaxation times (T1) were measured
Experimental Section
1
using the standard inversion-recovery method. Both the H and
General Comments. All air-sensitive manipulations were carried
out under a nitrogen atmosphere. All solvents were dried over an
appropriate drying agent and then distilled under nitrogen. Deu-
terated solvents were dried by distillation over molecular sieves
and stored under nitrogen. The ligands rac-BINAP (Strem), (R)-
BINAP and (S)-BINAP (Alfa Aesar), (R)-(+)-N,N-dimethyl-1-
phenylethylamine (Aldrich), (2R,3R)-Chiraphos and (2S,3S)-
Chiraphos (Acros), and silver salts (Aldrich) were purchased from
commercial sources and used as received. The chloro-bridged metal
complexes (PdClL)2 (1-6; L ) cyclometalated ligands (Schiff
base)), and the R or S N,N-dimethyl-1-phenylethylamine complex
7 were synthesized according to known literature procedures.45,46
The complexes 14 and 15 have been reported by Noyori26a and
McFarlane, respectively.41 1H, 31P, 13C, 19F, and 2D NMR spectra
19F diffusion experiments were processed using Bruker software
with an exponential multiplication (EM) window function and a
line broadening of 1.0 Hz. The measurements were carried out
without spinning at a set temperature of 299 K within the NMR
probe. As indicated in Tables 3 and 4, diffusion values were
measured on 2 mM CD2Cl2 and CDCl3 solutions. Cation diffusion
1
rates were measured using the H signal from the methyl protons
of either the N,N-dimethyl-1-phenylethylamine or Schiff base.
Anion diffusion data were obtained from the 19F resonances. The
solvent viscosities used for the calculation of rH were 0.414 and
0.534 for CD2Cl2 and CDCl3, respectively.
1
NOE Measurements. The H,1H NOESY NMR experiments
were acquired by the standard three-pulse sequence (noesyph) using
a 600 ms or 1 s relaxation delay and a 600 ms mixing time on a
Bruker spectrometer at a set temperature of 298 K with phase
cycling by the TPPI method. Typically, 16 transients (DS 16) were
acquired into 2K data points for each of the 512 values of t1. A
(45) Albinati, A.; Pregosin, P. S.; Ruedi, R. HelV. Chim. Acta 1985, 68,
2046-2061.
(46) Cope, A. C.; Friedrich, E. C. J. Am. Chem. Soc. 1968, 90, 909.

Pd-Cyclometalated BINAP and Chiraphos Complexes
Organometallics, Vol. 26, No. 20, 2007 4951
QSINE weighting function was used in each dimension prior to
Fourier transformation into a 2K × 1K data matrix. The spectral
width in each dimension was 5000 Hz, and the transmitter was set
at the center of the range. The 19F,1H-HOESY NMR experiments
were acquired using the standard four-pulse sequence (invhoesy)
with either a 600 or 800 ms mixing time. The doubly tuned TXI
probe head of the 400 MHz spectrometer was set at 298 K. The
experiment was carried out using phase cycling by the TPPI method
(pulse width: F1, 4000 Hz; F2, 1132.2 Hz). Typically, 16 transients
(DS 4) were acquired into 2K data points for each of the 512 or 1
K values of t1. A QSINE and EM weighting functions (F1 and F2
dimensions, respectively) were used prior to Fourier transformation
into a 2K × 1K data matrix. The delay between increments was
set to 2 s.
[Pd(rac-BINAP)(C14H11ClN)][BArF] (9b). To 1 equiv of [Pd-
(µ-Cl)(C14H11ClN)]2 (19.6 mg, 741.14 g mol-1, 30.7 × 10-3 mol)
were added 2 equiv of rac-BINAP (32.9 mg, 622.67 g mol-1, 53.0
× 10-3 mol) and 2 equiv of NaBArF (46.8 mg, 886.21 g mol-1
,
53.0 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C90H55BClF24NP2-
Pd] (9b): 91 mg, 0.0499 mol, 94%. Anal. Found (calcd) for [Pd-
(rac-BINAP)(C14H11ClN)][BArF]: C, 59.38 (59.36); H, 3.25 (3.04);
1
N, 0.82 (0.77). H NMR (CD2Cl2, 400 MHz, 25 °C): δ 2.07 (s,
4
3H), 6.15-8.30 (m, aromatic), 8.06 (d, JHP-trans ) 6.0 Hz). 31P-
2
{1H} NMR (CD2Cl2, 161 MHz, 25 °C): δ 13.7 (d, AB spin, JPP
2
) 47 Hz), 40.8 (d, AB spin, JPP ) 47 Hz). 19F NMR (CD2Cl2,
376.5 MHz, 25 °C): δ -63.3 (s). 13C{1H} NMR (CD2Cl2, 100
MHz, 25 °C): δ 20.8 (s, CH3), 115.4-178.0 (aromatic), 178.8 (t,
[Pd(rac-BINAP)(C15H14N)][CF3SO3] (8a). To 1 equiv of [Pd-
(µ-Cl)(C15H14N)]2 (33.4 mg, 700.3 g mol-1, 47.7 × 10-3 mol) were
added 2 equiv of rac-BINAP (59.4 mg, 622.67 g mol-1, 95.4 ×
10-3 mol) and 2 equiv of AgOTf (24.5 mg, 256.94 g mol-1, 95.4
× 10-3 mol) in dichloromethane. The reaction mixture was stirred
at 25 °C for 3 h. The resulting yellow solution was separated from
the solid and reduced in vacuo. The product was recrystallized by
dissolving in the minimum volume of dichloromethane and layering
with hexane, affording 8a as yellow crystals. Yield of [C60H46F3-
NO3P2PdS] (8a): 90 mg, 0.083 mol, 87%. Anal. Found (calcd) for
[Pd(rac-BINAP)(C15H14N)][CF3SO3]‚H2O: C, 65.16 (65.25); H,
1
dCH, JCP ) 4.0 Hz). MS (MALDI; m/z): M+ 958.2.
[Pd(rac-BINAP)(C14H11N2O2)][CF3SO3] (10a). To 1 equiv of
[Pd(µ-Cl)(C14H11N2O2)]2 (29.3 mg, 762.24 g mol-1, 38.4 × 10-3
mol) were added 2 equiv of rac-BINAP (47.9 mg, 622.67 g mol-1
,
76.9 × 10-3 mol) and 2 equiv of AgOTf (19.8 mg, 256.94 g mol-1
,
76.9 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. The product was recrystallized
by dissolving in the minimum volume of dichloromethane and
layering with hexane, affording 10a as yellow crystals. Yield of
[C59H43F3N2O5P2PdS] (10a): 79 mg, 0.071 mol, 92%. Anal. Found
(calcd) for [Pd(rac-BINAP)(C14H11N2O2)][CF3SO3]: C, 62.89
(63.42); H, 4.12 (3.88); N, 2.51 (2.51). 1H NMR (CD2Cl2, 400 MHz,
25 °C): 2.09 (s, 3H), 6.15-8.30 (m, aromatic), 8.26 (dd, 4JHP-trans
) 6.4 Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C): δ 14.1 (d,
AB spin, 2JPP ) 47 Hz), 40.1 (d, AB spin, 2JPP ) 47 Hz). 19F NMR
(CD2Cl2, 376.5 MHz, 25 °C): δ -79.3 (s). 13C{1H} NMR (CD2-
Cl2, 100 MHz, 25 °C): δ 20.9 (s, CH3), δ 115.4-178.0 (aromatic),
1
4.35 (4.38); N, 1.27 (1.27). H NMR (CD2Cl2, 400 MHz, 25 °C):
δ 1.62 (s, 3H), 2.07 (s, 3H), 6.15-7.78 (m, aromatic), 8.06 (dd,
4
4JHP-trans ) 6.4 Hz, JHP-cis ) 1.0 Hz). 31P{1H} NMR (CD2Cl2,
161 MHz, 25 °C): δ 13.5 (d, AB spin, 2JPP ) 47 Hz), 41.1 (d, AB
2
spin, JPP ) 47 Hz). 19F NMR (CD2Cl2, 376.5 MHz, 25 °C): δ
-79.3 (s). 13C{1H} NMR (CD2Cl2, 100 MHz, 25 °C): δ 20.6 (s,
1
CH3), 20.8 (s, Me), 115.4-178.0 (aromatic), 180.0 (t, dCH, JCP
) 4.2 Hz). MS (MALDI; m/z): M+ 938.2.
[Pd(rac-BINAP)(C15H14N)][BArF] (8b). To 1 equiv of [Pd(µ-
Cl)(C15H14N)]2 (21.5 mg, 700.3 g mol-1, 30.7 × 10-3 mol) were
added 2 equiv of rac-BINAP (38.2 mg, 622.67 g mol-1, 61.4 ×
10-3 mol) and 2 equiv of NaBArF (54.4 mg, 886.21 g mol-1, 61.4
× 10-3 mol) in dichloromethane. The reaction mixture was stirred
at 25 °C for 3 h. The resulting yellow solution was separated from
the solid and reduced in vacuo. Yield of [C91H58BF24NP2Pd] (8b):
104 mg, 0.0578 mol, 94%). Anal. Found (calcd) for [Pd(rac-
BINAP)(C15H14N)][BArF]: C, 60.98 (60.70); H, 3.43 (3.25); N,
0.79 (0.78). 1H NMR (CD2Cl2, 400 MHz, 25 °C): δ 2.06 (s, 3H),
1
178.6 (t, dCH, JCP ) 3.7 Hz). MS (MALDI; m/z): M+ 969.1.
[Pd(rac-BINAP)(C14H11N2O2)][BArF] (10b). To 1 equiv of [Pd-
(µ-Cl)(C14H11N2O2)]2 (22.0 mg, 762.24 g mol-1, 28.9 × 10-3 mol)
were added 2 equiv of rac-BINAP (35.9 mg, 622.67 g mol-1, 57.7
× 10-3 mol) and 2 equiv of NaBArF (51.2 mg, 886.21 g mol-1
,
57.7 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C90H55BF24N2O2P2-
Pd] (10b): 100 mg, 0.0546 mol, 94%. Anal. Found (calcd) for [Pd-
(rac-BINAP)(C14H11N2O2)][BArF]: C, 58.92 (59.02); H, 3.31
4
2.17 (s, 3H), 6.15-8.30 (m, aromatic), 8.05 (d, JHP-trans ) 6.9
1
(3.03); N, 1.57 (1.53). H NMR (CD2Cl2, 400 MHz, 25 °C): δ
Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C): δ 13.4 (d, AB
4
2.08 (s, 3H), 6.15-8.30 (m, aromatic), 8.23 (d, JHP-trans ) 6.8
2
2
spin, JPP ) 48 Hz), 41.1 (d, AB spin, JPP ) 48 Hz). 19F NMR
(CD2Cl2, 376.5 MHz, 25 °C): δ -63.3 (s). 13C{1H} NMR (CD2-
Cl2, 100 MHz, 25 °C): δ 20.5 (s, CH3), 20.8 (s, Me), 115.4-178.0
Hz, 4JHP-cis ) 1.2 Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C):
2
2
δ 14.1 (d, AB spin, JPP ) 47 Hz), 40.1 (d, AB spin, JPP ) 47
Hz). 19F NMR (CD2Cl2, 282 MHz, 25 °C): δ -63.3 (s). 13C{1H}
NMR (CD2Cl2, 100 MHz, 25 °C): δ 20.8 (s, CH3), δ 115.4-178.0
1
(aromatic), 179.9 (t, dCH, JCP ) 3.5 Hz). MS (MALDI; m/z):
M+ 938.2.
1
(aromatic), 178.4 (t, dCH, JCP ) 3.9 Hz). MS (MALDI; m/z):
[Pd(rac-BINAP)(C14H11ClN)][CF3SO3] (9a). To 1 equiv of [Pd-
(µ-Cl)(C14H11ClN)]2 (28.3 mg, 741.14 g mol-1, 38.2 × 10-3 mol)
were added 2 equiv of rac-BINAP (47.5 mg, 622.67 g mol-1, 76.4
M+ 969.2.
[Pd(rac-BINAP)(C14H11N2O2)][PF6] (10c). To 1 equiv of [Pd-
(µ-Cl)(C14H11N2O2)]2 (19.6 mg, 732.36 g mol-1, 25.7 × 10-3 mol)
were added 2 equiv of rac-BINAP (32.0 mg, 622.67 g mol-1, 51.4
× 10-3 mol) and 2 equiv of NH4PF6 (8.4 mg, 163 g mol-1, 51.4 ×
10-3 mol) in acetone. The reaction mixture was stirred at 25 °C
for 2 h. Water was then added and the mixture stirred for a further
1 h. The resulting precipitate was filtered off and dried in vacuo.
Yield of [C58H43F6N2O2P3Pd] (10c): 51 mg, 0.0458 mol, 89%.
Anal. Found (calcd) for [Pd(rac-BINAP)(C14H11N2O2)][PF6]: C,
× 10-3 mol) and 2 equiv of AgOTf (19.6 mg, 256.94 g mol-1
,
76.4 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C59H43ClF3NO3P2-
PdS] (9a): 80 mg, 0.072 mol, 94%. Anal. Found (calcd) for [Pd-
(rac-BINAP)(C14H11ClN)][CF3SO3]: C, 63.04 (64.02); H, 4.03
(3.92); N, 1.21 (1.27). 1H NMR (CD2Cl2, 400 MHz, 25 °C): 2.07
4
(s, 3H), 6.15-7.78 (m, aromatic), 8.08 (dd, 1H, JHP-trans ) 6.4
1
Hz, 4JHP-cis ) 1.0 Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C):
62.28 (62.57); H, 3.97 (3.89); N, 2.48 (2.52). H NMR (CDCl3,
2
2
400 MHz, 25 °C): δ 2.1 (s, 3H), 6.30-8.25 (m, aromatic), 8.25
δ 13.7 (d, AB spin, JPP ) 47 Hz), 40.6 (d, AB spin, JPP ) 47
Hz). 19F NMR (CD2Cl2, 376.5 MHz, 25 °C): δ -79.3 (s). 13C-
{1H} NMR (CD2Cl2, 100 MHz, 25 °C): δ 20.8 (s, CH3), δ 115.4-
4
(d, 1H, JHP-trans ) 6.8 Hz). 31P{1H} NMR (CDCl3, 161 MHz, 25
2
2
°C): δ 14.1 (d, AB spin, JPP ) 46 Hz), 40.1 (d, AB spin, JPP
)
46 Hz), -143.2 (sep, JPF ) 713 Hz). 19F NMR (CDCl3, 376.5
1
1
178.0 (aromatic), 178.3 (t, dCH, JCP ) 4.1 Hz). MS (MALDI;
m/z): M+ 958.2.
MHz, 25 °C): δ -73.8 (d, 1JFP ) 713 Hz). 13C{1H} NMR (CDCl3,

4952 Organometallics, Vol. 26, No. 20, 2007
Nama et al.
100 MHz, 25 °C): δ 20.8 (s, CH3), 115.4-178.0 (aromatic), 178.5
δ 20.8 (s, CH3), 21.8 (s, Me), 115.4-178.0 (aromatic), 180.0 (t,
1
(t, dCH, JCP ) 3.9 Hz). MS (MALDI; m/z): M+ 969.1.
1
dCH, JCP ) 4.6 Hz). MS (MALDI; m/z): M+ 938.2.
[Pd(rac-BINAP)(C15H14N)][BArF] (12b). To 1 equiv of [Pd-
(µ-Cl)(C15H14N)]2 (22.3 mg, 700.3 g mol-1, 31.8 × 10-3 mol) were
[Pd(rac-BINAP)(C15H14NO)][CF3SO3] (11a). To 1 equiv of
[Pd(µ-Cl)(C15H14NO)]2 (17.4 mg, 732.3 g mol-1, 24.0 × 10-3 mol)
were added 2 equiv of rac-BINAP (29.6 mg, 622.67 g mol-1, 48.0
added 2 equiv of the rac-BINAP 39.7 mg, 622.67 g mol-1, 63.7
(
× 10-3 mol) and 2 equiv of AgOTf (12.3 mg, 256.94 g mol-1
,
× 10-3 mol) and 2 equiv of NaBArF (56.4 mg, 886.21 g mol-1
,
48.0 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C60H46F3NO4P2-
PdS] (11a): 54 mg, 0.049 mol, 98%. 1H NMR (CDCl3, 400 MHz,
25 °C): δ 2.03 (s, 3H), 3.71 (s, 3H), 6.15-7.78 (m, aromatic),
8.07 (d, 1H, 4JHP-trans ) 6.4 Hz). 31P{1H} NMR (CDCl3, 161 MHz,
25 °C): δ 13.6 (d, AB spin, 2JPP ) 47 Hz), 41.2 (d, AB spin, 2JPP
63.7 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in Vacuo. [C91H58BF24NP2Pd] 12b
(Yield: 101 mg, 0.0561mol, 88%). Anal. Found (calcd) for [Pd-
(rac-BINAP)(C15H14N)][BArF] C {61.27 (60.70)} H {3.34 (3.25)}
1
N {0.78 (0.78)} H NMR (CD2Cl2, 400 MHz, 25 °C): δ 2.06 (s,
4
3H), 2.38 (s, 3H), 6.15-8.30 (m, aromatic), 8.02 (d, JHP-trans
)
1
) 47 Hz), -142.9 (sep, JPF ) 713 Hz). 19F NMR (CDCl3, 376.5
6.9 Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C): δ 13.3 (d, AB
MHz, 25 °C): δ -73.8 (d, 1JFP ) 713 Hz). 13C{1H} NMR (CDCl3,
100 MHz, 25 °C): δ 21.4 (s, CH3), 55.8 (s, OMe), 115.4-178.0
spin, JPP ) 48 Hz), 40.8 (d, AB spin, JPP ) 48 Hz). 19F NMR
(CD2Cl2, 376.5 MHz, 25 °C): δ -63.3 (s). 13C{1H} NMR (CD2-
Cl2, 100 MHz, 25 °C): δ 20.3 (s, CH3), 21.3 (s, Me), 115.4-178.0
2
2
1
(aromatic), 180.0 (t, dCH, JCP ) 4.1 Hz). MS (MALDI; m/z):
M+ 954.2.
1
(aromatic), 179.1 (t, dCH, JCP ) 4.1 Hz). MS (MALDI; m/z):
[Pd(rac-BINAP)(C15H14NO)][BArF] (11b). To 1 equiv of [Pd-
(µ-Cl)(C15H14NO)]2 (21.7 mg, 732.36 g mol-1, 29.6 × 10-3 mol)
were added 2 equiv of rac-BINAP (36.9 mg, 622.67 g mol-1, 59.3
M+ 938.2.
[Pd(rac-BINAP)(C14H11N2O2)][CF3SO3] (13a). To 1 equiv of
[Pd(µ-Cl)(C14H11N2O2)]2 (29.0 mg, 762.24 g mol-1, 38.0 × 10-3
× 10-3 mol) and 2 equiv of NaBArF (52.5 mg, 886.21 g mol-1
,
mol) were added 2 equiv of rac-BINAP (47.4 mg, 622.67 g mol-1
,
59.3 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C91H58BF24NOP2-
Pd] (11b): 100 mg, 0.055 mol, 92%. Anal. Found (calcd) for [Pd-
(rac-BINAP)(C15H14NO)][BArF]: C, 60.17 (60.29); H, 3.22 (3.38);
76.0 × 10-3 mol) and 2 equiv of AgOTf (19.6 mg, 256.94 g mol-1
,
76.0 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C59H43F3N2O5P2-
PdS] (13a): 80 mg, 0.071 mol, 94%. Anal. Found (calcd) for [Pd-
(rac-BINAP)(C14H11ClN)][CF3SO3]: C, 62.80 (63.42); H, 4.04
1
N, 0.77 (0.78). H NMR (CDCl3, 400 MHz, 25 °C): δ 2.03 (s,
4
3H), 3.70 (s, 3H), 6.15-7.78 (m, aromatic), 7.95 (d, JHP-trans
)
1
(3.88); N, 2.54 (2.51). H NMR (CD2Cl2, 400 MHz, 25 °C): δ
6.4 Hz). 31P{1H} NMR (CDCl3, 161 MHz, 25 °C): δ 13.4 (d, AB
4
2.09 (s, 3H), 6.15-8.30 (m, aromatic), 8.29 (d, 1H, JHP-trans
)
spin, JPP ) 47 Hz), 41.2 (d, AB spin, JPP ) 47 Hz). 19F NMR
(CDCl3, 376.5 MHz, 25 °C): δ -62.4 (s). 13C{1H} NMR (CDCl3,
100 MHz, 25 °C): δ 21.4 (s, CH3), 55.8 (s, OMe), 115.4-178.0
2
2
6.8 Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C): δ 14.3 (d, AB
spin, JPP ) 47 Hz), 39.9 (d, AB spin, JPP ) 47 Hz). 19F NMR
(CD2Cl2, 376.5 MHz, 25 °C): δ -79.3 (s). 13C{1H} NMR (CD2-
Cl2, 100 MHz, 25 °C): δ 20.9 (s, CH3), 115.4-178.0 (aromatic),
2
2
1
(aromatic), 180.0 (t, dCH, JCP ) 4.0 Hz). MS (MALDI; m/z):
M+ 954.2.
178.8 (t, dCH, JCP ) 3.8 Hz). MS (MALDI; m/z): M+ 969.2.
1
[Pd(rac-BINAP)(C15H14NO)][PF6] (11c). To 1 equiv of [Pd-
(µ-Cl)(C15H14NO)]2 (18.3 mg, 732.36 g mol-1, 25.0 × 10-3 mol)
were added 2 equiv of rac-BINAP (31.1 mg, 622.67 g mol-1, 50.0
× 10-3 mol) and 2 equiv of NH4PF6 (8.15 mg, 163 g mol-1, 50.0
× 10-3 mol) in acetone. The reaction mixture was stirred at 25 °C
for 2 h. Water was then added and the mixture stirred for a further
1 h. The resulting precipitate was filtered off and dried in vacuo.
Yield of [C59H46F6NOP3Pd] (11c): 44 mg, 0.044 mol, 80%. Anal.
Found (calcd) for [Pd(rac-BINAP)(C15H14NO)][PF6]: C, 64.52
(64.67); H, 4.22 (4.39); N, 1.28 (1.29). 1H NMR (CDCl3, 400 MHz,
25 °C): δ 2.03 (s, 3H), 3.71 (s, 3H), 6.15-7.78 (m, aromatic),
8.07 (d, 4JHP-trans ) 6.4 Hz). 31P{1H} NMR (CDCl3, 161 MHz, 25
[Pd(rac-BINAP)(C14H11N2O2)][BArF] (13b). To 1 equiv of [Pd-
(µ-Cl)(C14H11N2O2)]2 (21.5 mg, 762.24 g mol-1, 28.2 × 10-3 mol)
were added 2 equiv of rac-BINAP (35.1 mg, 622.67 g mol-1, 56.4
× 10-3 mol) and 2 equiv of NaBArF (50.0 mg, 886.21 g mol-1
,
56.4 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C90H55BF24N2O2P2-
Pd] (13b): 92 mg, 0.0502 mol, 89%. Anal. Found (calcd) for [Pd-
(rac-BINAP)(C14H11N2O2)][BArF]: C, 59.29 (59.02); H, 3.08
1
(3.03); N, 1.60 (1.53). H NMR (CD2Cl2, 400 MHz, 25 °C): δ
4
2.09 (s, 3H), 6.15-8.30 (m, aromatic), 8.23 (d, JHP-trans ) 6.8
Hz). 31P{1H} NMR (CD2Cl2, 161 MHz, 25 °C): δ 14.3 (d, AB
2
2
°C): δ 13.6 (d, AB spin, JPP ) 47 Hz), 41.2 (d, AB spin, JPP
)
2
2
1
spin, JPP ) 46 Hz), 39.9 (d, AB spin, JPP ) 46 Hz). 19F NMR
(CD2Cl2, 282 MHz, 25 °C): δ -63.3 (s). 13C{1H} NMR (CD2Cl2,
100 MHz, 25 °C): δ 20.8 (s, CH3), 115.4-178.0 (aromatic), 178.2
47 Hz), -142.9 (sep, JPF ) 713 Hz). 19F NMR (CDCl3, 376.5
MHz, 25 °C): δ -73.8 (d, 1JFP ) 713 Hz). 13C{1H} NMR (CDCl3,
100 MHz, 25 °C): δ 21.4 (s, CH3), 55.8 (s, OMe), 115.4-178.0
(t, dCH, JCP ) 3.8 Hz). MS (MALDI; m/z): M+ 969.1.
1
1
(aromatic), 180.0 (t, dCH, JCP ) 4.1 Hz). MS (MALDI; m/z):
M+ 954.2.
[Pd((S)-BINAP)((R)-C10H14N)][CF3SO3] (14a). To 1 equiv of
[Pd(µ-Cl)(C10H14N)]2 (30.3 mg, 600.35 g mol-1, 50.5 × 10-3 mol)
were added 2 equiv of (S)-BINAP (62.8 mg, 622.67 g mol-1, 110.9
[Pd(rac-BINAP)(C15H14N)][CF3SO3] (12a). To 1 equiv of [Pd-
(µ-Cl)(C15H14N)]2 (20.1 mg, 700.3 g mol-1, 28.7 × 10-3 mol) were
added 2 equiv of rac-BINAP (35.7 mg, 622.67 g mol-1, 57.4 ×
10-3 mol) and 2 equiv of AgOTf (14.7 mg, 256.94 g mol-1, 57.4
× 10-3 mol) in dichloromethane. The reaction mixture was stirred
at 25 °C for 3 h. The resulting yellow solution was separated from
the solid and reduced in vacuo. Yield of [C60H46F3NO3P2PdS]
(12a): 112 mg, 0.103 mol, 90%. 1H NMR (CD2Cl2, 400 MHz, 25
°C): δ 1.69 (s, 3H), 2.07 (s, 3H), 6.15-7.78 (m, aromatic), 8.05
× 10-3 mol) and 2 equiv of AgOTf (25.9 mg, 256.94 g mol-1
,
110.9 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C55H46F3NO3P2-
1
PdS] (14a): 102 mg, 98%. H NMR (CD2Cl2, 500 MHz, 25 °C):
4
4
1.92 (d, 3H, JPH ) 2.1 Hz), 2.12 (br t, 3H, JPH ) 3.5 Hz), 2.28
3
(d, 2H, JHH ) 6.3 Hz), 3.49 (m, 1H), 6.15-8.50 (m, aromatic).
31P{1H} NMR (CD2Cl2, 283 MHz, 25 °C): δ 11.1 (d, AB spin,
4
4
(dd, 1H, JHP-trans ) 6.9 Hz, JHP-cis ) 1.0 Hz). 31P{1H} NMR
2JPP ) 43 Hz), 38.2 (d, AB spin, JPP ) 43 Hz). 19F NMR (CD2-
2
2
(CD2Cl2, 161 MHz, 25 °C): δ 13.3 (d, AB spin, JPP ) 48 Hz),
Cl2, 282.4 MHz, 25 °C): δ -78.8 (s). 13C{1H} NMR (CD2Cl2,
125.8 MHz, 25 °C): δ 9.0 (s, CH3), 25.9 (s, CH3), 40.3 (s, NCH3),
40.8 (d, AB spin, JPP ) 48 Hz). 19F NMR (CD2Cl2, 376.5 MHz,
2
25 °C): δ -79.3 (s). 13C{1H} NMR (CD2Cl2, 100 MHz, 25 °C):

Pd-Cyclometalated BINAP and Chiraphos Complexes
Organometallics, Vol. 26, No. 20, 2007 4953
Table 5. Crystal Data and Strucure Refinement Details for 8a, 10a, and 14b,c
8a
10a
14b
14c
color, shape
empirical formula
yellow, cube
C63H50Cl5F3NO3-
P2PdS
yellow, cube
C62H49Cl6F3N2O5-
P2PdS
yellow, cube
C57H47Cl6F3NO3-
P2PdS
yellow, needle
C
110H92F6N2O6-
P4Pd2S2
formula wt
temp (K)
cryst syst
space group
a (Å)
1303.69
200(2)
triclinic
P1h
11.3820(11)
15.5502(14)
17.1910(16)
71.786(2)
84.497(2)
79.695(2)
2841.0(5)
2
1372.13
200(2)
Triclinic
P1h
13.2269(5)
14.3139(6)
16.4955(7)
75.4480(10)
82.3430(10)
85.9830(10)
2993.7 (2)
2
1264.06
200(2)
2052.66
200(2)
orthorhombic
P212121
11.8308(10)
12.8673(10)
36.642(3)
90.00
90.00
90.00
5578.0(8)
4
1.505
monoclinic
P21
17.6911(10)
11.5190(6)
23.0571(13)
90.00
90.8320(10)
90.00
4698.2(4)
2
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
calcd density (Mg m3)
1.524
0.713
1326
1.522
0.727
1392
1.451
0.566
2104
abs coeff (mm-1
F(000)
)
0.770
2564
cryst size (mm)
min, max θ (deg)
index ranges
0.49 × 0.27 × 0.19
1.57, 26.02
-14 e h e 14
-19 e k e 19
-21 e l e 21
25 009
0.54 × 0.28 × 0.27
1.47, 28.36
-17 e h e 17
-19 e k e 19
-22 e l e 22
55 615
0.51 × 0.48 × 0.28
1.68, 28.33
-15 e h e 15
-17 e k e 17
-48 e l e 48
58 341
0.51 × 0.46 × 0.40
0.88, 28.33
-23 e h e 23
-15< e k e 15
-30 e l e 29
49 277
no. of rflns collected
no. of indep rflns, R(int)
11 160, 0.0246
11 160/0/712
1.034
14 874, 0.0361
14 874/0/739
1.040
13 866, 0.0345
13 866/0/687
1.078
23 207, 0.0342
23 207/1/1189
1.043
no. of data/restraints/params
goodness of fit on F2
final R1, wR2 indices (I > 2σ(I))
final R1, wR2 indices (all data)
largest diff peak, hole/e Å-3
0.0572, 0.1462
0.0639, 0.1538
2.956, -2.584
0.0465, 0.1241
0.0540, 0.1306
1.785, -1.123
0.0371, 0.0918
0.0394, 0.0930
0.882, -0.598
0.0505, 0.1151
0.0577, 0.1199
1.605, -1.209
46.7 (s, NCH3), 49.5 (s, NCH3), 51.5 (s, NCH3), 74.4 (m, CH),
79.8 (m, CH), 115.4-180.0 (aromatic). MS (MALDI; m/z): M+
876.2.
[Pd((R)-BINAP)((R)-C10H14N)][CF3SO3] (14b). To 1 equiv of
[Pd(µ-Cl)(C10H14N)]2 (30.0 mg, 600.35 g mol-1, 49.9 × 10-3 mol)
were added 2 equiv of (R)-BINAP (62.2 mg, 622.67 g mol-1, 99.9
10-3 mol) were added 2 equiv of (2S,3S)-Chiraphos (40.8 mg,
426.47 g mol-1, 95.6 × 10-3 mol) and 2 equiv of AgOTf (24.6
mg, 256.94 g mol-1, 95.6 × 10-3 mol) in dichloromethane. The
reaction mixture was stirred at 25 °C for 3 h. The resulting colorless
solution was separated from the solid and reduced in vacuo. Yield
of [C39H42F3NO3P2PdS] (15a): 80 mg, 98%. 1H NMR (CDCl3, 400
× 10-3 mol) and 2 equiv of AgOTf (25.7 mg, 256.94 g mol-1
,
MHz, 25 °C): 1.05 (dd, 3H, JHH ) 6.4 Hz, JPH ) 2.4 Hz), 1.07
(d, 3H, 3JHH ) 6.4 Hz), 1.69 (d, 3H, 3JHH ) 6.4 Hz), 2.22 (m, 1H),
2.28 (d, 3H, 4JPH ) 1.2 Hz), 2.31 (m, 1H), 2.50 (t, 3H, 4JPH ) 3.6
Hz), 3.55 (m, 1H), 6.50-8.20 (m, aromatic). 31P{1H} NMR (CDCl3,
3
3
99.9 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C55H46F3NO3P2-
1
2
PdS] (14b): 100 mg, 97%. H NMR (CDCl3, 400 MHz, 25 °C):
161.9 MHz, 25 °C): δ 45.2 (d, AB spin, JPP ) 40 Hz), 63.3 (d,
1.33 (d, 2H, 3JHH ) 6.3 Hz), 1.51 (d, 3H, 4JPH ) 2.1 Hz), 2.54, (br
t, 3H, 4JPH ) 3.5 Hz), 5.46 (m, 1H), 6.15-8.50 (m, aromatic). 31P-
{1H} NMR (CDCl3, 161.9 MHz, 25 °C): δ 11.1 (d, AB spin, 2JPP
AB spin, 2JPP ) 40 Hz). 19F NMR (CDCl3, 376.5 MHz, 25 °C): δ
-78.4 (s). 13C{1H} NMR (CDCl3, 100 MHz, 25 °C): δ 13.9 (dd,
2
3
2
CH3, JCP ) 17.1 Hz, JCP ) 6.1 Hz), 15.4 (dd, CH3, JCP ) 18.6
2
3
1
) 43 Hz), 38.2 (d, AB spin, JPP ) 43 Hz); 19F NMR (CD2Cl2,
Hz, JCP ) 5.5 Hz), 26.6 (s, CH3), 38.4 (dd, CH, JCP ) 26.8 Hz,
282.4 MHz, 25 °C): δ -78.8 (s); 13C{1H} NMR (CD2Cl2, 125.8
MHz, 25 °C): δ 9.0 (s, CH3), 40.3 (s, NCH3), 49.5 (s, NCH3),
74.4 (m, CH), 115.4-180.0 (aromatic). MS (MALDI; m/z): M+
876.2.
2JCP ) 13.4 Hz), 39.9 (dd, CH, JCP ) 33.3 Hz, JCP ) 22 Hz),
1
2
3
3
50.4 (d, NCH3, JCP ) 5.2 Hz), 51.7 (d, NCH3, JCP ) 2.4 Hz),
78.8 (br t, CH), 115.4-180.0 (aromatic). MS (MALDI; m/z): M+
680.2.
[Pd(rac-BINAP)((R)-C10H14N)][CF3SO3] (14c). To 1 equiv of
[Pd(µ-Cl)(C10H14N)]2 (33.6 mg, 600.35 g mol-1, 55.9 × 10-3 mol)
were added 2 equiv of rac-BINAP (69.7 mg, 622.67 g mol-1, 111.9
[Pd(2R,3R)-Chiraphos)((R)-C10H14N)][CF3SO3] (15b). To 1
equiv of [Pd(µ-Cl)(C10H14N)]2 (30.5 mg, 600.35 g mol-1, 50.8 ×
10-3 mol) were added 2 equiv of (2R,3R)-Chiraphos (43.3 mg,
426.47 g mol-1, 101.6 × 10-3 mol) and 2 equiv of AgOTf (26.1
mg, 256.94 g mol-1, 101.6 × 10-3 mol) in dichloromethane. The
reaction mixture was stirred at 25 °C for 3 h. The resulting colorless
solution was separated from the solid and reduced in vacuo. Yield
of [C39H42F3NO3P2PdS] (15b): 80 mg, 95%. 1H NMR (CDCl3, 300
× 10-3 mol) and 2 equiv of AgOTf (28.8 mg, 256.94 g mol-1
,
111.9 × 10-3 mol) in dichloromethane. The reaction mixture was
stirred at 25 °C for 3 h. The resulting yellow solution was separated
from the solid and reduced in vacuo. Yield of [C55H46F3NO3P2-
PdS] (14c): 111 mg, 0.108 mol, 96%. 1H NMR (CD2Cl2, 700 MHz,
25 °C): 1.35 (d, 2H, 3JHH ) 6.3 Hz), 1.53 (d, 3H, 4JPH ) 2.1 Hz),
3
3
MHz, 25 °C): 1.04 (dd, 3H, JHH ) 6.8 Hz, JPH ) 2.9 Hz), 1.08
4
4
1.92 (d, 3H, JPH ) 2.1 Hz), 2.12 (br t, 3H, JPH ) 3.5 Hz), 2.28
(d, 3H, 3JHH ) 6.7 Hz), 1.41 (d, 3H, 3JHH ) 6.7 Hz), 2.09 (d, 3H,
3
4
4
(d, 2H, JHH ) 6.3 Hz), 2.51 (br t, 3H, JPH ) 3.5 Hz), 3.49 (m,
1H), 5.19 (m, 1H), 6.15-8.50 (m, aromatic). 31P{1H} NMR (CD2-
Cl2, 283 MHz, 25 °C): δ 10.5 (d, AB spin, 2JPP ) 44.2 Hz), 11.1
4JPH ) 1.6 Hz), 2.22 (m, 1H), 2.35 (m, 1H), 2.78 (t, 3H, JPH
)
2.5 Hz), 4.31 (m, 1H), 6.50-8.20 (m, aromatic). 31P{1H} NMR
(CDCl3, 121.5 MHz, 25 °C): δ 43.3 (d, AB spin, 2JPP ) 40.5 Hz),
62.5 (d, AB spin, 2JPP ) 40.5 Hz). 19F NMR (CDCl3, 376.5 MHz,
25 °C): δ -78.5 (s). 13C{1H} NMR (CDCl3, 100 MHz, 25 °C): δ
14.1 (dd, CH3, 2JCP ) 16.2 Hz, 3JCP ) 6.0 Hz), 15.4 (dd, CH3, 2JCP
2
2
(d, AB spin, JPP ) 43 Hz), 37.2 (d, AB spin, JPP ) 44.2 Hz),
38.2 (d, AB spin, JPP ) 43 Hz). 19F NMR (CD2Cl2, 282.4 MHz,
2
25 °C): δ -78.8 (s). 13C{1H} NMR (CD2Cl2, 175 MHz, 25 °C):
δ 25.9 (s, CH3), 46.7 (s, NCH3), 51.5 (s, NCH3), 79.8 (m, CH),
115.4-180.0 (aromatic). MS (MALDI; m/z): M+ 876.2.
) 17.8 Hz, 3JCP ) 5.2 Hz), 16.6 (s, CH3), δ 38.6 (dd, CH, 1JCP
)
)
)
2
1
2
26.5 Hz, JCP ) 12.7 Hz), 40.8 (dd, CH, JCP ) 33.1 Hz, JCP
3
[Pd(2S,3S)-Chiraphos)((R)-C10H14N)][CF3SO3] (15a). To 1
equiv of [Pd(µ-Cl)(C10H14N)]2 (28.7 mg, 600.35 g mol-1, 47.8 ×
21.5 Hz), 45.7 (s, NCH3), δ 52.1 (s, NCH3), 75.4 (t, CH, JCP
3.2 Hz), 115.4-180.0 (aromatic). MS (MALDI; m/z): M+ 680.3.

4954 Organometallics, Vol. 26, No. 20, 2007
Nama et al.
Solid-State Measurements. X-ray structural measurements were
carried out on a Bruker CCD diffractometer: Bruker SMART
PLATFORM, with CCD detector, graphite monochromator, Mo
KR (0.710 73 Å) radiation and a low-temperature device (200 K).
Crystals of 8, 10, and 14a,c, suitable for X-ray diffraction, were
obtained by crystallization from a saturated CH2Cl2/hexane solution
at low temperature. The single crystals were mounted in a poly-
(perfluoroalkyl ether) oil on top of a glass fiber and fixed with
some epoxy glue. Calculations were performed on a PC system
with SHELXTL (version 6.12) and SHELXL-97 (G. M. Sheldrick,
Go¨ttingen, Germany, 1997). The structures were solved by either
Patterson (8, 10, 14c) or direct (10) methods and successive
interpretation of the difference Fourier maps, followed by full-matrix
least-squares refinement (against F2). Non-hydrogen atoms were
refined freely with anisotropic displacement parameters. The
contribution of the hydrogen atoms, in their calculated positions,
was included in the refinement using a riding model for the X-ray
structures. Moreover, an empirical absorption correction using
SADABS (version 2.03) was applied to all structures. The dichlo-
romethane solvent found in the structure of 14a is disordered, and
the chlorine atoms were placed in two positions, each with an
occupancy of 50%, to achieve a satisfactory wR2 value.
Selected interatomic distances and bond angles are reported in
Table 2. Relevant data concerning crystallographic data, data
collection, and refinement details are compiled in Table 5. Further
details of the crystallographic studies have been deposited with the
Cambridge Crystallographic Data Centre: CCDC Nos. 640811-
640814 for 8, 10, and 14a,c, respectively.
Acknowledgment. P.S.P. thanks the Swiss National Science
Foundation and the ETH Zurich for support, as well as the
Johnson Matthey Organization for the loan of palladium salts.
Special thanks are due to Dr. H. Ru¨egger for his advice and
help.
Supporting Information Available: Figures giving NOE
spectra for 15a and 15b and CIF files giving complete crystal-
lographic data. This material is available free of charge via the
Internet at http://pubs.acs.org.
OM700299B