Electrophilic activation: Unexpected metal-metal bond-assisted Tl + chelation by a Pt-benzyl moiety instead of chloride abstraction

Article abstract of DOI:10.1021/om049282s

The major effect of replacing Ag(I) with Tl(I) salts, which are indiscriminately used as halide abstractors was investigated. It was found that in the absence of donor ligands such as, OTf^s-s or acetonitrile, abstraction of the halide from Pt(II) complex or AgBF₄ or AgPF ₆ in CH₂Cl₂ resulted in formation of a dynamic cationic complex. The bonding interactions between the d⁸ Pt(II) and s² Tl(I) center was assisted by π-donation from the benzyl ligand to the Tl⁺ ion.

Full text of DOI:10.1021/om049282s

Organometallics 2004, 23, 6311-6318
6311
Electrophilic Activation: Unexpected Metal-Metal
Bond-Assisted Tl+ Chelation by a Pt-Benzyl Moiety
Instead of Chloride Abstraction
Nicola Oberbeckmann-Winter,† Pierre Braunstein,*,† and Richard Welter‡
Laboratoire de Chimie de Coordination, UMR 7513 CNRS, Universite´ Louis Pasteur, 4 Rue
Blaise Pascal, 67070 Strasbourg Cedex, France, and Laboratoire DECMET, UMR 7513 CNRS,
Universite´ Louis Pasteur, 4 Rue Blaise Pascal, 67070 Strasbourg Cedex, France
Received September 14, 2004
One of the activation procedures most frequently used in late transition metal chemistry
consists in generating cationic metal complexes by halide abstraction from the metal center
in the presence of a weakly coordinating anion. We report here on the major effect of replacing
Ag(I) with Tl(I) salts, although they are often used indiscriminately as halide abstractors.
The Pt(II) complex [Pt(CH2Ph)Cl(PCH2-ox)] (1) (PCH2-ox ) κ2-P,N-(oxazolinylmethyl)-
diphenylphosphine) yielded the expected metathesis product [Pt(CH2Ph)(OTf)(PCH2-ox)] (2)
when treated with 1 equiv of AgOTf (OTf ) SO3CF3) in CH2Cl2. In a coordinating solvent
such as acetonitrile, chloride displacement readily afforded [Pt(CH2Ph)(NCCH3)(PCH2-ox)]X
(3), irrespective of the nature of the halide abstractor (M+ ) Ag+ or Tl+) and counterion (X-
-
-
) OTf-, BF4 , PF6 ) used. Reaction of 1 in CH2Cl2 with only half an equivalent of AgBF4
afforded the new, chloride-bridged dinuclear complex [{Pt(CH2Ph)(PCH2-ox)}2(µ-Cl)]BF4 (5‚
BF4), which results from trapping of the cation [Pt(η3-CH2Ph)(PCH2-ox)]+ (4) by unreacted
1. Similarly, the Pt/Pd heterometallic, single-chloride bridged complex [{Pt(CH2Ph)(PCH2-
ox)}(µ-Cl){PdMe(PCH2-ox)}]BF4 (6‚BF4) was obtained by reaction of 4 with [PdClMe(PCH2-
ox)] in a 1:1 ratio. When 1 was reacted in CH2Cl2 with Tl+ instead of Ag+, formation of 4
was not observed and the main product was an unexpected adduct of Tl+ to 1 whose X-ray
analysis established the formation of both a Pt-Tl bond and a η6-benzyl-Tl interaction.
This bimetallic complex, [(PCH2-ox)ClPtTl{µ-(η1-CH2;η6-C6H5)CH2Ph}(Pt-Tl)]PF6 (7‚PF6),
is to our knowledge the first metal-metal bonded Tl-Pt-Cl complex to be fully characterized.
The coordination geometry around Pt(II) is square-pyramidal, with Tl(I) in the apical position.
The Pt-Tl distance of 3.0942(9) Å corresponds to a metal-metal bond that results mainly
2
from donation of electron density from the Pt(II) 5dz orbital to the vacant Tl(I) 6pz orbital.
The Pt-Tl bond is not exactly orthogonal to the Pt(II) square-plane (angle of 70(3)°), but
parallel to the C(1)-C(2) bond, thus allowing better π-donation from the benzyl ligand to
Tl+. When the corresponding benzoyl complex [Pt{C(O)Ph}Cl(PCH2-ox)] (9) was reacted with
MX (M+ ) Ag+, Tl+) in CH2Cl2, only chloride abstraction and CO deinsertion occurred. Our
findings explain why halide abstraction to generate a cationic metal complex with enhanced
(catalytic) reactivity may not come to full completion or fail owing to trapping of the cationic
complex or “capture” of Tl+ by the neutral precursor acting, in our case, as an unprecedented
chelate through metal-metal bond formation and benzyl coordination. The crystal structures
of 1, 5‚BF4‚0.5CH2Cl2, 7‚PF6, 9‚0.5CH2Cl2, and 10‚PF6‚0.75C4H8O have been determined by
X-ray diffraction.
Introduction
at the metal center facilitates substrate binding and
activation. One of the activation procedures most fre-
quently used in late transition metal chemistry consists
in halide abstraction from the metal center in the
presence of a weakly coordinating anion (WCA).3 If the
Generating cationic metal complexes represents a
general strategy to enhance stoichiometric and catalytic
reactivity toward unactivated1 or electron-rich sub-
strates, which is very often performed in situ.2
A
potentially vacant or lightly stabilized coordination site
(2) (a) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000,
100, 1169-1203. (b) Mecking, S. Coord. Chem. Rev. 2000, 203, 325-
351. (c) Bianchini, C.; Meli, A. Coord. Chem. Rev. 2002, 225, 35-66.
(d) Robertson, R. A. M.; Cole-Hamilton, D. J. Coord. Chem. Rev. 2002,
225, 67-90. (e) Bianchini, C.; Meli, A.; Oberhauser, W. Dalton Trans.
2003, 2627-2635. (f) Nakano, K.; Kosaka, N.; Hiyama, T.; Nozaki, K.
Dalton Trans. 2003, 4039-4050. (g) Gibson, V. C.; Spitzmesser, S. K.
Chem. Rev. 2003, 103, 283-316.
* To whom correspondence should be addressed. E-mail:
braunst@chimie.u-strasbg.fr.
† Laboratoire de Chimie de Coordination.
‡ X-ray structure analyses, Laboratoire DECMET.
(1) For C-H bond activation in arenes and alkanes see: (a)
Activation and Functionalization of C-H Bonds; Goldberg, K. I.,
Goldman, A. S., Eds.; ACS Symposium Series 885; 2004. (b) Jia, C.;
Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34, 633-639. (c)
Crabtree, R. H. Dalton Trans. 2003, 3985-3990.
(3) (a) Beck, W.; Su¨nkel, K. Chem. Rev. 1988, 88, 1405-1421. (b)
Strauss, S. H. Chem. Rev. 1993, 93, 927-942. (c) Chen, E. Y.-X.; Marks,
T. J. Chem. Rev. 2000, 100, 1391-1434.
10.1021/om049282s CCC: $27.50 © 2004 American Chemical Society
Publication on Web 11/16/2004

6312 Organometallics, Vol. 23, No. 26, 2004
Oberbeckmann-Winter et al.
Figure 1. Views of the molecular structures of 1 (a) and 5 (b) in 5‚BF4‚0.5CH2Cl2. The hydrogen atoms, the counterion,
and the solvent have been omitted for clarity. Selected bond distances (Å) and angles (deg) for 1: Pt-C1 2.055(6), Pt-N
2.120(5), Pt-P 2.192(1), Pt-Cl 2.359(1), C1-C2 1.514(9); C1-Pt-P 98.0(2), N-Pt-P 81.7(1), C1-Pt-Cl 90.2(2), N-Pt-
Cl 90.4(1), C2-C1-Pt 115.9(4). Selected bond distances (Å) and angles (deg) for 5‚BF4‚0.5CH2Cl2: Pt1-C1 2.081(9), Pt1-
N1 2.137(7), Pt1-P1 2.179(3), Pt1-Cl 2.401(2), C2-C1 1.53(1), Pt2-C24 2.08(1), Pt2-N2 2.109(8), Pt2-P2 2.177(2), Pt2-
Cl 2.390(2), C24-C25 1.51(1); C1-Pt1-P1 94.5(3), N1-Pt1-P1 82.6(2), C1-Pt1-Cl 88.4(3), N1-Pt1-Cl 94.6(2), C2-
C1-Pt1 110.9(6), C24-Pt2-P2 93.8(3), N2-Pt2-P2 83.8(2), C24-Pt2-Cl 89.6(3), N2-Pt2-Cl 92.8(2), C25-C24-Pt2
119.2(6), Pt2-Cl-Pt1 119.1(1).
Scheme 1
influence of the anion on the nature and catalytic activ-
ity of the resulting cationic complex has been clearly
evidenced,3c,4 that of the halide-abstracting Lewis acid
(e.g., Ag+, Tl+, Na+, NR4+, or ZnCl2) should also be
carefully considered because of its possible relevance to
the activation procedure, as demonstrated here.
With the hope of isolating and fully characterizing
reaction intermediates that would be too reactive with
the catalytically most relevant metals, such as Pd(II),
we focused on Pt(II) systems and report here on the
major effect of replacing Ag(I) with Tl(I) salts, although
they are often used indiscriminately as halide abstrac-
tors. The Pt(II) complex [Pt(CH2Ph)Cl(PCH2-ox)] (1)
(PCH2-ox ) κ2-P,N-(oxazolinylmethyl)diphenylphos-
phine) (see Figure 1a) was chosen as a model system
and is related to Ni(II) and Pd(II) complexes recently
used in ethylene oligomerization,5 CO/olefin copoly-
merization,6 or allylic alkylation.7 Whereas 1 did not
react with NH4PF6 or NaBPh4 in THF, it quantitatively
yielded the expected metathesis product [Pt(CH2Ph)-
(OTf)(PCH2-ox)] (2) when treated with 1 equiv of AgOTf
(OTf ) SO3CF3) in CH2Cl2. In a coordinating solvent
like acetonitrile, chloride displacement readily afforded
[Pt(CH2Ph)(NCCH3)(PCH2-ox)]+X- (3), irrespective of
the nature of the halide abstractor (M+ ) Ag+ or Tl+)
and counterion (X- ) OTf-, BF4-, PF6-) used.
In the absence of relatively good donor ligands, such
as OTf- or acetonitrile, abstraction of the halide from 1
by 1 equiv of AgBF4 or AgPF6 in CH2Cl2 resulted in the
formation of a dynamic, cationic complex. It was for-
mulated as [Pt(CH2Ph)(PCH2-ox)]+ (4) on the basis of
its ES mass spectrum, which shows only one peak at
m/z 555 with the correct isotopic distribution. This
complex is likely to contain an η3-benzyl ligand,8 as
supported by its quantitative conversion to 3 upon
dissolution in CDCl3 containing a drop of acetonitrile
(31P{1H} NMR monitoring).
Reaction of 1 in CH2Cl2 with only half an equivalent
of AgBF4 afforded the new, chloride-bridged dinuclear
complex 5 (Scheme 2). It clearly results from trapping
of the cation 4 by unreacted 1, and accordingly, 5 was
also obtained by reaction of 4 with 1 equiv of 1 in CH2-
Cl2. Such complexes with a single halide bridge9 are
attracting renewed interest because they illustrate a
possible deactivation route of cationic catalytic inter-
mediates.10 Only four dinuclear, single-bridged Pt(II)
chloro complexes appear to have been structurally
characterized (CSD version 5.25).11 The Pt1-Cl-Pt2
angle in 5 is 119.1(3)°, and the Pt-Cl distances of
(8) There are two crystal structures reported in the literature for
related η3-benzyl Pt(II) complexes: (a) Sonoda, A.; Bailey, P. M.;
Maitlis, P. M. J. Chem. Soc., Dalton Trans. 1979, 346-350. (b) Crascall,
L. E.; Litster, S. A.; Redhouse, A. D.; Spencer, J. L. J. Organomet.
Chem. 1990, 394, C35-C38.
(9) (a) Cotton, F. A.; Frenz, B. A.; White, A. J. J. Organomet. Chem.
1973, 60, 147-152. (b) Mattson, B. M.; Graham, W. A. G. Inorg. Chem.
1981, 20, 3186-3189.
(4) Rappe´, A. K.; Skiff, W. M.; Casewit, C. J. Chem. Rev. 2000, 100,
1435-1456.
(5) Speiser, F.; Braunstein, P.; Saussine, L.; Welter, R. Organome-
tallics 2004, 23, 2613-2624.
(6) Braunstein, P.; Fryzuk, M. D.; Le Dall, M.; Naud, F.; Rettig, S.
J.; Speiser, F. J. Chem. Soc., Dalton Trans. 2000, 1067-1074.
(7) Helmchen, G.; Pfaltz, A. Acc. Chem. Res. 2000, 33, 336-345.

Electrophilic Activation
Scheme 2. Synthesis of 4 and 5
Organometallics, Vol. 23, No. 26, 2004 6313
CH2;η6-C6H5)CH2Ph}(Pt-Tl)]PF6 (7‚PF6), was also formed
when only half an equivalent of TlPF6 was used,
illustrating that Tl+ is less reactive than Ag+ toward
the Pt-Cl bond, although the bond formation enthalpies
for TlCl and AgCl are ∆Hf ) -204 and -127 kJ/mol,
respectively.13 Solutions of 7‚PF6 in CH2Cl2 are stable
for weeks, but in coordinating solvents, like acetone and
acetonitrile, elimination of TlCl occurs immediately with
formation of the corresponding solvento species [Pt(CH2-
Ph)(PCH2-ox)(solvent)]+.
To our knowledge, 7‚PF6 is the first metal-metal
bonded Tl-Pt-Cl complex to be fully characterized.14
The coordination geometry around Pt(II) is square-
pyramidal, with Tl(I) in the apical position (Figure 2).
The Pt-Tl distance of 3.0942(9) Å is in the range found
for the few other d8-s2 Pt(II)-Tl(I) bonds reported in
the literature: 2.79-3.14 Å (CSD version 5.25).15 The
metal-metal bond in 7‚PF6 is best described as result-
ing mainly from donation of electron density from the
Scheme 3
Pt(II) 5dz orbital to the vacant Tl(I) 6pz orbital.16 The
2
Pt-Tl bond is not exactly orthogonal to the Pt(II)
square-plane (angle of 70(3)°), but parallel to the C(1)-
C(2) bond (Figure 2b). This deviation is likely to allow
better π-donation from the benzyl ligand to Tl+. The
distances between the benzyl carbon atoms C(2)-C(7)
and Tl+ are in the range 3.015(5)-3.620(5) Å, so that
Tl+ is not perfectly above the centroid of the aromatic
ring. The occurrence of both metal-metal and benzyl-
Tl+ bonding results in an unprecedented “chelating”
behavior for a Pt-benzyl complex. We believe that these
interactions are, at least in part, retained in CH2Cl2
solution since no precipitation of TlCl (or TlPF6) was
observed. The 31P{1H} NMR spectrum shows no re-
2.401(2) and 2.390(2) Å are, as expected, slightly longer
than that in 1 (2.359(1) Å) (Figure 1b). The two metal
coordination planes are almost orthogonal to each other
(87(1)°).
Reaction pathway I in Scheme 2 suggests a possible
extension to the synthesis of heterometallic single-
chloride-bridged complexes. Reaction between 4 and
[PdClMe(PCH2-ox)]6 in a 1:1 ratio indeed yielded [{Pt-
(CH2Ph)(PCH2-ox)}(µ-Cl){PdMe(PCH2-ox)}]BF4 (6‚BF4).
Both, the Pt/Pt (5‚BF4) and Pt/Pd (6‚BF4) complexes
react irreversibly with acetonitrile by splitting of the
bridge to afford [Pt(CH2Ph)Cl(PCH2-ox)] (1) and the
solvento species [Pt(CH2Ph)(NCMe)(PCH2-ox)]BF4 (3‚
BF4), and 1 and the known [PdMe(NCMe)(PCH2-ox)]-
BF4,6 respectively,12 consistent in the latter case with
a stronger Pt-Cl than Pd-Cl bond in 6‚BF4.
2
solved J(P-Tl) coupling and only a minor change in
the 1J(Pt-P) coupling.15f No 1J(Pt-Tl) coupling was
detected in the 195Pt{1H} NMR spectrum in CD2Cl2 or
CDCl3 solution, and only a broadening of the signal was
observed (∆ν1/2 ca. 500 Hz). This is consistent with a
weak s-character17 and an important ionic contribution
to the Pt-Tl bond and/or a longer Pt-Tl distance in
solution, probably for the benefit of a stronger Tl-η6-
benzyl interaction no longer limited by geometrical
constraints. The weak intermolecular Tl-F interactions
of 2.91(1) and 3.09(1) Å are similar to those in Pt(II)-
Tl(I) complexes with C6F5 substituents at the Pt center.15e
Because no Tl-F coupling was detected in the 19F{1H}
NMR at room temperature, it is likely that the ion pair
7‚PF6 is more separate in solution. No significant
change in the NMR spectrum was observed down to -80
°C; in particular no diagnostic coupling to Tl was
detected. The structural features of 7‚PF6 are different
When Ag+ was replaced with Tl+ as chloride abstrac-
tor, 4 was not observed. TlCl appeared only in traces,
and the main product (7) turned out to be an unexpected
adduct of Tl+ to 1, which readily crystallized (Scheme
3). Its X-ray analysis established the formation of both
a Pt-Tl bond and a η6-benzyl-Tl interaction (Figure
2). This bimetallic complex, [(PCH2-ox)ClPtTl{µ-(η1-
(10) (a) Shen, H.; Jordan, R. F. Organometallics 2003, 22, 1878-
1887. (b) Foley, S. R.; Shen, H.; Qadeer, U. A.; Jordan, R. F.
Organometallics 2004, 23, 600-609. (c) van den Broeke, J.; Heeringa,
J. J. H.; Chuchuryukin, A. V.; Kooijman, H.; Mills, A. M.; Spek, A. L.;
van Lenthe, J. H.; Ruttink, P. J. A.; Deelman, B.-J.; van Koten, G.
Organometallics 2004, 23, 2287-2294.
(11) (a) Renn, O.; Albinati, A.; Lippert, B. Angew. Chem., Int. Ed.
Engl. 1990, 29, 84-85. (b) Baar, C. R.; Jenkins, H. A.; Jennings, M.
C.; Yap, G. P. A.; Puddephatt, R. J. Organometallics 2000, 19, 4870-
4877. (c) Dahlenburg, L.; Mertel, S. J. Organomet. Chem. 2001, 630,
221-243. (d) Albano, V. G.; Serio, M. D.; Monari, M.; Orabona, I.;
Panunzi, A.; Ruffo, F. Inorg. Chem. 2002, 41, 2672-2677.
(12) When a sample of 5‚BF4 was dissolved in CD3CN, selective
irradiation of the PCH2 protons of [Pt(CH2Ph)Cl(PCH2-ox)] (1) through
homonuclear decoupling showed no effect on the signal of the PCH2
protons of [Pt(CH2Ph)(NCCD3)(PCH2-ox)]+ (3), indicating no chemical
exchange. Moreover, dissolving equivalent amounts of 1 and 3‚BF4 in
CDCl3, in place of CD3CN, did not lead to the formation of 5‚BF4.
(13) Holleman, A. F.; Wiberg, E. Lehrbuch der Anorganischen
Chemie, 101st ed.; de Gruyter: Berlin, 1995; pp 1101 and 1344.
(14) For a non metal-metal bonded complex, see: Devic, T.; Batail,
P.; Fourmigue´, M.; Avarvari, N. Inorg. Chem. 2004, 43, 3136-3141.
(15) (a) Nagle, J. K.; Balch, A. L.; Olmstead, M. M. J. Am. Chem.
Soc. 1988, 110, 319-321. (b) Balch, A. L.; Rowley, S. P. J. Am. Chem.
Soc. 1990, 112, 6139-6140. (c) Renn, O.; Lippert, B. Inorg. Chim. Acta
1993, 208, 219-224. (d) Uson, R.; Fornies, J.; Tomas, M.; Garde, R.;
Merino, R. I. Inorg. Chem. 1997, 36, 1383-1387. (e) Ara, I.; Berenguer,
J. R.; Fornies, J.; Go´mez, J.; Lalinde, E.; Merino, R. I. Inorg. Chem.
1997, 36, 6461-6464. (f) Song, H.-B.; Zhang, Z.-Z.; Hui, Z.; Che, C.-
M.; Mak, T. C. W. Inorg. Chem. 2002, 41, 3146-3154. (g) Charmant,
J. P. H.; Fornie´s, J.; Go´mez, J.; Lalinde, E.; Merino, R. I.; Moreno, M.
T.; Orpen, A. G. Organometallics 2003, 22, 652-656.
(16) Ziegler, T.; Nagle, J. K.; Snijders, J. G.; Baerends, E. J. J. Am.
Chem. Soc. 1989, 111, 5631-5635.
(17) Maliarik, M.; Berg, K.; Glaser, J.; Sandstro¨m, M.; To´th, I. Inorg.
Chem. 1998, 37, 2910-2919.

6314 Organometallics, Vol. 23, No. 26, 2004
Oberbeckmann-Winter et al.
Figure 2. Two views of the molecular structure of 7 in 7‚PF6. The hydrogen atoms and the counterion have been omitted
for clarity. Selected bond distances (Å) and angles (deg): Pt-C1 2.084(5), Pt-N 2.107(4), Pt-P1 2.194(1), Pt-Cl 2.392(2),
Pt-Tl 3.0942(9), C1-C2 1.485(7), Tl-C2 3.015(5), Tl-C3 3.111(5), Tl-C4 3.404(5), Tl-C5 3.620(5), Tl-C6 3.555(5), Tl-
C7 3.255(5); C1-Pt-P1 93.5(2), N-Pt-P1 83.1(1), C1-Pt-Cl 92.1(2), N-Pt-Cl 91.5(1), C1-Pt-Tl 85.7(1), C2-C1-Pt
114.4(4). There is no significant Tl/Cl interaction, as indicated by a separation of 3.225(5) Å.
from those in a Ru(II) complex that contained TlCl as a
ligand but in which the separation of 3.545(2) Å between
Ru and Tl was too long to allow significant direct metal-
metal interaction.18 In this complex, two phenyl groups
from the tetraphosphine ligand were oriented toward
the Tl atom, but the shortest contacts between their
carbon atoms and Tl were 3.218(1) and 3.303(1) Å, i.e.,
much longer than the Tl-C(2) and Tl-C(3) distances
in 7‚PF6.
Scheme 4. Synthesis of 9 and 10
Figure 3. Views of the molecular structures of 9 (a) in
9‚0.5CH2Cl2 and of 10 (b) in 10‚PF6‚0.75C4H8O. The
hydrogen atoms, the counterion, and the solvent have been
omitted for clarity. Selected bond distances (Å) and angles
(deg) for 9‚0.5CH2Cl2: Pt-C1 2.02(1), Pt-N 2.137(9), Pt-P
2.205(3), Pt-Cl1 2.359(3); C1-Pt-P 98.0(3), N-Pt-P 82.6-
(2), C1-Pt-Cl1 88.1(3), N-Pt-Cl1 91.4(2), C2-C1-Pt
121(1), Pt-C1-C2-C3 164(1). Selected bond distances (Å)
and angles (deg) for 10‚PF6‚0.75C4H8O: Pt-C1 1.82(1),
Pt-N 2.045(8), Pt-C2 2.07(1), Pt-P1 2.333(3), C1-O2
1.16(1); C1-Pt-C2 88.1(5), N-Pt-C2 91.4(4), C1-Pt-P1
100.0(4), N-Pt-P1 80.7(3), O2-C1-Pt 179(1), Pt-C2-
C3-C4-180(1).
of [PtClPh(PCH2-ox)] (8) afforded [Pt{C(O)Ph}Cl(PCH2-
ox)] (9) (Figure 3a), which was reacted with MX (M+ )
Ag+, Tl+) in CH2Cl2. This resulted exclusively in chloride
abstraction and CO deinsertion (Scheme 4). That the
phenyl ligand in 10 is trans to P, in contrast to trans to
N in 8, was established by X-ray diffraction (Figure 3b)
and results from the respective trans influences of the
ligands. A comparison of the molecular structures of the
benzyl complex 1 and the benzoyl complex 9 shows that
although the Pt-C1-C2 angles are similar in both cases
(115.9(4)° (1), 121(1)° (9)), coordination of the aromatic
moiety of 9 to a Pt-bound Tl+ would not be possible due
to an unfavorable Pt-C-aryl torsion angle (Pt-C1-C2-
C3): 64.7(6)° (1), 87.1(5)° (7), 164(1)° (9). The orientation
of the aryl ring in 9 is due to the π-interaction with the
carbonyl group.
We then considered replacing the benzyl ligand with
the structurally related benzoyl ligand, also commonly
encountered in organometallic chemistry and homoge-
neous catalysis,2a,c-f which could form a similar Pt-C-
C
ipso(aryl) angle. Insertion of CO into the Pt-aryl bond
(18) Bianchini, C.; Masi, D.; Linn, K.; Mealli, C.; Peruzzini, M.;
Zanobini, F. Inorg. Chem. 1992, 31, 4036-4037.

Electrophilic Activation
Conclusion
Organometallics, Vol. 23, No. 26, 2004 6315
PCH2-ox,6 [Au(PPh3)Cl],22 [Cu(NCMe)4]BF4.23 Other chemicals
were commercially available and used as received. All yields
given are based on Pt.
Our findings explain why a procedure widely used to
abstract a halide ligand in order to generate a positively
charged metal complex with enhanced (catalytic) reac-
tivity may not come to full completion or fail owing to
either trapping of the cationic complex by the neutral
precursor molecule or unexpected “capture” of the Tl(I)
cation by the neutral complex acting, in our case, as an
unprecedented chelate through metal-metal bond for-
mation and η6-benzyl coordination. The bonding inter-
action between the d8 Pt(II) and s2 Tl(I) center is
assisted by π-donation from the benzyl ligand to the Tl+
ion. That such interactions were not evidenced in the
case of the benzoyl ligand emphasizes the importance
of relatively small structural differences (CO vs CH2)
on the reactivity of typical organometallic chloride
complexes toward usual halide abstractors. Similar
ligand-assisted metallophilic interactions may have a
broader scope in reactivity studies and catalysis than
previously thought. In this context, it is interesting to
note that related alkali metal cation-π interactions
involving unsaturated organic moieties continue to
attract considerable interest owing to their intrinsic
nature and their potential importance in biological
systems and for the synthesis of novel molecular de-
vices.19
Synthesis and Spectroscopic Data for [Pt(CH2Ph)Cl-
(PCH2-ox)] (1). Solid [Pt(CH2Ph)Cl(cod)] (0.39 g, 0.91 mmol)
and PCH2-ox (0.25 g, 0.93 mmol) were dissolved in CH2Cl2 (20
mL), and the resulting solution was stirred for 3 h at room
temperature. Removing all volatiles yielded an off-white
residue, which was washed with diethyl ether (2 × 15 mL)
and pentane (20 mL) and dried in vacuo to afford the product
as a white powder (0.49 g, 0.83 mmol, 91%). Anal. Calcd for
C23H23ClNOPPt (590.95): C 46.75, H 3.92, N 2.37. Found: C
46.69, H 3.93, N 2.47. Suitable single crystals for X-ray analy-
sis were obtained at room temperature by slow diffusion of
pentane into a solution in CH2Cl2/toluene (2:1). 1H NMR (CD2-
Cl2): δ 2.78 (d, 2H, JP-H ) 4.2 Hz, JPt-H ) 100 Hz, PtCH2-
Ph), 3.22 (dt, 2H, 2JP-H ) 10.0 Hz, 5JH-H ) 2.0 Hz, 3JPt-H ) 27
Hz, PCH2), 4.05 (tt, 2H, 3JH-H ) 9.7 Hz, 5JH-H ) 2.0 Hz, NCH2),
4.59 (t, 2H, 3JH-H ) 9.7 Hz, OCH2), 6.60-6.70 (m, 2H, o-aryl-
CH, PtCH2Ph), 6.75-6.85 (m, 3H, m-,p-aryl-CH, PtCH2Ph),
7.40-7.65 (m, 10H, aryl-CH, PPh2). 1H NMR (CDCl3): δ 2.88
3
2
3
2
(d, 2H, JP-H ) 4.0 Hz, JPt-H ) 101 Hz, PtCH2Ph), 3.14 (dt,
2
5
3
2H, JP-H ) 9.9 Hz, JH-H ) 2.0 Hz, JPt-H ) 28 Hz, PCH2),
3
5
4.04 (tt, 2H, JH-H ) 9.7 Hz, JH-H ) 2.0 Hz, NCH2), 4.56 (t,
2H, 3JH-H ) 9.7 Hz, OCH2), 6.78 (br s, 5H, aryl-CH, PtCH2Ph),
7.35-7.60 (m, 10H, aryl-CH, PPh2). 1H NMR (CD3CN): δ 2.68
3
2
(d, 2H, JP-H ) 4.1 Hz, JPt-H ) 99 Hz, PtCH2Ph), 3.33 (dt,
2
5
3
2H, JP-H ) 10.2 Hz, JH-H ) 2.0 Hz, JPt-H ) 28 Hz, PCH2),
3
5
3.91 (tt, 2H, JH-H ) 9.7 Hz, JH-H ) 1.9 Hz, NCH2), 4.58 (t,
3
2H, JH-H ) 9.7 Hz, OCH2), 6.60-6.70 (m, 2H, aryl-CH,
PtCH2Ph), 6.70-6.80 (m, 3H, aryl-CH, PtCH2Ph), 7.45-7.65
Experimental Section
(m, 10H, aryl-CH, PPh2). 13C{1H} NMR (CD2Cl2): δ 5.8 (d,
2JP-C ) 4.1 Hz, JPt-C ) 600 Hz, PtCH2Ph), 32.8 (d, JP-C
)
1
1
General Procedures. All manipulations were carried out
under inert dinitrogen atmosphere, using standard Schlenk-
line conditions and dried and freshly distilled solvents. The
1H, 1H{31P}, 13C{1H}, 19F{1H}, and 31P{1H} NMR spectra were
recorded on a Bruker Avance 300 instrument at 300.13, 75.47,
282.40, and 121.49 MHz, respectively, using TMS, CFCl3, or
H3PO4 (85% in D2O) as external standards. The 195Pt{1H} NMR
spectra were recorded on a Bruker Avance 400 at 86.02 MHz
using H6PtCl6 in D2O as external standard. The irradiation
experiments on 5‚BF4 were carried out on a Bruker Avance
500 at 500.13 MHz. All NMR spectra were measured at 298
K, unless otherwise specified. The assignment of the signals
was made by 1H,1H-COSY and 1H,13C-HMQC experiments. IR
spectra were recorded as KBr pellets on a FT-IR IFS66 Bruker
spectrometer. Elemental C, H, and N analyses were performed
by the “Service de Microanalyses”, Universite´ Louis Pasteur,
Strasbourg. ES mass spectra were recorded on a Bruker
Daltonics microTOF mass spectrometer.
40.1 Hz, 2JPt-C ) 11 Hz, PCH2), 52.0 (s, 2JPt-C ) 13 Hz, NCH2),
72.9 (s, 3JPt-C ) 12 Hz, OCH2), 122.9 (s, 5JPt-C ) 12 Hz, p-aryl-
CH, PtCH2Ph), 127.6 (s, 4JPt-C ) 10 Hz, m-aryl-CH, PtCH2Ph),
1
3
127.8 (d, JP-C ) 60.9 Hz, ipso-aryl, PPh2), 128.9 (s, JPt-C
)
23 Hz, o-aryl-CH, PtCH2Ph), 129.2 (d, 3JP-C ) 11.8 Hz, m-aryl-
4
CH, PPh2), 132.0 (d, JP-C ) 2.8 Hz, p-aryl-CH, PPh2), 134.0
2
3
(d, JP-C ) 11.8 Hz, JPt-C ) 36 Hz, o-aryl-CH, PPh2), 149.4
(s, 2JPt-C ) 48 Hz, ipso-aryl, PtCH2Ph), 175.1 (d, 2JP-C ) 13.8
Hz, CdN). 31P{1H} NMR (CD2Cl2): δ 12.6 (s, JPt-P ) 4731
1
Hz). 31P{1H} NMR (CDCl3): δ 12.9 (s, JPt-P ) 4818 Hz). 31P-
1
{1H} NMR (CD3CN): δ 12.1 (s, JPt-P ) 4663 Hz). 195Pt{1H}
1
NMR (CD2Cl2): δ -3989 (d, 1JP-Pt ) 4712 Hz). 195Pt{1H} NMR
(CD3CN): δ -3985 (d, 1JP-Pt ) 4640 Hz). IR: 1640 s cm-1 (νCd
N).
Synthesis and Spectroscopic Data for [Pt(CH2Ph)-
(OTf)(PCH2-ox)] (2). Solid [Pt(CH2Ph)Cl(PCH2-ox)] (1) (0.14
g, 0.24 mmol) was dissolved in CH2Cl2 (20 mL), and AgOTf
(0.07 g, 0.27 mmol) was added in one portion. A white
precipitate was formed immediately, and the mixture was
stirred at room temperature for 1.5 h. Some Celite was added
to the reaction mixture, stirring was continued for 15 min, and
the solution was filtered. Removing the solvent in vacuo
afforded the product as an off-white powder (0.16 g, 0.23 mmol,
96%). Anal. Calcd for C24H23F3NO4PPtS (704.57): C 40.91, H
3.29, N 1.99. Found: C 40.82, H 3.69, N 1.53. 1H NMR
(CDCl3): δ 2.76 (s, 2H, 2JPt-H ) 78 Hz, PtCH2Ph), 3.55 (d, 2H,
The 1H NMR spectra of oxazoline systems N-coordinated to
Pt always show the typical AA′BB′ system for the two
methylene groups; the NCH2 group can additionally show a
5JH-H to the PCH2 group. When BF4- was used as counterion,
the 19F{1H} spectra provided the appropriate signal with the
pattern typical for 10B-19F and 11B-19F.20
The following compounds were synthesized according to
literature procedures: [Pt(CH2Ph)Cl(cod)],21 [PtClPh(cod)],21
3
3
2JP-H ) 10.5 Hz, JPt-H ) 30 Hz, PCH2), 4.09 (br t, 2H, JHsH
(19) (a) Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303-
1324. (b) Nicholas, J. B.; Hay, B. P.; Dixon, D. A. J. Phys. Chem. A
1999, 103, 1394-1400. (c) Gokel, G. W.; Barbour, L. J.; Ferdani, R.;
Hu, J. Acc. Chem. Res. 2002, 35, 878-886. (d) Orner, B. P.; Salvatella,
X.; Quesada, J. S.; de Mendoza, J.; Giralt, E.; Hamilton, A. D. Angew.
Chem., Int. Ed. 2002, 41, 117-119. (e) Bock, H.; Havlas, Z.; Ghara-
gozloo-Hubmann, K.; Holl, S.; Sievert, M. Angew. Chem., Int. Ed. 2003,
42, 4385-4389. (f) Schmitt, W.; Anson, C. E.; Hill, J. P.; Powell, A. K.
J. Am. Chem. Soc. 2003, 125, 11142-11143. (g) Gokel, G. W. Chem.
Commun. 2003, 2847-2852.
(20) Kuhlmann, K.; Grant, D. M. J. Phys. Chem. 1964, 68, 3208-
3213.
(21) Clark, H. C.; Manzer, L. E. J. Organomet. Chem. 1973, 59, 411-
428.
3
) 9.6 Hz, NCH2), 4.71 (t, 2H, JH-H ) 9.6 Hz, OCH2), 6.45-
6.55 (m, 2H, aryl-CH, PtCH2Ph), 7.00-7.10 (m, 3H, aryl-CH,
PtCH2Ph), 7.60-7.95 (m, 10H, aryl-CH, PPh2). 13C{1H} NMR
(CDCl3): δ 8.2 (br s, PtCH2Ph), 31.8 (d, 1JP-C ) 45.8 Hz, PCH2),
1
53.0 (s, NCH2), 73.6 (s, OCH2), 120.5 (br q, JF-C ) 319.0 Hz,
CF3), 122.0 (br s, m-aryl-CH, PtCH2Ph), 125.3 (br s, p-aryl-
1
CH, PtCH2Ph), 126.3 (d, JP-C ) 70.3 Hz, ipso-aryl, PPh2),
(22) Braunstein, P.; Lehner, H.; Matt, D. Inorg. Synth. 1990, 27,
218-221.
(23) Kubas, G. J. Inorg. Synth. 1979, 19, 90-91.

6316 Organometallics, Vol. 23, No. 26, 2004
Oberbeckmann-Winter et al.
3
130.1 (br s, o-aryl-CH, PtCH2Ph), 130.3 (d, JP-C ) 12.4 Hz,
6.70-6.90 (br s, 2H, aryl-CH, PtCH2Ph), 7.45-7.85 (m, 13H,
aryl-CH, PtCH2Ph and PPh2). 1H NMR (CD2Cl2): δ 2.81 (s,
m-aryl-CH, PPh2), 133.5 (d, 4JP-C ) 2.8 Hz, p-aryl-CH, PPh2),
2
3
2
2
134.0 (d, JP-C ) 12.5 Hz, JPt-C ) 37 Hz, o-aryl-CH, PPh2),
2H, JPt-H ) 50 Hz, PtCH2Ph), 3.44 (br d, 2H, JP-H ) 10.0
2
2
3
3
146.8 (s, JPt-C ) 48 Hz, ipso-aryl, PtCH2Ph), 175.8 (d, JP-C
Hz, JPt-H ≈ 28 Hz, PCH2), 3.86 (br t, 2H, JH-H ≈ 10 Hz,
) 11.8 Hz, CdN). 19F{1H} NMR (CDCl3): δ -78.2 (s, OTf).
NCH2), 4.70 (t, 2H, JH-H ) 9.7 Hz, OCH2), 6.70-6.85 (br s,
3
31P{1H} NMR (CDCl3): δ 8.5 (s, JPt-P ) 5204 Hz). IR: 1637
2H, aryl-CH, PtCH2Ph), 7.25-7.85 (m, 13H, aryl-CH, PtCH2Ph
and PPh2). 13C{1H} NMR (CDCl3): δ 17.9 (br s, PtCH2Ph), 30.9
(br d, 1JP-C ) 41.5 Hz, PCH2), 52.4 (br s, NCH2), 73.1 (s, OCH2),
124-135 (br ms, PtCH2Ph and PPh2); CdN could not be
assigned. At 188 K, the 1H NMR pattern is not very well
resolved owing to dynamic behavior. 19F{1H} NMR (CDCl3):
1
s cm-1 (νCdN).
Synthesis and Spectroscopic Data for [Pt(CH2Ph)-
(NCMe)(PCH2-ox)]BF4 (3‚BF4). Solid [Pt(CH2Ph)Cl(PCH2-
ox)] (1) (0.21 g, 0.36 mmol) was dissolved in CH3CN (25 mL),
and AgBF4 (0.07 g, 0.36 mmol) was added in one portion. A
white precipitate was formed immediately, and the mixture
was stirred at room temperature for 1.5 h. The solvent was
removed in vacuo and the residue extracted with CH2Cl2 (2 ×
20 mL). After reducing the volume in vacuo, the product was
obtained as an off-white powder by addition of diethyl ether.
The elemental analysis proved the formation of a diethyl ether
adduct (0.24 g, 0.32 mmol, 89%). Anal. Calcd for C25H26BF4N2-
OPPt‚C4H10O (757.48): C 45.98, H 4.79, N 3.70. Found: C
45.70, H 4.72, N 3.17. 1H NMR (CD2Cl2): δ 1.21 (t, 6H, 3JH-H
1
δ -73.3 (d, JP-F ) 714 Hz, PF6). 31P{1H} NMR (CDCl3): δ
∼28 (br s). 31P{1H} NMR (CD2Cl2): δ ∼27 (br s, which becomes
sharp at 188 K). 31P{1H} NMR (188 K, CD2Cl2): δ 8.7 (s, 1JP-Pt
) 5179 Hz). 195Pt{1H} NMR (CDCl3): δ -4052 (d, 1JP-Pt ) 5216
Hz). IR: 1640 s cm-1 (νCdN). MS [ES, m/z (rel int %)]: 555.1
[M+ - PF6 (100)].
Synthesis and Spectroscopic Data for [{Pt(CH2Ph)-
(PCH2-ox)}2(µ-Cl)]BF4 (5‚BF4). Procedure A. To a solution
of [Pt(CH2Ph)Cl(PCH2-ox)] (1) (0.36 g, 0.61 mmol) in CH2Cl2
(20 mL) was added AgBF4 (0.06 g, 0.31 mmol) in one portion.
The mixture was stirred for 2 h at room temperature, some
Celite was added, and the mixture was stirred for additional
30 min. The solution was then filtered and the solvent removed
in vacuo to yield 5‚BF4 as an off-white powder. Purification
by recrystallization from CH2Cl2/Et2O afforded the product as
a CH2Cl2 adduct (0.76 g, 0.58 mmol, 95%). Anal. Calcd for
C46H46BClF4N2O2P2Pt2‚CH2Cl2 (1318.18): C 42.83, H 3.67, N
2.13. Found: C 42.65, H 3.88, N 1.85. These crystals were
suitable for single-crystal X-ray analysis. 1H NMR (CDCl3): δ
5
) 7.0 Hz, OCH2CH3, Et2O), 2.30 (br d, 3H, JP-H ) 0.7 Hz,
PtNCCH3), 2.67 (d, 2H, 3JP-H ) 4.3 Hz, 2JPt-H ) 87 Hz, PtCH2-
Ph), 3.41 (dt, 2H, 2JP-H ) 10.4 Hz, 5JH-H ) 2.0 Hz, 3JPt-H ) 26
Hz, PCH2), 3.49 (t, 4H, 3JH-H ) 7.0 Hz, OCH2CH3, Et2O), 4.08
3
5
(tt, 2H, JH-H ) 9.7 Hz, JH-H ) 2.0 Hz, NCH2), 4.75 (t, 2H,
3JH-H ) 9.7 Hz, OCH2), 6.60-6.70 (m, 2H, o-aryl-CH, PtCH2Ph),
6.90-7.05 (m, 3H, m-,p-aryl-CH, PtCH2Ph), 7.50-7.80 (m,
10H, aryl-CH, PPh2). 1H NMR (CD3CN): δ 1.98 (br s, 3H,
PtNCCH3), 2.62 (d, 2H, 3JP-H ) 4.2 Hz, 2JPt-H ) 88 Hz, PtCH2-
Ph), 3.51 (dt, 2H, 2JP-H ) 10.6 Hz, 5JH-H ) 1.9 Hz, 3JPt-H ) 26
Hz, PCH2), 3.93 (tt, 2H, 3JH-H ) 9.7 Hz, 5JH-H ) 1.9 Hz, NCH2),
4.67 (t, 2H, 3JH-H ) 9.7 Hz, OCH2), 6.50-6.60 (m, 2H, o-aryl-
CH, PtCH2Ph), 6.90-6.95 (m, 3H, m-,p-aryl-CH, Pt-
CH2Ph), 7.55-7.75 (m, 10H, aryl-CH, PPh2). 13C{1H} NMR
(CD2Cl2): δ 3.2 (br s, PtNCCH3), 6.3 (d, 2JP-C ) 4.8 Hz, 1JPt-C
3
2
2.83 (d, 2H, JP-H ) 2.1 Hz, JPt-H ) 86 Hz, PtCH2Ph), 3.32
(br d, 2H, 2JP-H ) 10.2 Hz, PCH2), 3.94 (br t, 2H, 3JH-H ) 9.5
Hz, NCH2), 4.56 (t, 2H, JH-H ) 9.5 Hz, OCH2), 5.30 (s, 2H,
3
CH2Cl2), 6.60-6.70 (br m, 2H, o-aryl-CH, PtCH2Ph), 6.75-
6.85 (br m, 3H, m-,p-aryl-CH, PtCH2Ph), 7.30-7.65 (m, 10H,
aryl-CH, PPh2). 13C{1H} NMR (CDCl3): δ 7.2 (br m, PtCH2-
1
) 590 Hz, PtCH2Ph), 15.1 (s, OCH2CH3, Et2O), 32.2 (d, JP-C
) 42.9 Hz, PCH2), 53.2 (s, NCH2), 65.9 (s, OCH2CH3, Et2O),
73.8 (s, OCH2), 120.4 (br s, PtNCCH3), 124.0 (s, p-aryl-CH,
1
Ph), 32.1 (br d, JP-C ) 42.8 Hz, PCH2), 52.9 (br s, NCH2),
53.4 (s, CH2Cl2), 73.0 (s, OCH2), 123.2 (br s, p-aryl-CH,
1
1
PtCH2Ph), 125.8 (d, JP-C ) 67.1 Hz, ipso-aryl, PPh2), 128.2
PtCH2Ph), 127.6 (br s, m-aryl-CH, PtCH2Ph), 128.2 (d, JP-C
(s, m-aryl-CH, PtCH2Ph), 128.3 (s, 3JPt-C ) 21 Hz, o-aryl-CH,
PtCH2Ph), 129.9 (d, 3JP-C ) 12.5 Hz, m-aryl-CH, PPh2), 133.1
) 63.3 Hz, ipso-aryl, PPh2), 128.6 (br s, o-aryl-CH, PtCH2Ph),
129.1 (d, 3JP-C ) 11.4 Hz, m-aryl-CH, PPh2), 132.2 (br d, 4JP-C
) 2.5 Hz, p-aryl-CH, PPh2), 133.4 (d, 2JP-C ) 11.8 Hz, o-aryl-
CH, PPh2), 148.2 (br s, ipso-aryl, PtCH2Ph), 175.0 (br s, Cd
N). 19F{1H} NMR (CDCl3): δ -154.0 (BF4). 31P{1H} NMR
(CDCl3): δ 11.5 (br s, 1JPt-P ) 5209 Hz, PPh2). 195Pt{1H} NMR
4
2
(d, JP-C ) 2.8 Hz, p-aryl-CH, PPh2), 133.8 (d, JP-C ) 11.8
3
Hz, JPt-C ) 39 Hz, o-aryl-CH, PPh2), 147.3 (s, ipso-aryl,
PtCH2Ph), 176.7 (d, JP-C ) 12.5 Hz, CdN). 19F{1H} NMR
2
(CD3CN): δ -152.2 (BF4). 31P{1H} NMR (CD2Cl2): δ 10.4 (s,
1JPt-P ) 4802 Hz). 31P{1H} NMR (CD3CN): δ 9.8 (s, JPt-P
)
1
1
(CDCl3): δ -4051 (d, JP-Pt ) 5177 Hz). 195Pt{1H} NMR (193
4736 Hz). 195Pt{1H} NMR (CD2Cl2): δ -4194 (d, 1JP-Pt ) 4808
Hz). 195Pt{1H} NMR (CD3CN): δ -4198 (d, 1JP-Pt ) 4750 Hz).
IR: 1637 s cm-1 (νCdN).
1
K, CD2Cl2): δ -4090 (d, JP-Pt ) 5220 Hz). IR: 1639 s cm-1
(νCdN). MS [ES, m/z (rel int %)]: 1146.2 [M+ - BF4 (5)], 555.1
[(C23H23NOPPt)+ (100)].
Alternatively, cation 3 can also be prepared from TlPF6 or
AgOTf instead of AgBF4. 3‚BF4 was also obtained when 1 equiv
of [Cu(NCMe)4]BF4 in CH2Cl2/THF was used.
When a sample of 5‚BF4 was dissolved in CD3CN, selective
irradiation of the PCH2 protons of [Pt(CH2Ph)Cl(PCH2-ox)] (1)
through homonuclear decoupling showed no effect on the signal
of the PCH2 protons of [Pt(CH2Ph)(NCCD3)(PCH2-ox)]+ (3).
Synthesis and Spectroscopic Data for [Pt(η3-CH2Ph)-
(PCH2-ox)]PF6 (4‚PF6). Solid [Pt(CH2Ph)Cl(PCH2-ox)] (0.20
g, 0.34 mmol) was dissolved in THF (15 mL), the solution was
cooled to -60 °C, and AgPF6 (0.09 g, 0.36 mmol) was added in
one portion. The mixture was stirred for 2 h at room temper-
ature, some Celite was added, and the mixture was stirred
for an additional 30 min. The solution was then filtered and
the solvent removed in vacuo to yield the product as a white
powder, which was washed with pentane (20 mL) (0.20 g, 0.29
mmol, 85%). The reaction can also be carried out in CH2Cl2
and with AgBF4 instead of AgPF6. Anal. Calcd for C23H23F6-
NOP2Pt (700.46): C 39.44, H 3.31, N 2.00. Found: C 39.05, H
3.83, N 1.66. Further purification by recrystallization led to
decomposition of the product, so that no better elemental
analysis could be obtained. The product is especially unstable
in chlorinated solvents at room temperature. 1H NMR
Procedure B. Cation 5 could also be obtained by using 1
equiv of ZnCl2 in THF,24 and Zn2Cl5 was formed as counte-
-
rion.25 The product can be recrystallized from CH2Cl2/pentane.
Anal. Calcd for C46H46ClN2O2P2Pt2‚Zn2Cl5‚CH2Cl2: C, 36.67;
H 3.14; N, 1.82. Found: C, 36.32; H, 3.31; N, 1.64.
Procedure C. Solid [AuCl(PPh3)] (0.14 g, 0.28 mmol) in
CH2Cl2 (7 mL) was cooled to -78 °C and AgBF4 (0.06 g, 0.31
mmol) added in one portion. The mixture was stirred for 2 h
at -78 °C, and then the precipitate was allowed to settle. The
filtered solution of [Au(PPh3)]BF4 was added via cannula to a
solution of [Pt(CH2Ph)Cl(PCH2-ox)] (1) (0.17 g, 0.29 mmol) in
CH2Cl2 (10 mL) at -78 °C. The mixture was stirred for 3 h
while kept at this temperature. Removing the solvent in vacuo
(24) Anderson, T. J.; Vicic, D. A. Organometallics 2004, 23, 623-
625.
(25) Abbott, A. P.; Capper, G.; Davies, D. L.; Rasheed, R. Inorg.
Chem. 2004, 43, 3447-3452.
2
(CDCl3): δ 2.74 (s, 2H, JPt-H ) 52 Hz, PtCH2Ph), 3.43 (br d,
2
3
2H, JP-H ) 9.6 Hz, JPt-H ≈ 28 Hz, PCH2), 3.94 (br t, 2H,
3JH-H ≈ 10 Hz, NCH2), 4.70 (t, 2H, JH-H ) 9.6 Hz, OCH2),
3

Electrophilic Activation
Organometallics, Vol. 23, No. 26, 2004 6317
was followed by extraction of the residue at -60 °C with CH2-
Cl2. NMR spectra showed the existence of mixture of [Au-
(PPh3)]BF4 and [{Pt(CH2Ph)(PCH2-ox)}2(µ-Cl)]BF4 (5‚BF4).
Procedure D. A mixture of equimolar amounts of 1 and
4‚BF4 in CDCl3 also led to the formation of 5‚BF4; the reaction
was monitored by 31P{1H} NMR spectroscopy.
PtCH2Ph), 6.90 (br t, 1H, 3JH-H ≈ 7.2 Hz, p-aryl-CH, PtCH2Ph),
3
7.00 (pseudo t, 2H, JH-H ≈ 7.3 Hz, m-aryl-CH, PtCH2Ph),
7.50-7.80 (m, 10H, aryl-CH, PPh2). 13C{1H} NMR (CD2Cl2):
2
1
δ 4.4 (d, JP-C ) 4.7 Hz, PtCH2Ph), 32.8 (d, JP-C ) 42.8 Hz,
PCH2), 52.2 (br s, NCH2), 73.5 (s, 3JPt-C ) 10 Hz, OCH2), 124.7
(s, p-aryl-CH, PtCH2Ph), 127.1 (d, 1JP-C ) 63.9 Hz, ipso-aryl,
3
PPh2), 129.1 (s, m-aryl-CH, PtCH2Ph), 130.1 (d, JP-C ) 11.8
Synthesis and Spectroscopic Data for [{Pt(CH2Ph)-
(PCH2-ox)}(µ-Cl){PdMe(PCH2-ox)}]BF4 (6‚BF4). To a solu-
tion of [Pt(CH2Ph)Cl(PCH2-ox)] (1) (0.16 g, 0.27 mmol) in
CH2Cl2 or THF (15 mL) at -60 °C was added AgBF4 (0.06 g,
0.31 mmol) in one portion. The mixture was stirred for 1.5 h
at room temperature, some Celite was added, and the mixture
was stirred for an additional 30 min. The solution was then
filtered into a solution of [PdMeCl(PCH2-ox)] (0.12 g, 0.27 mol)
in CH2Cl2 or THF (15 mL) at -60 °C, and stirring was
continued for an additional 2 h. After removing the solvent in
vacuo, the residue was extracted with THF (20 mL) and the
volume of the solution was reduced again. Addition of diethyl
ether afforded a beige powder of the product as a THF adduct
(0.26 g, 0.23 mmol, 85%). Anal. Calcd for C40H42BClF4N2O2P2-
PtPd‚C4H8O (1140.60): C 46.33, H 4.42, N 2.46. Found: C
46.60, H 4.57, N 2.33. 1H NMR (CDCl3): δ 0.55 (s, 3H, PdCH3),
Hz, m-aryl-CH, PPh2), 130.4 (s, o-aryl-CH, PtCH2Ph), 133.1
(br d, 4JP-C ) 3.1 Hz, p-aryl-CH, PPh2), 133.9 (d, 2JP-C ) 11.8
3
Hz, JPt-C ) 34 Hz, o-aryl-CH, PPh2), 152.0 (br s, ipso-aryl,
PtCH2Ph), 176.8 (br s, CdN). 19F{1H} NMR (CD2Cl2): δ -70.8
(d, JP-F ) 716 Hz, PF6). 31P{1H} NMR (CD2Cl2): δ -143.0
1
1
1
(sept, JP-F ) 716 Hz, PF6), 13.0 (s, JPt-P ) 4467 Hz, PPh2).
31P{1H} NMR (CDCl3): δ -143.2 (sept, JP-F ) 713 Hz, PF6),
1
12.7 (s, JPt-P ) 4598 Hz, PPh2). 195Pt{1H} NMR (CD2Cl2): δ
1
-3803 (br d, JP-Pt ) 4476 Hz). 195Pt{1H} NMR (CDCl3): δ
1
∼-3830 (br d, JP-Pt ≈ 4560 Hz). IR: 1637 s cm-1 (νCdN).
1
Synthesis and Spectroscopic Data for [PtClPh(PCH2-
ox)] (8). A mixture of [PtClPh(cod)] (0.61 g, 1.47 mmol) and
PCH2-ox (0.40 g, 1.49 mmol) was dissolved in CH2Cl2 (35 mL),
and the resulting solution was stirred for 3 h at room
temperature. Removing all volatiles in vacuo yielded the
product as an off-white residue, which was washed with
diethyl ether (15 mL) and pentane (2 × 15 mL) and dried in
vacuo to afford 8 as a white powder (0.82 g, 1.42 mmol, 97%).
Anal. Calcd for C22H21ClNOPPt (576.92): C, 45.80; H, 3.67;
N, 2.43. Found: C, 45.87; H, 3.92; N, 2.27. 1H NMR (CD2Cl2):
δ 3.37 (dt, 2H, 2JP-H ) 9.9 Hz, 5JH-H ) 2.1 Hz, 3JPt-H ) 24 Hz,
3
1.85 (m, 4H, OCH2CH2, THF), 2.83 (d, 2H, JP-H ) 3.5 Hz,
2
2JPt-H ) 93 Hz, PtCH2Ph), 3.35 (d, 2H, JP-H ) 10.3 Hz,
PtPCH2), 3.44 (d, 2H, 2JP-H ) 10.6 Hz, PdPCH2), 3.74 (m, 4H,
OCH2CH2, THF), 4.01 (br m, 2H, PdNCH2), 4.20 (br t, 2H,
3JH-H ) 9.3 Hz, PtNCH2), 4.60 (t, 2H, 3JH-H ) 9.6 Hz, OCH2-
(Pd)), 4.66 (br t, 2H, 3JH-H ) 9.3 Hz, OCH2(Pt)), 6.60-6.75 (br
m, 2H, o-aryl-CH, PtCH2Ph), 6.75-6.85 (br m, 3H, m-,p-aryl-
CH, PtCH2Ph), 7.35-7.75 (m, 20H, aryl-CH, PPh2). 13C{1H}
NMR (CDCl3): δ -2.5 (s, PdCH3), 6.8 (br s, PtCH2Ph), 25.6
(s, OCH2CH2, THF), 32.4 (br d, 1JP-C ≈ 39 Hz, PCH2), 32.5 (d,
1JP-C ) 33.2 Hz, PCH2), 52.6 (br s, NCH2), 53.1 (s, NCH2), 68.0
(s, OCH2CH2, THF), 72.7 (s, OCH2), 72.8 (br s, OCH2), 122.9
(s, p-aryl-CH, PtCH2Ph), 127.5 (br s, m-aryl-CH, PtCH2Ph),
128.0-133.6 (m, aryl-CH and ipso-aryl, PtCH2Ph, PtPPh2 and
PdPPh2), 148.6 (br s, ipso-aryl, PtCH2Ph), 172.1 (m, CdN(Pd)),
175.2 (m, CdN(Pt)). 19F{1H} NMR (CDCl3): δ -154.0 (BF4).
31P{1H} NMR (CDCl3): δ 11.9 (br s, 1JPt-P ) 5012 Hz, PtPPh2),
34.0 (s, PdPPh2). IR: 1639 s cm-1 (νCdN). MS [ES, m/z (rel int
%)]: 981.1 [M+ - BF4 (28)], 555.1 [(C23H23NOPPt)+ (30)], 431
(100), 390.0 [(C17H19NOPPd)+ (30)].
3
5
PCH2), 4.17 (tt, 2H, JH-H ) 9.7 Hz, JH-H ) 2.1 Hz, NCH2),
3
4.71 (t, 2H, JH-H ) 9.7 Hz, OCH2), 6.68-6.74 (m, 3H, m-,
3
p-aryl-CH, PtPh), 6.88-7.08 (m, 2H, JPt-H ) 46 Hz, o-aryl-
CH, PtPh), 7.40-7.60 (ms, 10H, aryl-CH, PPh2). 1H NMR
(CDCl3): δ 3.30 (dt, 2H, 2JP-H ) 9.9 Hz, 5JH-H ) 2.0 Hz, 3JPt-H
) 24 Hz, PCH2), 4.24 (tt, 2H, 3JH-H ) 9.7 Hz, 5JH-H ) 2.0 Hz,
NCH2), 4.68 (t, 2H, 3JH-H ) 9.7 Hz, OCH2), 6.70-6.80 (m, 3H,
m-,p-aryl-CH, PtPh), 6.88-7.08 (m, 2H, 3JPt-H ) 46 Hz, o-aryl-
CH, PtPh), 7.40-7.60 (ms, 10H, aryl-CH, PPh2). 13C{1H} NMR
1
2
(CDCl3): δ 31.8 (d, JP-C ) 39.7 Hz, PCH2), 51.7 (s, JPt-C
)
15 Hz, NCH2), 72.6 (s, 3JPt-C ) 10 Hz, OCH2), 122.6 (s, p-aryl-
3
CH, PtPh), 127.0 (s, JPt-C ) 54 Hz, m-aryl-CH, PtPh), 127.8
1
3
(d, JP-C ) 63.3 Hz, ipso-aryl, PPh2), 128.8 (d, JP-C ) 11.2
4
Hz, m-aryl-CH, PPh2), 131.7 (d, JP-C ) 2.8 Hz, p-aryl-CH,
2
3
PPh2), 133.2 (d, JP-C ) 11.8 Hz, JPt-C ) 34 Hz, o-aryl-CH,
Synthesis and Spectroscopic Data for [(PCH2-ox)-
ClPtTl{µ-(η1-CH2;η6-C6H5)CH2Ph}(Pt-Tl)]PF6 (7‚PF6). Solid
[Pt(CH2Ph)Cl(PCH2-ox)] (1) (0.18 g, 0.30 mmol) was dissolved
in CH2Cl2 (25 mL), and TlPF6 (0.11 g, 0.31 mmol) was added
in one portion. The suspension was stirred at room tempera-
ture for 2 h, some Celite was added to the reaction mixture
(to facilitate removal of traces of TlCl by filtration), and stirring
was continued for an additional 15 min. The solution was
filtered via cannula and the solvent slowly removed to allow
the product to crystallize. (Alternatively, the product can be
dissolved in a minimum amount of CH2Cl2 (0.5-1 mL) and
allowed to crystallize overnight.) It was purified by washing
with cold THF (5 mL) and pentane (15 mL), affording an off-
white crystalline powder of 7‚PF6 (0.18 g, 0.19 mmol, 63%).
Anal. Calcd for C23H23ClF6NOP2PtTl (940.30): C 29.38, H 2.47,
N 1.49. Found: C 29.56, H 2.37, N 1.31. Suitable single crystals
for X-ray analysis were obtained at room temperature from a
2
3
PPh2), 137.3 (d, JPt-C ) 15 Hz, JP-C ) 3.1 Hz, o-aryl-CH,
PtPh), 175.5 (d, 2JP-C ) 14.3 Hz, CdN); ipso-aryl for PtPh not
assigned. 31P{1H} NMR (CD2Cl2): δ 9.5 (s, 1JPt-P ) 4512 Hz).
195Pt{1H} NMR (CD2Cl2): δ -3850 (d, JP-Pt ) 4539 Hz). IR:
1
1643 s cm-1 (νCdN).
Synthesis and Spectroscopic Data for [Pt{C(O)Ph}-
Cl(PCH2-ox)] (9). A solution of [PtClPh(PCH2-ox)] (8) (0.26
g, 0.45 mmol) in CH2Cl2 (25 mL) was placed under CO
atmosphere and stirred for 2.5 days at room temperature.
Removing all volatiles in vacuo and purification of the product
by filtration through Celite with CH2Cl2/toluene (1:1) yielded
9 as a pale yellow residue (0.26 g, 0.43 mmol, 96%). Anal. Calcd
for C23H21ClNO2PPt (604.93): C, 45.67; H, 3.50; N, 2.32.
Found: C, 45.45; H, 3.79; N, 2.16. Single crystals suitable for
X-ray structure analysis were obtained from toluene/CH2Cl2
(1:1), which was layered with pentane. 1H NMR (CDCl3): δ
3.37 (dt, 2H, 2JP-H ) 10.1 Hz, 5JH-H ) 2.0 Hz, 3JPt-H ) 27 Hz,
1
CD2Cl2 solution in an NMR tube. H NMR (CD2Cl2): δ 2.92
3
2
3
5
(d, 2H, JP-H ) 4.3 Hz, JPt-H ) 96 Hz, PtCH2Ph), 3.52 (dt,
PCH2), 4.13 (tt, 2H, JH-H ) 9.7 Hz, JH-H ) 2.0 Hz, NCH2),
4.68 (t, 2H, 3JH-H ) 9.7 Hz, OCH2), 7.03-7.08 (m, 2H, m-aryl-
CH, C(O)Ph), 7.14-7.20 (m, 1H, p-aryl-CH, C(O)Ph), 7.29-
7.35 (m, 4H, aryl-CH, PPh2), 7.37-7.43 (m, 2H, aryl-CH, PPh2),
7.54-7.61 (m, 4H, aryl-CH, PPh2), 7.76-7.80 (m, 2H, o-aryl-
2
5
3
2H, JP-H ) 10.4 Hz, JH-H ) 1.9 Hz, JPt-H ) 24 Hz, PCH2),
4.02 (tt, 2H, JH-H ) 9.7 Hz, JH-H ) 1.9 Hz, NCH2), 4.72 (t,
3
5
3
3
2H, JH-H ) 9.7 Hz, OCH2), 6.44 (br d, 2H, JH-H ≈ 7.2 Hz,
3
o-aryl-CH, PtCH2Ph), 6.93 (br t, 1H, JH-H ≈ 7.2 Hz, p-aryl-
3
1
CH, PtCH2Ph), 7.09 (pseudo t, 2H, JH-H ≈ 7.2 Hz, m-aryl-
CH, C(O)Ph). 13C{1H} NMR (CDCl3): δ 30.8 (d, JP-C ) 39.7
1
CH, PtCH2Ph), 7.60-7.85 (m, 10H, aryl-CH, PPh2). H NMR
Hz, 2JPt-C ) 9 Hz, PCH2), 51.2 (s, 2JPt-C ) 11 Hz, NCH2), 72.6
(s, OCH2), 122.6 (s, p-aryl-CH, C(O)Ph), 127.0 (s, o-aryl-CH,
C(O)Ph), 127.9 (d, 1JP-C ) 63.0 Hz, ipso-aryl, PPh2), 128.8 (d,
3JP-C ) 11.4 Hz, m-aryl-CH, PPh2), 129.5 (s, m-aryl-CH, C(O)-
Ph), 131.6 (d, 4JP-C ) 3.0 Hz, p-aryl-CH, PPh2), 132.8 (d, 2JP-C
(CDCl3): δ 2.94 (d, 2H, 3JP-H ) 4.3 Hz, 2JPt-H ) 98 Hz, PtCH2-
2
3
Ph), 3.44 (br d, 2H, JP-H ) 10.3 Hz, JPt-H ) 23 Hz, PCH2),
4.11 (br t, 2H, 3JH-H ) 9.8 Hz, NCH2), 4.72 (t, 2H, 3JH-H ) 9.8
3
Hz, OCH2), 6.60 (br d, 2H, JH-H ≈ 7.1 Hz, o-aryl-CH,

6318 Organometallics, Vol. 23, No. 26, 2004
Oberbeckmann-Winter et al.
) 12.3 Hz, 3JPt-C ) 36 Hz, o-aryl-CH, PPh2), 146.2 (d, 3JP-C
)
(I); 2.62° < θ < 34.96°; 253 parameters. Final results: R1 )
0.0511; wR2 ) 0.1392, Gof ) 1.001, max./min. residual
2
4.6 Hz, ipso-aryl, C(O)Ph), 175.0 (d, JP-C ) 13.7 Hz, CdN),
2
210.3 (d, JP-C ) 3.8 Hz, CdO). 31P{1H} NMR (CDCl3): δ 7.0
electronic density ) 4.548/-3.877 e Å-3
.
1
(s, JPt-P ) 4721 Hz). 195Pt{1H} NMR (CDCl3): δ -3576 (d,
Complex 5‚BF4‚0.5CH2Cl2: C46H46BClF4N2O2P2Pt2‚0.5CH2-
Cl2; M ) 1275.69; monoclinic, P21/n; a ) 16.000(1) Å, b )
13.307(2) Å, c ) 23.089(2) Å, â ) 94.49(4)°; V ) 4900.8(9) Å3,
Z ) 4, Dc ) 1.729 g cm-3, µ ) 5.930 mm-1, F(000) ) 2468;
Tmin/max ) 0.730/0.893. Colorless prisms, dimensions 0.08 ×
0.07 × 0.05 mm3; total number of collected reflections 38 110
(independent 14 301), with 8787 having I > 2σ(I); 1.50° < θ <
30.05°; 568 parameters. Final results: R1 ) 0.0700; wR2 )
0.1820, Gof ) 1.044, max./min. residual electronic density )
1JP-Pt ) 4703 Hz). IR: 1637 s (νCdN), 1614 s cm-1 (νCdO).
Synthesis and Spectroscopic Data for [PtPh(CO)-
(PCH2-ox)]PF6 (10‚PF6). A mixture of [Pt{C(O)Ph}Cl(PCH2-
ox)] (0.21 g, 0.35 mmol) and TlPF6 (0.13 g, 0.37 mmol) was
suspended in CH2Cl2 (30 mL), and the mixture was stirred
for 2 h at room temperature. Removing all volatiles in vacuo
was followed by extraction of the residue with CH2Cl2 (15 mL).
The product (10‚PF6) was obtained as an off-white solid by
removing the solvent in vacuo (0.24 g, 0.34 mmol, 97%). Anal.
Calcd for C23H21F6NO2P2Pt (714.44): C 38.67, H 2.96, N 1.96.
Found: C 38.94, H 3.18, N 1.87. Recrystallization from CH2-
Cl2/THF (2:1) and slow removal of the solvents at room
temperature afforded single crystals of 10‚PF6‚0.75C4H8O
suitable for X-ray analysis. 1H NMR (CD2Cl2): δ 3.48 (tt, 2H,
1.023/-1.102 e Å-3
.
Complex 7‚PF6: C23H23ClF6NOP2PtTl; M ) 940.27; tri-
clinic, P1h; a ) 8.864(1) Å, b ) 11.287(1) Å, c ) 13.984(1) Å, R
) 80.83(3)°, â ) 72.74(3)°, γ ) 84.38(3)°; V ) 1317.1(2) Å3, Z
) 2, Dc ) 2.371 g cm-3, µ ) 11.698 mm-1, F(000) ) 872; Tmin/max
) 0.214/0.339. Colorless needles, dimensions 0.12 × 0.10 ×
0.11 mm3; total number of collected reflections 9064 (indepen-
dent 6017), with 5346 having I > 2σ(I); 1.54° < θ < 27.46°;
325 parameters. Final results: R1 ) 0.0284; wR2 ) 0.0920,
Gof ) 1.209, max./min. residual electronic density ) 0.901/-
3JH-H ) 9.8 Hz, 5JH-H ) 1.7 Hz, NCH2), 3.88 (dt, 2H, 2JP-H
)
5
3
10.5 Hz, JH-H ) 1.7 Hz, PCH2), 4.74 (t, 2H, JH-H ) 9.8 Hz,
OCH2), 7.15-7.22 (m, 1H, p-aryl-CH, PtPh), 7.29-7.36 (m, 2H,
o-aryl-CH, PtPh), 7.45-7.80 (ms, 12H, aryl-CH, PtPh and
PPh2). 1H{31P} NMR (CD2Cl2): δ 3.48 (tt, 2H, 3JH-H ) 9.8 Hz,
5JH-H ) 1.7 Hz, NCH2), 3.87 (br s, 2H, PCH2), 4.74 (t, 2H, 3JH-H
) 9.8 Hz, OCH2), 7.15-7.22 (m, 1H, p-aryl-CH, PtPh), 7.30-
7.35 (m, 2H, aryl-CH, PtPh), 7.45-7.80 (m, 12H, aryl-CH, PtPh
and PPh2). 13C{1H} NMR (CD2Cl2): δ 29.4 (d, 1JP-C ) 41.7 Hz,
2JPt-C ) 15 Hz, PCH2), 52.5 (d, 4JP-C ) 2.1 Hz, 2JPt-C ) 59 Hz,
2.403 e Å-3
.
Complex 9‚0.5CH2Cl2: C23H21ClNO2PPt‚0.5CH2Cl2; M )
647.38; monoclinic, P21/a; a ) 11.094(1) Å, b ) 12.717(1) Å, c
) 16.605(1) Å, â ) 104.04(5)°; V ) 2272.7(3) Å3, Z ) 4, Dc )
1.892 g cm-3, µ ) 6.501 mm-1, F(000) ) 1252, Tmin,max ) 0.574/
0.602. Pale yellow prisms, dimensions 0.08 × 0.07 × 0.07 mm3;
total number of collected reflections 11 590 (independent 6631),
with 3687 having I > 2σ(I); 1.26° < θ < 30.02°; 270 parameters.
Final results: R1 ) 0.1201; wR2 ) 0.1404, Gof ) 1.119, max./
min. residual electronic density ) 2.43/-1.86 e Å-3. The heavy
atoms of the solvent molecules have only been refined isotro-
pically. A disordered CH2Cl2 molecule (occupancy factor ) 0.5)
was found near to the -1 symmetry center (0,0,0.5), which
could account for the relatively large wR2 value.
Complex 10‚PF6‚0.75C4H8O: C23H21F6NO2P2Pt‚0.75C4H8O;
M ) 768.52; orthorhombic, P21221; a ) 9.849(1) Å, b ) 12.830-
(3) Å, c ) 22.661(5) Å; V ) 2864(1) Å3, Z ) 4, Dc ) 1.783 g
cm-3, µ ) 5.078 mm-1, F(000) ) 1496. Off-white prisms,
dimensions 0.08 × 0.07 × 0.07 mm3; total number of collected
reflections 25 904 (independent 6565), with 5301 having I >
2σ(I); 1.59° < θ < 27.47°; 334 parameters. Final results: R1
) 0.0550; wR2 ) 0.1311, Gof ) 1.033, max./min. residual
electronic density ) 1.712/-1.912 e Å-3; Flack parameter
0.004(13). The heavy atoms of the solvent molecules have only
been refined isotropically, leading to one residue corresponding
to a THF molecule with occupancy factor 0.5 and another THF
molecule with occupancy factor 0.25.
Crystallographic data for these structures have been de-
posited with the Cambridge Crystallographic Data Centre as
Supplementary Publication nos. CCDC 241929-241933. Cop-
ies of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (44)
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
Acknowledgment. This work was supported by the
CNRS, the Ministe`re de la Recherche, and the COST
Action D-30 of the European Commission. N.O.-W. is
grateful to the European Community for a Marie Curie
fellowship (HPMF-CT-2002-01659) and to the French
Embassy in Berlin and the Ministe`re des Affaires
Etrange`res (Paris) for a postdoctoral grant. We thank
the NMR Service of the Centre de Recherche Chimie
(ULP) for assistance.
3
1
NCH2), 74.5 (s, JPt-C ) 35 Hz, OCH2), 125.8 (d, JP-C ) 54.8
4
Hz, ipso-aryl, PPh2), 126.7 (br s, JPt-C ) 7 Hz, p-aryl-CH,
2
2
PtPh), 130.2 (d, JP-C ) 16.9 Hz, JPt-C ) 44 Hz, o-aryl-CH,
3
PtPh), 130.5 (d, JP-C ) 11.7 Hz, m-aryl-CH, PPh2), 133.0 (d,
4JP-C ) 13.1 Hz, JPt-C ) 13 Hz, m-aryl-CH, PtPh), 133.3 (d,
3
4JP-C ) 2.8 Hz, p-aryl-CH, PPh2), 136.0 (d, JP-C ) 2.8 Hz,
2
3JPt-C ) 24 Hz, o-aryl-CH, PPh2), 144.1 (d, JP-C ) 46.7 Hz,
2
1JPt-C ) 641 Hz, ipso-aryl, PtPh), 165.1 (d, JP-C ) 6.9 Hz,
2
1JPt-C ) 1827 Hz, CdO), 188.1 (d, JP-C ) 23.5 Hz, JPt-C
)
2
2
46 Hz, CdN). 19F{1H} NMR (CD2Cl2): δ -73.4 (d, 1JP-F ) 712
Hz, PF6). 31P{1H} NMR (CD2Cl2): δ -143.3 (sept, 1JP-F ) 712
Hz, PF6), 25.8 (s, 1JPt-P ) 1390 Hz, PPh2). 195Pt{1H} NMR (CD2-
Cl2): δ -4256 (br d, 1JP-Pt ) 1371 Hz). IR: 2091 s (νCdO) cm-1
,
1641 w, 1614 ms cm-1
.
Cation 10 can also be prepared from 9 and 1 equiv of AgBF4
or 1 equiv of [Au(PPh3)]BF4 in CH2Cl2 to yield 10‚BF4.
X-ray Crystal Structure Determination of 1, 5‚BF4‚
0.5CH2Cl2, 7‚PF6, 9‚0.5CH2Cl2, and 10‚PF6‚0.75C4H8O. The
diffraction data were collected on a Nonius Kappa-CCD area
detector diffractometer (Mo KR, λ ) 0.71070 Å; phi scan) at T
) 173(2) K. The complete conditions of the data collection
(Denzo software) and structural refinements are given below.
The cell parameters were determined from reflections taken
from one set of 10 frames (1.0° steps in phi angle), each at 20
s exposure. The structures were solved using direct methods
(SHELXS97) and refined against F2 using the SHELXL97
software. The absorption was corrected empirically (with
Sortav)26a for compounds 1, 5‚BF4‚0.5CH2Cl2, 7‚PF6, and 9‚0.5-
CH2Cl2. Largest peaks are near the Pt atoms (at 0.88 and 0.92
Å). All non-hydrogen atoms were refined anisotropically unless
otherwise specified. Hydrogen atoms were generated according
to stereochemistry and refined using a riding model in
SHELXL97.26b
Complex 1: C23H23ClNOPPt; M ) 590.93; monoclinic, P21/
a; a ) 16.103(2) Å, b ) 8.642(1) Å, c ) 17.032(2) Å, â ) 114.11-
(5)°; V ) 2163.4(4) Å3, Z ) 4, Dc ) 1.814 g cm-3, µ ) 6.697
mm-1, F(000) ) 1144; Tmin/max ) 0.318/0.408. Colorless prisms,
dimensions 0.14 × 0.13 × 0.11 mm3; total number of collected
reflections 9400 (independent 9399), with 6804 having I > 2σ-
Supporting Information Available: ORTEP plots for the
metal complex part of 1, 5‚BF4‚0.5CH2Cl2, 7‚PF6, 9‚0.5CH2-
Cl2, and 10‚PF6‚0.75C4H8O; crystallographic data are available
as CIF files. This material is available free of charge via the
Internet at http://pubs.acs.org.
(26) (a) Blessing, R. H. Crystallogr. Rev. 1987, 1, 3. (b) Sheldrick,
G. M. SHELXL97, Program for the refinement of crystal structures;
University of Go¨ttingen: Germany, 1997.
OM049282S