Planar-to-axial chirality relay in phospharuthenocenes. A rotationally hindered 2-(2′-diphenylphosphinonaphth-1′-yl)phospharuthenocene

Article abstract of DOI:10.1021/om0610905

Competing steric pressures within the coordination sphere of 2-(2′-X-naphth-1′-yl)-3,4-dimethyl-5-phenyl-η⁵- phospholyl(pentamethylcyclopentadienyl)ruthenium(II) complexes (X = OMe (1), OH (3), OTf (4), PPh₂(O) (5), PPh₂ (6)) give rise to a well-defined and predictable axial chirality about the phospharuthenocene- naphthyl bond. Crystal structure analysis of the platinum complex cis-[Pt(6)Cl₂] (7) shows a very different geometry from that found in cis-[Pt(1)(PEt₃)Cl₂] (2) because of the leverage exerted on the Pt coordination sphere by the (2′-PPh₂-naphth-1′- yl) functionality.

Full text of DOI:10.1021/om0610905

2964
Organometallics 2007, 26, 2964-2970
Articles
Planar-to-Axial Chirality Relay in Phospharuthenocenes.
A Rotationally Hindered
2-(2′-Diphenylphosphinonaphth-1′-yl)phospharuthenocene
Duncan Carmichael,* Louis Ricard, and Nicolas Seeboth
Laboratoire “He´te´roe´le´ments et Coordination”, Ecole Polytechnique, CNRS,
91128 Palaiseau Cedex, France
ReceiVed NoVember 30, 2006
Competing steric pressures within the coordination sphere of 2-(2′-X-naphth-1′-yl)-3,4-dimethyl-5-
phenyl-η5-phospholyl(pentamethylcyclopentadienyl)ruthenium(II) complexes (X ) OMe (1), OH (3), OTf
(4), PPh2(O) (5), PPh2 (6)) give rise to a well-defined and predictable axial chirality about the
phospharuthenocene-naphthyl bond. Crystal structure analysis of the platinum complex cis-[Pt(6)Cl2]
(7) shows a very different geometry from that found in cis-[Pt(1)(PEt3)Cl2] (2) because of the leverage
exerted on the Pt coordination sphere by the (2′-PPh2-naphth-1′-yl) functionality.
Introduction
The development of functionalized metallocene-based
“pseudobiaryl” ligands, which can be used as replacements for
more classical biaryl ligand systems,1 has been treated in some
depth recently. Eyecatching examples include Johannsen’s
MOPF class2-6 and DMAP analogues,7 Weissensteiner’s Wal-
phos ligands,8 and Knochel’s series (e.g., ferrocenylQuinap)9,10
derived from the Kagan sulfoxide10,11 (Figure 1).
Rather than using classical metallocenes, we and others have
been interested for some time in exploring the potential for
building ligands around phosphametallocene (phosphacyclo-
pentadienyl, Figure 2) complexes,12 so as to exploit the unusual
coordination properties of the sp2-hybridized phosphorus atom.
* Corresponding author. Fax: int + 33 1 69333990. Tel: int + 33 1
69334571. E-mail: Duncan.Carmichael@polytechnique.fr.
(1) Shimizu, H.; Nagasaki, I.; Saito, T. Tetrahedron 2005, 61, 5405-
5432.
(2) Pedersen, H. L.; Johannsen, M. Chem. Commun. 1999, 2517-2518.
(3) Jensen, J. F.; Sotofte, I.; Sorensen, H. O.; Johannsen, M. J. Org.
Chem. 2002, 68, 1258-1265.
(4) Pedersen, H. L.; Johannsen, M. J. Org. Chem. 2002, 67, 7982-7994.
(5) Jensen, J. F.; Svendsen, B. Y.; la Cour, T. V.; Pedersen, H. L.;
Johannsen, M. J. Am. Chem. Soc. 2002, 124, 4558-4559.
(6) Jensen, J. F.; Johannsen, M. Org. Lett. 2003, 5, 3025-3028.
(7) Seitzberg, J. G.; Dissing, C.; Sotofte, I.; Norrby, P. O.; Johannsen,
M. J. Org. Chem. 2005, 70, 8332-8337.
Figure 1. Above: Some pseudobiaryl ligands. Below: Potential
influence of the relative positions of the metal and the five-
membered ring plane on the nature of the chirality in flexible
structures.
(8) Sturm, T.; Weissensteiner, W.; Spindler, F. AdV. Synth. Catal. 2003,
345, 160-164. For selected applications of the Walphos series, see: Kabat,
M. M.; Garofalo, L. M.; Daniewski, A. R.; Hutchings, S. D.; Liu, W.; Okabe,
M.; Radinov, R.; Zhou, Y. F. J. Org. Chem. 2001, 66, 6141-6150. Tanaka,
K.; Hagiwara, Y.; Noguchi, K. Angew. Chem., Int. Ed. 2005, 44, 7260-
7263. Houpis, I. N.; Patterson, L. E.; Alt, C. A.; Rizzo, J. R.; Zhang, T. Y.;
Haurez, M. Org. Lett. 2005, 7, 1947-1950. Barbaro, P.; Bianchini, C.;
Giambastiani, G.; Parisel, S. L. Coord. Chem. ReV. 2004, 248, 2131-2150.
Morgan, J. B.; Morken, J. P. J. Am. Chem. Soc. 2004, 126, 15338-15339.
Feringa, B. L.; Badorrey, R.; Pena, D.; Harutyunyan, S. R.; Minnaard, A.
J. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5834-5838.
(9) Lotz, M.; Kramer, G.; Knochel, P. Chem. Commun. 2002, 2546-
2547.
Figure 2.
The preparation of axially chiral ligands constitutes an obvious
goal.13 Conferring useful axial chirality upon classically func-
tionalized metallocenes is usually quite straightforward; the
presence of a functional group having a lone pair that will
generally be oriented away from the cyclopentadienyl plane
(e.g., -PPh2) reinforces the natural tendency of flexible ligands
(10) Kloetzing, R. J.; Knochel, P. Tetrahedron: Asymmetry 2006, 17,
116-123.
(11) Guillaneux, D.; Kagan, H. B. J. Org. Chem. 1995, 60, 2502-2505.
10.1021/om0610905 CCC: $37.00 © 2007 American Chemical Society
Publication on Web 05/05/2007

Planar-to-Axial Chirality Relay in Phospharuthenocenes
Organometallics, Vol. 26, No. 12, 2007 2965
Scheme 1. Synthesis of Ligand 6a
to adopt an axially chiral motif (Figure 1).4 However, if the
lone pair lies in the plane of the five-membered ring, as in a
donor heterometallocene, any second coordinating functionality
in a nonrestrained system is likely to be drawn toward the ring
(12) For uses in enantioselection, see: Carmichael, D.; Goldet, G.;
Klankermeyer, J.; Ricard, L; Seeboth, N.; Stankevicˇ, M. Chem. Eur. J., in
press. Fu, G. C. Acc. Chem. Res. 2006, 39, 853-860. Ganter, C.;
Glinsbo¨ckel, C.; Ganter, B. Eur. J. Inorg. Chem. 1998, 1163-1168. Qiao,
S.; Fu, G. C. J. Org. Chem. 1998, 63, 4168-4169. Ganter, C.; Kaulen, C.;
Englert, U. Organometallics 1999, 18, 5444-5446. Shintani, R.; Lo, M.
M. C.; Fu, G. C. Org. Lett. 2000, 2, 3695-3697. Tanaka, K.; Qiao, S.;
Tobisu, M.; Lo, M. M. C.; Fu, G. C. J. Am. Chem. Soc. 2000, 122, 9870-
9871. Tanaka, K.; Fu, G. C. J. Org. Chem. 2001, 66, 8177-8186. Shintani,
R.; Fu, G. C. Org. Lett. 2002, 4, 3699-3702. Shintani, R.; Fu, G. C. J.
Am. Chem. Soc. 2003, 125, 10778-10779. Shintani, R.; Fu, G. C. Angew.
Chem., Int. Ed. 2003, 42, 4082-4085. Suarez, A.; Downey, C. W.; Fu, G.
C. J. Am. Chem. Soc. 2005, 127, 11244-11245. For racemates, see: Le
Floch, P. Coord. Chem. ReV. 2006, 250, 627-681. Carmichael, D.; Mathey,
F. Top. Curr. Chem. 2002, 220, 27-51. Weber, L. Angew. Chem., Int. Ed.
2002, 41, 563-572. Mathey, F. Angew. Chem., Int. Ed. 2003, 42, 1578-
1604, and references therein.
(13) The axial chirality of menthyl-substituted 1,1′-diphospharu-
thenocenes has previously been the subject of a study by Hayashi,
Ogasawara, et al.; see: Ogasawara, M.; Yoshida, K.; Hayashi, T. Orga-
nometallics 2003, 22, 1783-1786.
(14) Roca, F. X.; Motevalli, M.; Richards, C. J. J. Am. Chem. Soc. 2005,
127, 2388-2389.
(15) A good example is provided in the comparison of the structures of
Richards et al.’s essentially ring-coplanar metalated ferrocene A14 with
Knochel et al.’s B (best interplane angle: 76.8°).9
a Reagents and Conditions: i: LiPPh2 (3 equiv), THF, 80 °C, 5 h,
87%. ii: 4-Nitrophenyltriflate (1.2 equiv), K2CO3 (4 equiv), 18C6 (2
equiv), THF, 12 h. 73%. iii: Ph2P(O)H (1.5 equiv), NaHCO3 (2 equiv),
Pd(OAc)2 (0.2 equiv), dppp (0.2 equiv), DMSO, 80 °C, 3 h, 72%. iV:
(MeHSiO)n (100 equiv), Ti(OiPr)4 (1.5 equiv), THF, 66 °C, 4 h, 93%.
plane, with the result that the default geometry will often be
closer to simple planar chirality.14,15 For ligands containing
heterometallocene and related functionalities, it may therefore
be beneficial to incorporate structural elements that actively
promote axial chirality, should this be desired.16
As part of an investigation into this area, we recently
described the synthesis and tropos characteristics of the naph-
thyl-substituted phospharuthenocene 1, along with its incorpora-
tion into specimen platinum complexes 2 (Figure 2).17
A number of elements within its coordination sphere suggest
that 1 should be a good source of axially chiral phospharu-
thenocenes.18 It shows a surmountable maximum in the coplanar
configuration {∆G*endofexo 77(1) kJ mol-1}, which results from
nonbonding interactions between the naphthyl ring and the
3-methyl group, and also exhibits further nonbonding interac-
tions between the naphthyl and Cp* groups. Solutions of 1 exist
as equilibrating (S*Rc,aS*)-(()-exo and (S*Rc,aR*)-(()-endo
conformers19 (Scheme 1) because the naphthyl component has
similar spatial requirements in each orientation, but increasing
the volume of the group in the naphthyl 2-position will obviously
destabilize the endo form (Figure 3). With the coplanar
configuration also disfavored, this should generate an exo
In more general terms, compare the near-coplanarity of the oxazoline imine
and phenyl functionalities in the structures of PHOX ligands at group 10
metal centers: Schaffner, S.; Macko, L.; Neuburger, M.; Zehnder, M. HelV.
Chim. Acta 1997, 80, 463-471. Lloyd-Jones, G. C.; Butts, C. P. Tetrahedron
1998, 54, 901-914. Liu, S. Y.; Muller, J. F. K.; Neuburger, M.; Schaffner,
S.; Zehnder, M. J. Organomet. Chem. 1997, 549, 283-293. Bray, K. L.;
Butts, C. P.; Lloyd-Jones, G. C.; Murray, M. J. Chem. Soc., Dalton Trans.
1998, 1421-1422. Schaffner, S.; Muller, J. F. K.; Neuburger, M.; Zehnder,
M. HelV. Chim. Acta 1998, 81, 1223-1232. Blacker, A. J.; Clarke, M. L.;
Loft, M. S.; Mahon, M. F.; Williams, J. M. J. Organometallics 1999, 18,
2867-2873. Lee, S.; Lim, C. W.; Song, C. E.; Kim, K. M.; Jun, C. H. J.
Org. Chem. 1999, 64, 4445-4451. Gomez, M.; Jansat, S.; Muller, G.;
Panyella, D.; van Leeuwen, P.; Kamer, P. C. J.; Goubitz, K.; Fraanje, J.
Organometallics 1999, 18, 4970-4981. Blacker, A. J.; Clarke, M. L.; Loft,
M. S.; Mahon, M. F.; Humphries, M. E.; Williams, J. M. J. Chem.-Eur. J.
2000, 6, 353-360. Bernardinelli, G. H.; Kundig, E. P.; Meier, P.; Pfaltz,
A.; Radkowski, K.; Zimmermann, N.; Neuburger-Zehnder, M. HelV. Chim.
Acta 2001, 84, 3233-3246. Kollmar, M.; Goldfuss, B.; Reggelin, M.;
Rominger, F.; Helmchen, G. Chem.-Eur. J. 2001, 7, 4913-4927. Vazquez,
J.; Goldfuss, B.; Helmchen, G. J. Organomet. Chem. 2002, 641, 67-70.
Zehnder, M.; Neuburger, M.; Schaffner, S.; Jufer, M.; Plattner, D. A. Eur.
J. Inorg. Chem. 2002, 1511-1517. Kollmar, M.; Steinhagen, H.; Janssen,
J. P.; Goldfuss, B.; Malinovskaya, S. A.; Vazquez, J.; Rominger, F.;
Helmchen, G. Chem.-Eur. J. 2002, 8, 3103-3114. Zehnder, M.; Schaffner,
S.; Neuburger, M.; Plattner, D. A. Inorg. Chim. Acta 2002, 337, 287-298.
Kollmar, M.; Helmchen, G. Organometallics 2002, 21, 4771-4775. Masui,
D.; Ohnuki, M.; Yamaguchi, M.; Yamagishi, T. Acta Crystallogr., Sect. C:
Cryst. Struct. Commun. 2003, 59, M487-M490. Pican, P.; Gaumont, A.
C. Chem. Commun. 2005, 2393-2395. Armstrong, P. B.; Bennett, L. M.;
Constantine, R. N.; Fields, J. L.; Jasinski, J. P.; Staples, R. J.; Bunt, R. C.
Tetrahedron Lett. 2005, 46, 1441-1445. Tang, X. B.; Zhang, D. H.; Jie, S.
Y.; Sun, W. H.; Chen, J. T. J. Organomet. Chem. 2005, 690, 3918-3928
with the highly pronounced axial chirality of biphep complexes: Ogasawara,
M.; Yoshida, K.; Hayashi, T. Organometallics 2000, 19, 1567-1571, Tudor,
M. D.; Becker, J. J.; White, P. S.; Gagne, M. R. Organometallics 2000, 19,
4376-4384. Becker, J. J.; White, P. S.; Gagne, M. R. J. Am. Chem. Soc.
2001, 123, 9478-9479. Mikami, K.; Aikawa, K.; Yusa, Y. Org. Lett. 2002,
4, 95-97. Mikami, K.; Aikawa, K.; Yusa, Y.; Hatano, M. Org. Lett. 2002,
4, 91-94. Aikawa, K.; Mikami, K. Angew. Chem., Int. Ed. 2003, 42, 5458-
5461. Mikami, K.; Kakuno, H.; Aikawa, K. Angew. Chem., Int. Ed. 2005,
44, 7257-7260 containing the same metals (data as available from CCDC
on 10/25/2006).
(16) This seems to be a problem of recurring interest; see, for example,
ref 7.
(17) Carmichael, D.; Ricard, L.; Seeboth, N.; Brown, J. M.; Claridge,
T. D. W.; Odell, B. Dalton Trans. 2005, 2173-2181.
(18) For treatments of phospharuthenocenes, see refs 13, 17, 52 and:
Loschen, R.; Loschen, C.; Frank, W.; Ganter, C. Eur. J. Inorg. Chem. 2007,
553-561. Ogasawara, M.; Ito, A.; Yoshida, K.; Hayashi, T. Organometallics
2006, 25, 2715-2718. Carmichael, D.; Mathey, F.; Ricard, L.; Seeboth,
N. Chem. Commun. 2002, 2976-2977. Ogasawara, M.; Nagano, T.;
Yoshida, K.; Hayashi, T. Organometallics 2002, 21, 3062-3065. Herberich,
G. E.; Ganter, B.; Englert, U. Struct. Chem. 1998, 9, 359-363. Herberich,
G. E.; Ganter, B. Organometallics 1997, 16, 522-524. Carmichael, D.;
Ricard, L.; Mathey, F. J. Chem. Soc., Chem. Commun. 1994, 1167-1168.
(19) All compounds presented here are racemates. For nomenclature,
see: Hey, E.; Willis, A. C.; Wild, S. B. Z. Naturforsch. B: Chem. Sci.
1989, 44, 1041-1046.

2966 Organometallics, Vol. 26, No. 12, 2007
Carmichael et al.
Figure 3. Projected effect of increasing R-group volume in tropos-type naphthalene-substituted sandwich complexes.
conformer wherein competing steric pressures provide a more
rigid and controlled axial chirality than is available in metal-
locene-derived ligands having less encumbered substitution
schemes. This approach is developed here through the synthesis
of the configurationally restricted phosphametallocene phosphine
ligand 6, whose geometry is confirmed in the crystal structure
of the platinum complex 7.
avoid a rapid decomposition, which set in after complete
conversion into 6 had been achieved.37 For optimum results,
the reaction was followed in situ by 31P NMR and halted after
95% conversion.
The stereochemistry of naphth-1-ylmetallocenes can be
investigated conveniently by NMR spectroscopy because the
strong ring currents experienced by the naphthyl-8 proton in
exo structures provoke a significant high-frequency shift relative
to the endo form4,38 (for a definition of the naphthyl-8 proton
see 1b in Scheme 1; typical shifts are δH8 ) 9.86 in 1a, 8.00
ppm in 1b {C6D6}).17 Compounds 3-6 each show only one
conformer in solution within the limits of detection by 31P and
1H NMR spectroscopy. These were subjected to COSY, HSBC,
and HSQC analyses, which provided unambiguous identifica-
tions of the 8-H protons and allowed definitive configurational
assignments to be made in each case. The highly deshielded
protons found in compounds 4, 5, and 6, (δ1H ) 9.79, 9.66,
and 9.39 ppm for H-8 in C6D6, respectively) lie close to the
value in the crystallographically established 1a and confirm exo
conformations. However, the chemical shift (δ1H ) 7.54 ppm
in CDCl3) for H-8 in 3, containing the smaller OH substituent,
clearly indicates an endo configuration, and this was confirmed
for the solid state by a crystal structure analysis (Figure 4).39
The atypical reactivity observed during the triflation reaction
therefore probably reflects the inaccessible position of the OH
functionality, which is embedded within the core of the
metallocene. The data also show that the relative bulk of the
naphthyl substituent {OH < MeO < TfO < PPh2(O)} correlates
broadly with the disappearance of the endo form (OH > MeO
> TfO, PPh2(O)), in accordance with the proposed model
wherein the handedness of the axial chirality is governed
primarily by hindrance that drives the naphthyl group through
the phospholyl plane into the lowest energy configuration.
The overall outcome of the opposing steric effects in the
phospharuthenocenephosphine 6 is not obvious ab initio, but
its formulation as a ligand having pronounced axial chirality
was confirmed through an X-ray analysis of its complex at a
PtCl2 center, 7 (eq 1, Figure 5).
The preparation of 6 is easily effected from compound 1
according to the protocol given in Scheme 1. While the
elementary steps are classical, some of the reagents are less so.
Oxidation reactions appeared to prevent access to naphthol 3
by a number of methods20-22 that are routinely employed for
the demethylation of aryl methyl ethers (TMSI,23,24 Me2S‚
BCl325), but the compound could be prepared essentially
quantitatively under reducing conditions using lithium diphe-
nylphosphide.26,27 Attempted triflation of 3 under standard
conditions (Tf2O, DMAP28 or pyridine,29,30 THF or THP) also
failed, apparently because of competing solvent ring-opening
when the reaction was performed in THF and very sluggish
reactivity in THP; however, good isolated yields of 4 (73%)
were obtained through the SN2 reaction of the corresponding
potassium naphtholate with 4-nitrophenyltriflate.31,32 The phos-
phorus center was installed very smoothly using Ph2P(O)H under
Hayashi-Morgans conditions,29,33 in a reaction that proved
much faster than in the case reported for Quinap,34 possibly
because of precoordination of the Pd(0) center to the sp2
phosphorus atom. Finally, reduction of 5 was effected using a
polymethyl-hydrosiloxane/Ti(OiPr)4 protocol,35,36 which proved
far superior to NEt3/SiHCl3-based methods. Nonetheless, the
duration of the reaction had to be controlled carefully so as to
(20) Vickery, E. H.; Pahler, L. F.; Eisenbraun, E. J. J. Org. Chem. 1979,
44, 4444-4446.
(21) Bhatt, M. V.; Kulkarni, S. U. Synthesis (Stuttgart) 1983, 249-282.
(22) Magano, J.; Chen, M. H.; Clark, J. D.; Nussbaumer, T. J. Org. Chem.
2006, 71, 7103-7105, and references therein.
(23) Jung, M. E.; Lyster, M. A. Organic Syntheses; Wiley: New York,
1988; Collect. Vol. VI, 353-357.
(24) Jung, M. E.; Lyster, M. A. J. Org. Chem. 1977, 42, 3761-3764.
(25) Williard, P. G.; Fryhle, C. B. Tetrahedron Lett. 1980, 21, 3731-
3734.
(26) Ireland, R. E.; Walba, D. M. Organic Syntheses; Wiley: New York,
1988, Collect. Vol. VI, 567-570.
(37) This effect has precedent in MOPF chemistry; see ref 4.
(27) Mann, F. G.; Pragnell, M. J. J. Chem. Soc. 1965, 4120.
(28) Ohta, T.; Ito, M.; Inagaki, K.; Takaya, H. Tetrahedron Lett. 1993,
34, 1615-1616.
(38) Note that half-sandwich binap-derived 2-diphenylphosphinonaph-
thalen-1-yl groups do not show 8-H protons outside the normal aromatic
range: Geldbach, T. J.; Pregosin, P. S. Eur. J. Inorg. Chem. 2002, 1907-
1918. Geldbach, T. J.; den Reijer, C. J.; Worle, M.; Pregosin, P. S. Inorg.
Chim. Acta 2002, 330, 155-160. Geldbach, T. J.; Pregosin, P. S.; Albinati,
A. Organometallics 2003, 22, 1443-1451. Geldbach, T. J.; Breher, F.;
Gramlich, V.; Kumar, P. G. A.; Pregosin, P. S. Inorg. Chem. 2004, 43,
1920-1928. Geldbach, T. J.; Pregosin, P. S.; Rizzato, S.; Albinati, A. Inorg.
Chim. Acta 2006, 359, 962-969. Equally, the lack of a highly deshielded
1H proton resonance in Knochel’s “ferrocenylquinap” may provide a clue
as to its performance difference10 with respect to Quinap itself.
(29) Uozumi, Y.; Tanahashi, A.; Lee, S. Y.; Hayashi, T. J. Org. Chem.
1993, 58, 1945-1948.
(30) Shen, H. C.; Tang, J. M.; Chang, H. K.; Yang, C. W.; Liu, R. S. J.
Org. Chem. 2005, 70, 10113-10116.
(31) Neuville, L.; Bigot, A.; Dau, M.; Zhu, J. P. J. Org. Chem. 1999,
64, 7638-7642.
(32) Zhu, J. P.; Bigot, A.; Dau, M. Tetrahedron Lett. 1997, 38, 1181-
1182.
(33) Kurz, L.; Lee, G.; Morgans, D.; Waldyke, M. J.; Ward, T.
Tetrahedron Lett. 1990, 31, 6321-6324.
(39) The structure can be compared with the phosphaferrocene homo-
logue where, unlike in 3, the hydrogen of the OH functionality is oriented
away from the metal center.17 Thus the electronic stabilization resulting
from the O-H‚‚‚Ru interaction is probably small. For a related system, see:
Paley, R. S.; Estroff, L. A.; McCulley, D. J.; Martinez-Cruz, L. A.; Sanchez,
A. J.; Cano, F. H. Organometallics 1998, 17, 1841-1849. For a theoretical
analysis of this kind of interaction: Vrcek, V.; Buhl, M. Organometallics
2006, 25, 358-367, and references therein.
(34) Alcock, N. W.; Brown, J. M.; Hulmes, D. I. Tetrahedron: Asym-
metry 1993, 4, 743-756.
(35) Coumbe, T.; Lawrence, N. J.; Muhammad, F. Tetrahedron Lett.
1994, 35, 625-628.
(36) Vandyck, K.; Matthys, B.; Willen, M.; Robeyns, K.; Van Meervelt,
L.; Van der Eycken, J. Org. Lett. 2006, 8, 363-366.

Planar-to-Axial Chirality Relay in Phospharuthenocenes
Organometallics, Vol. 26, No. 12, 2007 2967
substituent (2) in Figure 6.41 The Pt-P{sp2} and Pt-Cl (trans
to P{sp2}) bond lengths are both significantly shorter in 7 than
2, so that the position of the platinum atom above the phospholyl
plane in 7 appears to lessen the p-character in the Pt-P bond
with an associated reduction in trans influence. The very
different metal positions in the two complexes are consistent
with the generally held tenet42,43 that the potential surface for
the motion of a metal atom about the sp2-hybridized phosphorus
is relatively flat because of the spherical nature of the lone pair,
the implication being that the position of the metal is influenced
strongly by the sp3 phosphorus atom, so that the axial chirality
constitutes a dominant structural element within the complex.
The modification of the competing steric influences upon the
naphthyl lever, through variation of the bulk of the phospholyl
3-substituent, the nature of the cyclopentadienyl ring, and the
covalent radius of the metallocene metal center in ligands such
as 6 should therefore provide a means of performance optimiza-
tion. For classical biaryl-based diphosphines (segphos,44 syn-
phos,45,46 tunaPhos,47 etc.48) it is widely accepted that a decrease
in interplanar angle generally translates into a more intimate
ligand-substrate interaction during catalysis and thus better
performance; thus, even if the system is very different from
those containing the classical biaryls above, the relatively small
interplane observed in 6 (compare PdCl2‚Segphos: 60.1°,49
PdCl2‚binap: 70.2°49,50) suggests a favorable projection of the
aryl groups into the metal coordination sphere (Table 1).
The pathways above provide useful phosphametallocene
intermediates, and, in utilizing both conformers of 1, furnish
an atom-economical and simple means of relaying the planar
chirality of the phosphametallocene into a well-ordered axial
chirality about the phospholyl-naphthyl link. Given that a very
wide variety of useful C1-symmetrical ligands have been
prepared from naphthyl triflates51 and that optically pure 2-aryl-
substituted phosphametallocenes are, in principle, easy to
prepare,52 this approach promises to provide an attractive and
chirally economical route to a variety of enantiopure axially
chiral phosphametallocenes.
Figure 4. Molecular structure of 3. Distances (Å): Ru(1)-P(1),
2.4192(5); Ru(1)-C(1), 2.221(2); Ru(1)-C(2), 2.192(2); Ru(1)-
C(3), 2.201(2); Ru(1)-C(4), 2.254(2); Ru(1)-C(23), 2.198(2); Ru-
(1)-C(24), 2.205(2); Ru(1)-C(25), 2.224(2); Ru(1)-C(26), 2.204-
(2); Ru(1)-C(27), 2.186(2); P(1)-C(1), 1.791(2); P(1)-C(4),
1.787(2); C(1)-C(2), 1.437(3); C(2)-C(3), 1.437(3); C(3)-C(4),
1.420(3); C(4)-C(5), 1.494(2); C(1)-C(15), 1.482(3). Angles
(deg): phospholyl-C(4)-C(5), 10.6; intersection of best phospholyl
and naphthyl planes: 78.2.
Two features stand out. The first is the angle defined by the
best phospholyl and naphthyl group planes (54.5°), which,
although significant, lies toward the low end of the range for
normal biaryl-type structures in platinum complexes.40 The
second is the localization of the platinum atom well above the
best phospholyl plane (by 1.06 Å, phospholyl centroid-P-Pt
) 149.0° for 7; compare to 0.62 Å, phospholylcentroid-P-Pt
) 161.8° for 2). This combination of effects provokes an
unusual PPh2 geometry wherein the face-oriented equatorial aryl
has its C2-axis lying essentially coplanar with the best plane
about the platinum atom, and the edge-on axial phenyl group
is tilted in a fashion that orients the para carbon (C26) closer
to the plane passing through the Pt and bisecting the two chlorine
atoms than the ipso carbon (C23).
Experimental Section
All operations were performed either using cannula techniques
on Schlenk lines under an atmosphere of dry nitrogen or in a Braun
(41) For other structures of phosphametallocene phosphine
complexes at group 10 metal centers, see: Ganter, C.; Brassat, L.;
Glinsbo¨ckel, C.; Ganter, B. Organometallics 1997, 16, 2862. Ogasawara,
M.; Ge, Y. H.; Nakajima, K.; Takahashi, T. Inorg. Chim. Acta 2004, 357,
3943.
(42) Deschamps, B.; Mathey, F.; Fischer, J.; Nelson, J. H. Inorg. Chem.
1984, 23, 3455-3462.
(43) Sava, X.; Ricard, L.; Mathey, F.; Le Floch, P. Organometallics 2000,
19, 4899-4903.
(44) Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi, T.; Sayo, N.; Miura,
T.; Kumobayashi, H. AdV. Synth. Catal. 2001, 343, 264-267.
(45) Jeulin, S.; de Paule, S. D.; Ratovelomanana-Vidal, V.; Genet, J. P.;
Champion, N.; Dellis, P. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5799-
5804.
The parameters about platinum in 7 are compared with those
found in the related complex containing a methoxynaphthyl
(46) de Paule, S. D.; Jeulin, S.; Ratovelomanana-Vidal, V.; Genet, J. P.;
Champion, N.; Deschaux, G.; Dellis, P. Org. Process Res. DeV. 2003, 7,
399-406.
(40) Examples available in CCDC are: KOSKUY: Alcock, N. W.;
Brown, J. M.; Perez-Torrente, J. J. Tetrahedron Lett. 1992, 33, 389-392.
KOSKUY10: Brown, J. M.; Perez-Torrente, J. J.; Alcock, N. W. Orga-
nometallics 1995, 14, 1195-1203. PAXFID: Nozaki, K.; Sato, N.;
Tonomura, Y.; Yasutomi, M.; Takaya, H.; Hiyama, T.; Matsubara, T.; Koga,
N. J. Am. Chem. Soc. 1997, 119, 12779-12795. QEJNIC: Wicht, D. K.;
Kovacik, I.; Glueck, D. S.; Liable-Sands, L. M.; Incarvito, C. D.; Rheingold,
A. L. Organometallics 1999, 18, 5141-5151. SEQROV: Wicht, D. K.;
Zhuravel, M. A.; Gregush, R. V.; Glueck, D. S.; Guzei, I. A.; Liable-Sands,
L. M.; Rheingold, A. L. Organometallics 1998, 17, 1412-1419. ULILAC:
Grant, G. J.; Pool, J. A.; Van Der Veer, D. G. Dalton Trans. 2003, 3981-
3984. ZIHHUT: Tominaga, N.; Sakai, K.; Tsubomura, T. J. Chem. Soc.,
Chem. Commun. 1995, 2273-2274. ICILIQ and ICILOW: Yin, G. Q.;
Wei, Q. H.; Shi, L. X.; Zhang, L. Y.; Chen, Z. N. Chin. J. Struct. Chem.
2006, 25, 395-401.
(47) Wu, S. L.; Wang, W. M.; Tang, W. J.; Lin, M.; Zhang, X. M. Org.
Lett. 2002, 4, 4495-4497.
(48) For a very recent review, see: Wu, J.; Chan, A. S. C. Acc. Chem.
Res. 2006, 39, 711-720.
(49) Mikami, K.; Aikawa, K.; Kainuma, S.; Kawakami, Y.; Saito, T.;
Sayo, N.; Kumobayashi, H. Tetrahedron: Asymmetry 2004, 15, 3885-
3889.
(50) Ozawa, F.; Kubo, A.; Matsumoto, Y.; Hayashi, T.; Nishioka, E.;
Yanagi, K.; Moriguchi, K. Organometallics 1993, 12, 4188-4196.
(51) Kocˇovsky´, P.; Vyskocˇil, S.; Smrcˇina, M. Chem. ReV. 2003, 103,
3213-3245.
(52) Carmichael, D.; Klankermayer, J.; Ricard, L.; Seeboth, N. Chem.
Commun. 2004, 1144-1145.

2968 Organometallics, Vol. 26, No. 12, 2007
Carmichael et al.
Figure 5. Two views of the molecular structure of 7. Selected distances (Å): Pt(1)-P(1), 2.203(1); Pt(1)-P(2), 2.242(1); Pt(1)-Cl(2),
2.322(1); Pt(1)-Cl(1), 2.361(1); Ru(2)-C(35), 2.188(4); Ru(2)-C(36), 2.197(4); Ru(2)-C(39), 2.199(4); Ru(2)-C(37), 2.205(4); Ru-
(2)-C(38), 2.208(4); Ru(2)-C(2), 2.223(4); Ru(2)-C(1), 2.249(4); Ru(2)-C(3), 2.272(4); Ru(2)-P(1), 2.297(1); Ru(2)-C(4), 2.314(4);
P(1)-C(4), 1.764(4); P(1)-C(1), 1.768(4); C(1)-C(2), 1.419(5); C(1)-C(15), 1.487(5); C(2)-C(3), 1.451(5); C(3)-C(4), 1.436(5); C(4)-
C(5), 1.498(5). Intersection of best phospholyl and naphthyl planes: 54.5°.
Table 1. Summary of Data Pertaining to the Crystal
Structures and Refinements of Compounds 3 and 7a
3‚0.5C7H8
611.69
7‚2CH2Cl2
1169.63
M/Da
space group
a/Å
b/Å
P1h
P21/n
8.512(1)
11.989(1)
15.228(1)
110.950(1)
90.330(1)
100.160(1)
1424.5(2)
2
11.315(1)
20.571(1)
19.376(1)
90
98.406(1)
90
4461.5(5)
4
1.741
c/Å
Figure 6. Internuclear separations (Å) and angles (deg) in (()-2
(normal text, Ar ) 2-methoxynaphth-1-yl, R ) Et) and (()-7 (bold,
Ar, PR3 ) 2-diphenylphosphanylnaphth-1-yl).
R/deg
â/deg
γ/deg
U/Å3
Z
Labmaster 130 drybox under dry purified argon. Column chroma-
tography was performed on 63-200 µm silica or 50-160 µm
neutral alumina as appropriate. Compound 1 was obtained as
described previously.17 Solvents were distilled under dry nitrogen,
THF from sodium-benzophenone ketyl, pentane from sodium-
benzophenone ketyl-tetraglyme, diethyl ether from sodium hydride,
DMSO from calcium hydride, and dichloromethane from P4O10.
Solvents for chromatography were degassed by bubbling with
nitrogen but otherwise used as received. Deuterobenzene was used
as received from Eurisotop (Saclay); chloroform and deuterochlo-
roform were deacidified through neutral alumina prior to use. NMR
measurements were made on a Bruker Avance 300 spectrometer
and are referenced to internal C6D5H or CHCl3 and external H3-
PO4 as appropriate. Mass spectra were obtained under 70 eV
electron impact or chemical ionization using ammonia on a Hewlett-
Packard 5989B spectrometer. Combustion analyses were performed
by Marie-Franc¸oise Bricot at the “Service de microanalyse du
CNRS”, Gif sur Yvette, France.
Dc/g cm-3
F(000)
1.426
634
0.634
-11 to 11
-16 to 16
-21 to 21
0.20 × 0.20 × 0.20
8224
7206
0.1048
0.0375
1.019
1.089(0.093);
-1.534(0.093)
629054
2304
3.935
µ/cm-1
h/deg
k/deg
l/deg
-15 to 15
-23 to 28
-27 to 27
0.20 × 0.16 × 0.04
12 988
9412
0.1075
0.0418
1.000
size/mm
no. of indep reflns
no. of refined reflns
wR2 [I > 2σ(I)]
R1
GOF on F2
max. peak;
hole/e Å-3
CCDC entry
1.919(0.151);
-2.556(0.151)
629055
a All structures were measured and collected on a Kappa CCD diffrac-
tometer using graphite-monochromated Mo KR radiation having λ )
0.71070 Å at 150 K. In all cases reflections with intensity >2σ(I) were
refined on F2 using direct methods in SHELXL. Full data have been
deposited with the Cambridge Crystallographic Data Centre and can be
obtained free from www.ccdc.cam.ac.uk/conts/retrieving.html.
3: Compound 1 (1.16 g, 2.0 mmol) and Ph2PLi‚2THF (1.34 g,
4.0 mmol, 2 equiv) were dissolved in freeze-thaw cycled THF
(75 mL), and the solution was refluxed under monitoring by 31P
NMR. After 16 h, the signals due to the reagent 1 (-19.7, -24.8
ppm) had disappeared and were replaced by a peak corresponding
to Ph2PMe (-26 ppm). The solution was hydrolyzed with water
(ca. 0.2 mL) and dried over MgSO4. Evaporation to dryness and
column chromatography on silica (pentane/CH2Cl2, 9:1) gave fast-
running bands of Ph2PMe and Ph2PH, which were discarded. The
product was subsequently eluted in pure CH2Cl2 and was obtained
as a white solid, which darkened to pale yellow upon exposure to
air. Yield: 985 mg (87%).
boiling toluene. In this case, the crystals observed contain one-
half mole of toluene of solvation.
31P NMR (CDCl3): δ -35.1. 1H NMR (CDCl3): δ 8.51 (d, JPH
) 1.4 Hz, 1H, OH), 7.73 (d, JHH ) 7.4 Hz, 1H, 5-Np), 7.68 (d,
JHH ) 8.9 Hz, 1H, 4-Np), 7.54 (d, JHH ) 8.5 Hz, 1H, 8-Np), 7.37
(Ψt, JHH ) 7 Hz, 1H, 7-Np), 7.36 (Ψd, JHH ) 8, JHH ) 7.5 Hz,
1H, 6-Np), 7.19 (d, JHH ) 8.9 Hz, 1H, 3-Np), 7.17 (Ψt, JHH ) 7.5
Hz, 1H, p-Ph), 2.27 (s, 3H, MeCCPh), 1.75 (s, 15H, Cp*), 1.65 (s,
3H, MeCCNp). 13C NMR (CDCl3): δ 150.2 (d, JPC ) 2.0 Hz,
2-Np), 138.7 (d, JPC ) 16.9 Hz, i-Ph), 133.6 (d, JPC ) 2.2 Hz,
8a-Np), 129.1 (d, JPC ) 8.2 Hz, o-Ph), 128.7 (4a-Np), 128.6 (4-
Np), 128.3 (5-Np), 127.9 (m-Ph), 126.1 (7-Np), 125.9 (p-Ph), 125.2
(8-Np), 122.6 (6-Np), 117.3 (3-Np), 113.2 (d, JPC ) 13.7 Hz, 1-Np),
On a larger scale, the chromatographic step can be avoided
through crystallization of the crude reaction hydrolyzate from

Planar-to-Axial Chirality Relay in Phospharuthenocenes
Organometallics, Vol. 26, No. 12, 2007 2969
102.3 (d, JPC ) 59.9 Hz, PCPh), 97.2 (d, JPC ) 3.5 Hz, PCCMe),
93.7 (d, JPC ) 58.5 Hz, PCNp), 92.0 (d, JPC ) 4.1 Hz, PCCMe),
89.4 (Cp*), 13.8 (MeCCPh), 13.6 (MeCCNp), 10.4 (MeCp*). Anal.
Calcd for C32H33OPRu (3‚1/2C7H8): C, 69.7; H, 6.10. Found: C,
70.12; H, 6.04. EI-MS (m/z, %): 566, 100.
(d, JPC ) 13.5 Hz, 3-Np), 129.2 (d, JPC ) 8.7 Hz, o-Ph), 128.6 (d,
JPC ) 6.0 Hz, 8-Np), 128.2 (d, JPC ) 11.6 Hz, m-PhP(O)), 128.1
(d, JPC ) 12.1 Hz, m-PhP(O)), 127.8 (6-Np), 127.5 (5-Np), 127.4
(m-Ph), 125.6 (d, JPC ) 13.4 Hz, 4-Np), 125.3 (7-Np), 125.1 (p-
Ph), 101.7 (dd, JPC ) 61.2 Hz, JPC ) 5.8 Hz, PCNp), 99.8 (d, JPC
) 58.3 Hz, PCPh), 98.0 (d, JPC ) 3.6 Hz, PCCMe), 90.3 (d, JPC
)
4: Compound 3 (100 mg, 0.177 mmol), anhydrous potassium
carbonate (49 mg, 0.35 mmol, 2 equiv), 18C6 (183 mg, 3.9 equiv),
and 4-nitrophenyltriflate (54.3 mg, 1.13 equiv) were dissolved in
THF (10 mL), and the mixture was stirred at room temperature for
12 h. Excess potassium chloride (ca. 50 mg) was then added, and
the solvent was removed under reduced pressure. The crude mixture
was taken up in dichloromethane (5 mL) and washed with NaOH
(10% aq, 15 mL) and water (2 × 15 mL) to eliminate 4-nitrophe-
nolate prior to drying over anhydrous magnesium sulfate. After
filtration and removal of solvents under reduced pressure, the
mixture was purified by chromatography on silica (pentane/CH2-
Cl2, 4:1), whereupon the product was eluted as a yellow band (90
mg, 73%). Recrystallization from MeOH/Et2O gave an analytically
pure sample.
3.9 Hz, PCCMe), 88.5 (Cp*), 15.3 (MeCCP), 13.9 (MeCCP), 10.6
(MeCp*). CI-MS (+ve NH3) (m/z, %): 751, 100. Yellow crystals
obtained from slow cooling of a dichloromethane/methanol solution
turned opaque upon drying and contain one-half equivalent of
methanol. Anal. Calcd for C89H88O3P4Ru2 (5‚1/2MeOH): C, 69.79;
H, 5.79. Found: C, 69.83; H, 5.72.
6: Compound 5 (50 mg, 0.066 mmol), poly(methylhydrosiloxane)
(400 µL, ca. 7.8 mmol of monomer), and titanium tetra(isopro-
poxide) (30 µL, 0.11mmol) were mixed in THF (2.5 mL) and heated
to reflux for 4 h, whereupon conversion into 6 had reached 95%
according to 31P NMR monitoring. The solution was cooled in an
ice bath, and aqueous sodium hydroxide solution (2 M, 3 mL) was
cautiously added dropwise. The organic layer was separated, and
the aqueous layer was extracted with dichloromethane (2 × 5 mL).
The dichloromethane layers were combined and dried over anhy-
drous magnesium sulfate. After filtration and removal of dichlo-
romethane under reduced pressure, the product was obtained as a
yellow solid (45 mg, 93%), which was sufficiently pure for further
use.
31P NMR (CDCl3): δ -5.7 (d, JPP ) 38.5 Hz) (sp3), -19.3 (d,
JPP ) 38.5 Hz) (sp2). 1H NMR (CDCl3): δ 9.39 (d, JHH ) 8.3 Hz,
1H, 8-Np), 7.77 (dd, JHH ) 8.1 Hz, JHH ) 1.3 Hz, 1H, 5-Np), 7.62
(d, JHH ) 8.4 Hz, 1H, 4-Np), 7.56 (ddd, JHH ) 8.3 Hz, JHH ) 6.9
Hz, JHH ) 1.4 Hz, 1H, 7-Np), 7.56 (ddd, JHH ) 8.1 Hz, JHH ) 6.9
Hz, JHH ) 1.5 Hz, 1H, 6-Np), 7.37-7.22 (m, 10H, Ph), 7.20-7.00
(m, 6H, Ph and 3-Np), 2.09 (s, 3H, MeCCP), 1.73 (s, 15H, Cp*),
2.69 (s, 3H, MeCCP). 13C NMR (CDCl3): δ 137.1 (dd, JPC ) 13.2
Hz, JPC ) 6.8 Hz, 1-Np), 135.7 (d, JPC ) 10.0 Hz), 134.8 (d, JPC
) 1.8 Hz), 132.1 (d, JPC ) 13 Hz), 131.7 (d, JPC ) 2.6 Hz), 131.3
(d, JPC ) 5.9 Hz), 131.2 (d, JPC ) 5.7 Hz), 131.0 (d, JPC ) 5.9
Hz), 130.9 (d, JPC ) 2.5 Hz), 129.5 (dd, JPC ) 5.2 Hz, JPC ) 3.6
Hz), 128.9, 128.7, 128.6, 128.5, 128.1, 128.0, 127.9, 127.7, 126.7,
1
31P NMR (C6D6): δ -20.8. H (C6D6): δ 9.79 (d, JHH ) 8.8
Hz, 1H, 8-Np), 7.52-7.45 (m, 2H, 5-Np and 7-Np), 7.44 (Ψd, JHH
) 8 Hz, 2H, o-Ph), 7.28 (d, JHH ) 9.1 Hz, 1H, 4-Np), 7.27 (m,
1H, 6-Np), 7.18 (d, JHH ) 9.1 Hz, 1H, 3-Np), 7.15 (Ψt, JHH ) 8
Hz, 2H, m-Ph), 7.05 (Ψt, JHH ) 8 Hz, 1H, p-Ph), 2.07 (s, 3H),
2.00 (s, 3H), 1.48 (s, 15H, Cp*). 13C NMR (C6D6): 145.6 (d, JP-C
) 3.4 Hz, 2-Np), 139.2 (d, JP-C ) 17.6 Hz, ipso-Ph), 133.3 (4a-
Np), 132.0 (8a-Np), 130.1 (d, JP-C ) 14.6 Hz, 1-Np), 129.8 (d,
JP-C ) 7.6 Hz, o-Ph), 128.8 (d, JP-C ) 8.9 Hz, 8-Np), 128.6 (4-
Np, 5-Np, or 7-Np), 128.3 (4-Np, 5-Np, or 7-Np), 128.2 (4-Np,
5-Np, or 7-Np), 127.0 (6-Np), 126.2 (p-Ph), 126.0 (5-Np or 7-Np),
120.0 (3-Np), 119.2 (q, JF-C ) 321 Hz, CF3), 104.2 (d, JP-C
)
59.6 Hz, PCCPh), 94.5 (d, JP-C ) 62.5 Hz, PCCNp), 93.9 (d, JP-C
) 4.0 Hz, PCC), 92.7 (d, JP-C ) 3.9 Hz, PCC), 88.9 (Cp*), 14.6,
13.4, 10.6 (Cp*). CI-MS (+ve NH3) (m/z, %): 699 ([M + H]+,
100), 566 (M + H - CF3SO2, 10%). Anal. Calcd for C33H32F3O3-
PRuS: C, 56.81; H, 4.62. Found: C, 56.76; H, 4.56.
5: Compound 4 (140 mg, 0.20 mmol) was added to a mixture
containing 1,3-bis(diphenylphosphino)propane (16.8 mg, 0.041
mmol, ca. 20 mol %), freshly prepared diphenylphosphineoxide
(158.2 mg, 0.78mmol), yellow palladium acetate (28 mg, 0.041
mmol), and sodium hydrogen carbonate (98 mg, 1.17 mmol, 6
equiv) in freshly distilled DMSO (10 mL). The solution was heated
to 85 °C for 1.5 h, whereupon 31P NMR showed the complete
disappearance of the starting triflate 4. CH2Cl2 (50 mL) was added,
and the organic phase was washed with brine (2 × 50 mL), saturated
aqueous sodium carbonate (50 mL), and again brine (50 mL). After
drying over anhydrous sodium sulfate, the dichloromethane was
removed under reduced pressure and the oily, red crude product
was purified by chromatography on silica gel. After a short period
of washing the column with pentane/dichloromethane (1:1) the
product was eluted as a broad yellow band using a gradient of
pentane/ethyl acetate (8:2 rising to 7:3). Removal of the solvent
under reduced pressure gave a yellow solid (110 mg, 72%).
125.2, 124.7, 123.9, 124.7 (7-Np), 101.9 (dd, JPC ) 56 Hz, JPC
)
11.2 Hz, PC), 99.8 (d, JPC ) 59 Hz, PC), 96.3 (dd, JPC ) 3.7 Hz,
JPC ) 3.9 Hz, PCCMe), 89.8 (d, JPC ) 3.9 Hz, PCCMe), 88.4 (Cp*),
14.4 (d, JPC ) 12.1 Hz, MeCCP), 13.9 (MeCCP), 10.8 (MeCp*).
CI-MS (+ve NH3) (m/z, %): 735, 100.
7: Compound 6 (45 mg, 0.061mmol) was dissolved in chloroform
(1 mL) and added to a stirred chloroform (1 mL) solution of [PtCl2-
(1,5-cod)] (22.8 mg, 0.061 mmol) at -60 °C. The solution was
further stirred for 15 min, warmed to room temperature, and
evaporated to dryness under reduced pressure. Crystallization by
slow diffusion of methanol (2 mL) into a solution of the crude
reaction product dissolved in dichloromethane (0.5 mL) gave
compound 7 as fine yellow plates (39 mg, 64%).
31P NMR (CH2Cl2): δ 65.7 (JPP ) 14.4 Hz, JPPt ) 3166 Hz)
1
(sp3), 36.5 (d, JPP ) 14.4 Hz, JPPt ) 4207 Hz) (sp2). H NMR
(CDCl3): δ 8.21 (d, JHH ) 8.7 Hz, 1H, 8-Np), 7.87 (dd, JHH ) 8.2
Hz, JHH ) 2.7 Hz, 5-Np), 7.77 (d, JHH ) 8.85 Hz, 4-Np), 7.59
(ddd, JHH ) 7.4 Hz, JHH ) 7.4 Hz, JHH ) 2.7 Hz, 1H, 6-Np or
7-Np), 7.57 (ddd, JHH ) 7.5 Hz, JHH ) 7.5 Hz, JHH ) 2.2 Hz 6-Np
or 7-Np), 7.52-7.19 (m, 15H, Ph), 7.03 (dd, JPH ) 10.4 Hz, JHH
) 8.8 Hz 1H, 3-Np), 1.78 (s, 15H, Cp*), 1.71 (s, 3H), 1.53 (s,
3H). 13C NMR (CDCl3): δ 137.1 (dd, JP-C ) 13.3 Hz, JP-C ) 6.8
Hz, 2-Np), 135.7 (d, JP-C ) 10.0 Hz), 134.8, 132.1(d, JP-C ) 13.0
Hz), 131.7 (d, JP-C ) 2.6 Hz), 131.3 (d, JP-C ) 5.9 Hz), 131.2 (d,
JP-C ) 5.7 Hz), 131.0 (d, JP-C ) 5.9 Hz), 130.9 (d, JP-C ) 2.9
Hz), 129.5 (dd, JP-C ) 5.2 Hz, JP-C ) 3.6 Hz), 128.9, 128.7, 128.6,
128.5, 128.1, 128.0, 127.9, 127.7, 126.7, 125.2, 124.7, 123.9, 98.9
(d, JP-C ) 9.7 Hz, PCC), 93.0 (Cp*), 92.2 (d, JP-C ) 8.6 Hz, PCC),
31P NMR (CDCl3): δ 26.7 (sp3), -13.5 (sp2). 1H NMR
(CDCl3): δ 9.66 (d, JHH ) 8.6 Hz, 1H, 8-Np), 7.81 (d, JHH ) 7.6
Hz, 1H, 5-Np), 7.70-7.55 (m, 5H, 4-Np, 6-Np, 7-Np, o-PhPdO),
7.51-7.30 (m, 6H, 3-Np, o-PhPdO, m-PhPdO, p-PhPdO), 7.22
(Ψt, JHH)7.1 Hz, 2H, m-Ph), 7.17-7.05 (m, 6H, o-Ph, p-Ph,
m-PhPdO, p-PhPdO), 2.03 (s, 6H, MeCCP), 1.58 (s, 15H, Cp*).
13C NMR (CDCl3): δ 144.2 (dd, JPC ) 14.9 Hz, JPC ) 6.9 Hz,
1-Np), 139.3 (d, JPC ) 17.3 Hz, ipso-Ph), 136.2 (d, JPC ) 104.5
Hz, ipso-PhP(O)), 134.6 (d, JPC ) 2.2 Hz, 4a-Np), 133.6 (d, JPC
)
10.4 Hz, ipso-PhP(O)), 131.7 (d, JPC ) 8.8 Hz, o-Ph2P(O)), 131.4
(d, JPC ) 10.9 Hz, 8a-Np), 131.1 (dd, JPC ) 104 Hz, JPC ) 3.9 Hz,
2-Np), 130.9 (d, JPC ) 2.7 Hz, p-PhP(O)), 130.8 (p-PhP(O)), 130.7

2970 Organometallics, Vol. 26, No. 12, 2007
Carmichael et al.
79.5 (dd, JP-C ) 18.6 Hz, JP-C ) 18.6 Hz, PC), 78.1 (d, JP-C
)
Supporting Information Available: Additional crystallographic
1
data and H and 13C NMR spectra. This material is available free
21 Hz, PC), 14.7(d, JP-C ) 3.6 Hz, Me), 13.4 (d, JP-C ) 4.2 Hz,
Me), 11.2 (Cp*). Anal. Calcd for C46H46Cl6P2PtRu (7‚2CH2Cl2):
C, 47.23; H, 3.96. Found: C, 47.39; H, 4.07.
of charge via the Internet at http://pubs.acs.org.
Acknowledgment. We acknowledge CNRS and Ecole
Polytechnique (Gaspard Monge grant to N.S.) for funding.
OM0610905