Syntheses and X-ray structures of (2,2′-biphosphinine)-(η5-pentamethylcyclopentadienyl)- ruthenium(I) dimer and ruthenium(0) complexes

Article abstract of DOI:10.1021/om0004491

Reduction of the [Ru(Cp^*)(tmbp)Cl] complex (tmbp = 4,4′,5,5′-tetramethyl-2,2′-biphosphinine) with 1 and 2 equiv of sodium naphthalenide respectively yield a dimeric [Ru(Cp^*)(tmbp)]₂ complex and a [Ru(Cp^*)(tmbp)][Na(DME)₂] complex which were both structurally characterized. Trapping the Ru(0) complex with MeI, Ph₃SnCl, Me₃SnCl, or H⁺ affords the corresponding Ru(II) derivatives.

Full text of DOI:10.1021/om0004491

Organometallics 2000, 19, 5247-5250
5247
Syn th eses a n d X-r a y Str u ctu r es of
(2,2′-Bip h osp h in in e)-(η5-p en ta m eth ylcyclop en ta d ien yl)-
r u th en iu m (I) Dim er a n d Ru th en iu m (0) Com p lexes
Patrick Rosa, Louis Ricard, Franc¸ois Mathey,* and Pascal Le Floch*
Laboratoire “He´teroe´le´ments et Coordination”, UMR CNRS 7653, Ecole Polytechnique, 91128
Palaiseau Cedex, France
Received May 30, 2000
Ch a r t 1
Summary: Reduction of the [Ru(Cp*)(tmbp)Cl] complex
(tmbp ) 4,4′,5,5′-tetramethyl-2,2′-biphosphinine) with 1
and 2 equiv of sodium naphthalenide respectively yield
a dimeric [Ru(Cp*)(tmbp)]2 complex and a [Ru(Cp*)-
(tmbp)][Na(DME)2] complex which were both structur-
ally characterized. Trapping the Ru(0) complex with
MeI, Ph3SnCl, Me3SnCl, or H+ affords the corresponding
Ru(II) derivatives.
In tr od u ction
Owing to an adequate electronic balance between
their poor σ-donating and their strong π-accepting
abilities, phosphinines are particularly well-suited for
the stabilization of low-valent and reduced transition
metal complexes.1 Some years ago, we reported the
synthesis and reactivity of an (η5-pentamethylcyclopen-
tadienyl)chlororuthenium biphosphinine complex [Ru-
(Cp*)(tmbp)Cl] (Cp* ) η5-C5Me5) (tmbp ) 4,4′,5,5′-
tetramethyl-2,2′-biphosphinine) (1).2 During this study,
which mainly focused on the synthesis of various
cationic Ru(II) derivatives, we observed that complex 1
could be electrochemically reduced to the corresponding
Ru(0) complex which was found to be stable on the cyclic
voltammetry time scale. Interestingly, we also noted
that the outcome of this reduction was strongly depend-
ent on the scan rate used. Thus, whereas at high scan
rate (10 V s-1) the Ru(0) species could be produced via
two successive monoelectronic transfers, an irreversible
two-electron transfer process was observed at low scan
rate. On the basis of these results, we postulated the
formation of a dimeric Ru(I) complex of general formula
[Ru(Cp*)(tmbp)]2 as intermediate in this reduction
process (Chart 1).
(Cp*)(η4-C6H10)Cl].3 The reduction of 1 was carried out
using sodium naphthalenide as reducing agent in DME
at room temperature. Whatever the solvent used, reac-
tion of 1 equiv of NaNp with 1 yielded a very insoluble
compound 2. Due to its low solubility, 2 could not be
identified by conventional NMR techniques. Fortu-
nately, single crystals could be obtained by heating the
powder obtained in hot DME (80 °C) overnight and an
X-ray crystallographic study was carried out. As ex-
pected from our initial electrochemical experiments, the
structure of 2 results from the formal dimerization of
the [Ru(Cp*)(tmbp)] radical fragment resulting from the
loss of the chloride anion (eq 1).
To confirm this hypothesis we investigated the chemi-
cal reduction of complex 1. Furthermore, we were also
highly interested in synthesizing and studying the
synthetic potential of the Ru(0) species. Herein we
report on these investigations.
An ORTEP view of 2 is presented in Figure 1, and
the most relevant bond distances and angles are listed
below. Its structure is close to that of classical [M(Cp)-
(η1-CO)2(µ2-CO)2] (Cp ) C5H5, M ) Fe, Ru) dimers.4 In
each biphosphinine, one phosphorus atom bridges the
two Ru centers whereas the other is classically η1-
bonded. This type of bonding mode is not unprecedented.
In 1992, Venanzi et al. reported the X-ray structure of
a dicationic iridium(I) dimer [Ir2(niphos)2(COD)2][SbF6]2
of the 2-(2′-pyridyl)phosphinine ligand (niphos) in which
Resu lts a n d Discu ssion
As we previously reported, complex 1 was easily
prepared from the reaction of the tmbp2 ligand with [Ru-
(1) See, for example: (a) Mathey, F.; Le Floch, P. Chem. Ber. 1996,
129, 263. (b) Avarvari, N.; Me´zailles, N.; Ricard, L.; Le Floch, P.;
Mathey, F. Science 1998, 280, 1587. (c) Elschenbroich, C.; Nowontny,
M.; Behrendt, A.; Massa, W.; Wocadlo, S. Angew. Chem., Int. Ed. Engl.
1992, 31, 1343.
(2) (a) Le Floch, P.; Carmichael, D.; Ricard, L.; Mathey, F. J . Am.
Chem. Soc. 1991, 113, 667. (b) Le Floch, P.; Carmichael, D.; Ricard,
L.; Mathey, F. Organometallics 1992, 11, 2475. (c) Rosa, P.; Me´zailles,
N.; Mathey, F.; Le Floch, P. J . Org. Chem. 1998, 63, 4826.
(3) Le Floch, P.; Mansuy, S.; Ricard, L.; Mathey, F.; J utand, A.;
Amatore, C. Organometallics 1996, 15, 3267.
(4) See, for example: (a) Forrow, N. J .; Knox, S. A. R. J . Chem. Soc.
Chem. Commun. 1984, 679. (b) Mills, O. S.; Nice, J . P. J . Organomet.
Chem. 1967, 9, 339. (c) Mague, J . T. Acta Crystallogr. 1995, C51, 831.
(d) Steiner, A.; Gornitza, H.; Stalke, D.; Edelmann, F. T. J . Organomet.
Chem. 1992, 431, C21-C25. (e) Nataro, C.; Angelici, R. J . Inorg. Chem.
1998, 37, 2975.
10.1021/om0004491 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 11/02/2000

5248 Organometallics, Vol. 19, No. 24, 2000
Notes
Additional evidence for the structure of 3 was given
by an X-ray crystallographic study. Whereas some X-ray
structures of anionic [Fe(Cp or Cp*)L2] complexes (L )
CO,8a-c P,8d ethylene8e-h or L2 ) diene8i) are known, to
the best of our knowledge, no X-ray structures of their
ruthenium counterparts have been reported so far.
Complex 3 turns out to be the first example. An ORTEP
view of 3 is presented in Figure 2, and important bond
distances and angles are gathered below.
Complex 3 adopts a distorted three-legged piano stool
structure, the ruthenium Cp* centroid axis being nearly
in-plane with the tmbp (Θ ) 170°). The Na+ cation only
slightly interacts with the metal as shown by the Ru-
Na bond distance (3.072(2) Å) which exceeds the sum
of the covalent radii (2.80 Å). One may propose that the
weakness of this interaction results from the steric
repulsion caused by the two coordinated DME ligands.
Bond lengths in phosphinine units are very close to
those recorded for the [Ru(η6-C10H14)(tmbp)] complex.7b
As noted previously for 2, lengthening of internal PdC
bonds and a shortening of the C-C bridge point out
toward an electronic transfer from the metal to the π*
LUMO of tmbp. This phenomenon is also evidenced by
short Ru-P bonds (2.191(1) and 2.194(1) Å), compared
to those recorded in the [Ru(Cp*)(tmbp)Cl] complex
(2.2375(7) and 2.2475(7) Å).
F igu r e 1. ORTEP drawing of complex 2. Hydrogen atoms
are omitted for clarity. Ellipsoids are scaled to enclose 50%
of the electron density. Selected bond distances (Å): Ru1-
Ru1′, 2.949(1); P1-Ru1, 2.351(1); P1-Ru1′, 2.320(1); P2-
Ru1, 2.227(1); P1-C1, 1.747(3); C1-C2, 1.388(4); C2-C3,
1.407(5); C3-C4, 1.392(5); C4-C5, 1.401(4); P1-C5, 1.769-
(3); P2-C6, 1.745(3); C5-C6, 1.451(4); C6-C7, 1.401(4);
C7-C8, 1.395(4); C8-C9, 1.413(5); C9-C10, 1.390(5); P2-
C10, 1.722(3), Ru1-centroid, 1.905(3). Selected bond angles
(deg): Ru1-P1-Ru1′, 78.28(3); C1-P1-C5, 101.3(2); C6-
P2-C10, 104.2(2); Ru1′-Ru1-P1, 50.39(3); P1-Ru1′-P2,
96.33(3).
each phosphinine bridges the Ir2 core in a µ2-fashion.5
Furthermore, very recently, the X-ray structure of a
trinuclear triangulo Pd3 cluster incorporating three µ2-
coordinated monophosphinines has been reported.6 In
2, though they are coordinated in a different fashion,
both phosphinine units in tmbp nearly show the same
geometrical features. A noticeable lengthening of the
internal PdC bond distances is observed in both rings,
as well as a shortening of the internal C-C bond of the
bridge (1.451(4) vs 1.490(8) Å in the cis-free ligand).2b
As previously noted in other tmbp complexes, this
phenomenon reflects the electronic transfer from the
metal to the π* LUMO of the ligand.7 These geometrical
alterations are only limited to the PCCP unit, and no
noticeable disruption of aromaticity can be observed
within both rings when examining the carbocyclic
backbones.
Complex 3 is a suitable precursor of Ru(II) biphos-
phinine complexes. Electrophiles such as MeI, Ph3SnCl,
and Me3SnCl cleanly react at the metal to give the
expected Ru-Me 4, Ru-SnR3 (5, R ) Ph; 6, R ) Me)
derivatives. All of these complexes were successfully
The existence of this dimer being established, we
focused our work on the dielectronic reduction of
complex 1. Reaction of 2 equiv of NaNp with 1 in DME
at room temperature cleanly yielded complex 3 as an
oxygen-sensitive solid which was fully characterized by
NMR techniques. Complex 3 displays a remarkable
thermal stability, and it can be stored for days at room
temperature in DME solutions. Additionally we also
found that 3 could be generated from the dielectronic
reduction of dimer 2 in DME at room temperature.
characterized by NMR spectroscopy and elemental
analyses when possible. Additionally, we found that
quenching with CH3CO2H yielded the Ru-H derivative
79 which exhibits in 1H NMR a classical hydride
2
resonance at -14.85 ppm (t, J (P-H) ) 32.40 Hz).10
(8) See, for example: (a) Burlitch, J . M.; Hayes, S. E.; Whitwell, G.
E., II Organometallics 1982, 1, 1074. (b) Petersen, R. B.; Ragosta, J .
M.; Whitwell, G. E., II; Burlitch, J . M. Inorg. Chem. 1983, 22, 3407.
(c) Hey-Hawkins, E.; von Schnering, H.-G. Z. Naturforsch. 1990, 46b,
621. (d) Felkin, H.; Knowles, P. J .; Meunier, B.; Mitschler, A.; Ricard,
L.; Weiss, R. J . Chem. Soc., Chem. Commun. 1974, 44. (e) J onas, K.;
Schiferstein, L. Angew. Chem. Int. Ed. Engl. 1979, 18, 549. (f) J onas,
K.; Schiferstein, L.; Angew. Chem., Int. Ed. Engl. 1979, 18, 550. (g)
J onas, J . Adv. Organomet. Chem., 1981, 19, 97. (h) J onas, K. Angew.
Chem., Int. Ed. Engl. 1985, 24, 295. (i) Fagan, P. J .; Mahoney, W. S.;
Calabrese, J . C.; Williams, I. D. Organometallics 1990, 9, 1843.
(5) Schmid, B.; Venanzi, L. M.; Gerfin, A. T.; Gramlich, V.; Mathey,
F. Inorg. Chem. 1992, 31, 5117.
(6) Reetz, M.; Bohres, E.; Goddard, R.; Holthausen, M. C.; Thiel,
W. Chem. Eur. J . 1999, 7, 2101.
(7) (a) Rosa, P.; Ricard, L.; Le Floch, P.; Mathey, F.; Sini, G.;
Eisenstein, O. Inorg. Chem. 1998, 37, 3154. (b) Rosa, P.; Ricard, L.;
Mathey, F.; Le Floch, P. Organometallics 1999, 18, 3348.

Notes
Organometallics, Vol. 19, No. 24, 2000 5249
du CNRS”, at Gif sur Yvette, France. 4,4′,5,5′-Tetramethyl-
2,2′-biphosphinine2 and complex 1 were prepared according
to reported procedures.3
Syn th esis of [Ru (Cp *)(tm bp )]2 (2). A solution of sodium
naphthalenide in DME (10 mL, 0.5 mmol) was added to solid
complex 1 (0.26 g, 0.5 mmol) in the glovebox at room temper-
ature. After 1 h the volume of solvent was reduced to 5 mL,
and complex 2 precipitated overnight. Filtration and washings
with THF (2 × 5 mL) allowed the elimination of naphthalene
and the major part of NaCl salts. After drying, 2 was recovered
as a dark oxygen-sensitive powder. The presence of traces of
NaCl salts precluded calculation of a precise yield. Suitable
crystals for the X-ray crystallographic study were obtained by
heating the powder obtained in a sealed tube in DME at 80
°C overnight. Complex 2 was too insoluble to be characterized
by conventional 1H and 13C NMR techniques. IR (KBr): n, 1636
(br), 1557 (s), 1360 (s), 1360 (s), 1304 (s), 1262 (s), 1081 (s),
998 (s), 686 (s), 670 (s) cm-1. Anal. Calcd for C48H62P4Ru2: C,
59.74; H, 6.48. Found: C, 60.05; H, 6.63.
Syn th esis of [Ru (Cp *)(tm bp )][Na (DME)2] (3). A solution
of sodium naphthalenide in DME (20 mL, 1 mmol) was added
to solid complex 1 (0.26 g, 0.5 mmol) in the glovebox at room
temperature. After 5 min of stirring, a control by 31P NMR
indicated the complete formation of complex 3. After filtration,
the solvent was evaporated, and naphthalene was sublimed
to yield 3 as a deep-purple oxygen- and moisture-sensitive
powder. The overall yield of the reaction could not be estimated
since NaCl salts could not be totally eliminated. Suitable
crystals for the X-ray crystallographic study were obtained by
heating the resulting deep-purple powder at 80 °C overnight
F igu r e 2. ORTEP drawing of complex 3. Hydrogen atoms
are omitted for clarity. Ellipsoids are scaled to enclose 50%
of the electron density. The crystallographic labeling is
arbitrary and different from the numbering used for
assignments in the 13C NMR spectrum. Selected bond
distances (Å): P1-Ru1, 2.191(1); P2-Ru1, 2.194(1); P1-
C1, 1.738(4); C1-C2, 1.369(6); C2-C3, 1.407(6); C3-C4,
1.400(5); C4-C5, 1.405(5); C5-P1, 1.768(4); C5-C6, 1.445-
(4); Ru1-Na1, 3.072(2); Na1-O1, 2.427(3); Na1-O2, 2.402-
(3); Na1-O3, 2.346(3); Na1-O4, 2.564(3). Bond angles
(deg): P1-Ru1-P2, 78.69(4); C1-P1-C5, 101.9(2), C6-
P2-C10, 101.(2); P1-Ru1-Na1, 73.19(5), P2-Ru1-Na1,
75.64(5), P1-Ru1-Ct(Cp*), 139.41; P2-Ru1-Ct(Cp*),
140.38.
in
a
sealed tube in
a
mixture of DME/Et2O. 31P NMR
1
4
(C4D8O): δ 184.40. H NMR (C4D8O): δ 2.23 (t, 15H, J (P-
H) ) 1.80, Me of Cp*), 2.27 and 2.42 (s, 2 × 6H, Me of
C
C
C
14H16P2), 7.70 (m, AA′XX′, 2H, ΣJ (P-H) ) 26.85, H3,3′ of
14H16P2), 8.12 (m, AA′XX′, 2H, ΣJ (P-H) ) 17.10, H6,6′ of
14H16P2). 13C NMR (C4D8O): δ 13.65 (s, Me of Cp*), 22.55 (s,
In conclusion, we have shown that reduction of
complex 1 effectively proceeds via the formation of dimer
2. Most importantly, we also demonstrated that biphos-
phinine can efficiently stabilize the anionic [Ru(Cp*)]-
fragment. Further studies now focus on the reactivity
of this anion.
Me of C14H16P2), 24.55 (vt, AXX′, ΣJ (P-C) ) 8.85, Me of
C
14H16P2), 87.75 (t, 2J (P-C) ) 2.65, Cipso of Cp*), 115.95 (vt,
AXX′, ΣJ (P-C) ) 14.00, C5,5′ or C4,4′ of C14H16P2), 126.70 (vt,
AXX′, ΣJ (P-C) ) 20.40, C3,3′ or C6,6′ of C14H16P2), 129.00 (vt,
AXX′, ΣJ (P-C) ) 15.85, C6,6′ or C3,3′ of C14H16P2), 135.70 (vt,
AXX′, ΣJ (P-C) ) 73.65, C2,2′ of C14H16P2), 139.00 (vt, AXX′,
ΣJ (P-C) ) 11.20, C5,5′ or C4,4′ of C14H16P2). Complex 3 turned
out to be too moisture- and oxygen-sensitive to be characterized
by elemental analysis.
Exp er im en ta l Section
All reactions were routinely performed under an inert
atmosphere of argon or nitrogen by using Schlenk and glovebox
techniques and dry deoxygenated solvents. Dry Et2O, THF,
DME, and hexanes were obtained by distillation from Na/
benzophenone and dry CH2Cl2 from P2O5. Deuterated solvents
were dried with 4 Å Linde molecular sieves. Nuclear magnetic
resonance spectra were recorded on a Bruker AC-200 SY
spectrometer operating at 200.13 MHz for 1H, 50.32 MHz for
13C, and 81.01 MHz for 31P. Solvent peaks are used as internal
Syn th esis of [Ru (Cp *)(tm bp )Me] (4). Methyl iodide (32
µL, 0.5 mmol) was added at room temperature to a solution of
anion 3 prepared as described above from complex 1 (0.26 g,
0.5 mmol) and naphthalene sodium. After 5 min of stirring, a
31P NMR control indicated the complete formation of 4. The
solvent was evaporated, dichloromethane (40 mL) was added,
and the resulting solution was filtrated. After evaporation of
dichloromethane, the resulting dark solid obtained was washed
with hexanes (15 mL) and Et2O (15 mL). Traces of naphthalene
were totally removed by drying the powder obtained overnight.
Complex 4 was finally isolated as a dark-red oxygen- and
moisture-sensitive solid. Yield: 125 mg (50%). 31P NMR (CD2-
1
reference relative to Me4Si for H and 13C NMR chemical shifts
(ppm); 31P NMR chemical shifts are relative to a 85% H3PO4
external reference. Coupling constants are given in hertz. The
following abbreviations are used: s, singlet; d, doublet; t,
triplet; m, multiplet; p, pentuplet; v, virtual. IR data were
collected on a Perkin-Elmer 297 spectrometer. Mass spectra
were obtained at 70 eV with a HP 5989B spectrometer coupled
to a HP 5980 chromatograph by the direct inlet method.
Elemental analyses were performed by the “Service d’analyze
1
3
Cl2): δ 237.30. H NMR (CD2Cl2): δ -1.15 (t, 3H, J (P-H) )
4
5.60, Ru-Me), 1.98 (t, 15H, J (P-H) ) 2.30, Me of Cp*), 2.37
(vd, AA′XX′, 6H, ΣJ (P-H) ) 3.50, Me of C14H16P2), 2.47 (s,
6H, Me of C14H16P2), 7.97 (vd, AA′XX′, 2H, ΣJ (P-H) ) 25.05,
H
3,3′ of C14H16P2), 8.20 (vd, AA′XX′, 2H, ΣJ (P-H) ) 17.25, H6,6′
of C14H16P2). 13C NMR (CD2Cl2): δ -21.80 (t, 2J (P-C) ) 13.50,
(9) Personal communication from Prof. R. Morris: complex 7 was
previously synthesized by reduction of complex 1. Fong, T. Ph.D.
Thesis, University of Toronto, Canada, 1999.
Ru-Me), 10.95 (s, Me of Cp*), 22.30 (s, Me of C14H16P2), 24.15
2
(vt, AXX′, ΣJ (P-C) ) 9.00, Me of C14H16P2), 95.40 (t, J (P-C)
) 2.90, Cipso of Cp*), 127.90 (vt, AXX′, ΣJ (P-C) ) 19.80, C5,5′
or C4,4′ of C14H16P2), 129.20 (m, AXX′, ΣJ (P-C) ) 40.55, C3,3′
of C14H16P2), 135.60 (vt, AXX′, ΣJ (P-C) ) 17.35, C6,6′ of
(10) For selected references, see: (a) J ia, G.; Morris, R. Inorg. Chem.
1990, 29, 582. (b) J ia, G.; Lough, A. J .; Morris, R. Organometallics
1992, 11, 161. (c) Keady, M. S.; Koola, J .; Ontko, A. C.; Merwin, R. K.;
Roddick, D. M. Organometallics 1992, 11, 3417. (d) Lemke, F.;
Brammer, L. Organometallics 1995, 14, 3980. (e) Brammer, L.;
Klooster, W. T.; Lemke, F. R. Organometallics 1996, 15, 1721.
C
14H16P2), 144.10 (vt, AXX′, ΣJ (P-C) ) 13.60, C5,5′ or C4,4′ of
C14H16P2), 148.65 (vt, AXX′, ΣJ (P-C) ) 68.25, C2,2′ of C14H16P2).

5250 Organometallics, Vol. 19, No. 24, 2000
Notes
(CDCl3): δ -0.53 (s, 9H, 2J (117/119Sn-H) ) 39.85 and 41.65,
Me of SnMe3), 2.12 (t, 15H, J (P-H) ) 2.30, Me of Cp*), 2.38
Ta ble 1. Cr ysta llogr a p h ic Da ta a n d Exp er im en ta l
P a r a m eter s for th e Str u ctu r es of 2 a n d 3
4
(vd, AA′XX′, 6H, ΣJ (P-H) ) 3.50, Me of C14H16P2), 2.49 (s,
6H, Me of C14H16P2), 7.87 (vd, AA′XX′, 2H, ΣJ (P-H) ) 24.30,
2
3
mol formula
mol wt
cryst descripn
habit/size (mm))
C
48H62P4Ru2
C32H51NaO4P2Ru
685.73
deep purple needle
H
3,3′ of C14H16P2), 8.23 (vd, AA′XX′, 2H, ΣJ (P-H) ) 19.50, H6,6′
482.50
of C14H16P2). 13C NMR (CD2Cl2): δ -7.95 (t, J (P-C) ) 1.90,
Me of SnMe3), 12.10 (s, Me of Cp*), 22.35 (s, Me of C14H16P2),
24.35 (vd, AXX′, ΣJ (P-C) ) 10.50, Me of C14H16P2), 94.50 (t,
2J (P-C) ) 2.35, Cipso of Cp*), 127.20 (vd, AXX′, ΣJ (P-C) )
20.35, C4,4′ or C5,5′ of C14H16P2), 128.95 (m, AXX′, ΣJ (P-C) )
27.10, C3,3′ of C14H16P2), 134.70 (vt, AXX′, ΣJ (P-C) ) 25.20,
C6,6′ of C14H16P2), 144.30 (vt, AXX′, ΣJ (P-C) ) 17.75, C5,5′ or
C4,4′ of C14H16P2), 147.00 (vt, AXX′, ΣJ (P-C) ) 72.15, C2,2′ of
3
red plate
0.18 × 0.18 × 0.16 0.22 × 0.10 × 0.08
cryst syst
space group
a (Å)
b (Å)
c (Å)
triclinic
P1h
orthorhombic
P212121
10.629(5)
17.561(5)
18.872(5)
10.778(5)
10.920(5)
11.546(5)
67.620(5)
69.280(5)
61.900(5)
1082.8(8)
2
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
C
14H16P2). MS (m/z, rel. intensities): 631 (13, M+ - Me), 483
(30, M+ - SnMe3), 165 (100, SnMe3+). Anal. Calcd for C27H40P2-
3523(2)
4
1.293
1440
0.580
RuSn: C, 50.17; H, 6.24. Found: C, 49.85; H, 6.18.
D (g/cm3)
F(000)
1.480
498
0.878
150.0(1)
27.47
Syn th esis of [Ru (Cp *)(tm bp )H] (7). The procedure for
the synthesis of 7 is identical to that described above. Complex
7 was obtained by addition of CH3CO2H (32 µL, solution 90%
in water, 0.5 mmol) to a solution of anion 3 (0.5 mmol).
Complex 7 was isolated as a dark-red solid. Yield: 145 mg
µ (cm-1
T (K)
)
150.0(1)
28.28
max θ (deg)
hkl ranges
-13 to +13;
-14 to +14;
-14 to +11
6926
-13 to +13;
-22 to +23;
-25 to +12
16433
(60%). 31P NMR (CD2Cl2): δ 227.80. 1H NMR (CDCl3):
δ
2
4
-14.85 (t, 1H, J (P -H) ) 32.40, Ru-H), 2.20 (t, 15H, J (P-
H) ) 2.20, Me of Cp*), 2.36 (vd, AA′XX′, 6H, ΣJ (P-H) ) 3.60,
Me of C14H16P2), 2.48 (s, 6H, Me of C14H16P2), 8.04 (vd, AA′XX′,
2H, ΣJ (P-H) ) 24.70, H3,3′ of C14H16P2), 8.17 (vd, AA′XX′, 2H,
ΣJ (P-H) ) 18.45, H6,6′ of C14H16P2). 13C NMR (CD2Cl2): δ 12.35
(s, Me of Cp*), 22.25 (s, Me of C14H16P2), 24.15 (m, AXX′, ΣJ (P-
no. of rflns measd
no. of indep rflns
no. of rflns used
Rint
refinement type
H atoms
4887
4370
0.0247
Fsqd
mixed
7787
6237
0.0577
Fsqd
mixed
374
0.52(3)
16
0.0873
0.0402
>2σ(I)
1.018
no. of params refined 253
2
C) ) 14.80, Me of C14H16P2), 96.05 (t, J (P-C) ) 2.45, Cipso of
Flack param
rfln/param ratio
wR2
R1
criterion
not applicable
Cp*), 127.20 (vt, AXX′, ΣJ (P-C) ) 19.45, C4,4′ or C5,5′ of
C14H16P2), 128.90 (m, AXX′, ΣJ (P-C) ) 28.55, C3,3′ of C14H16P2),
135.30 (vt, AXX′, ΣJ (P-C) ) 21.95, C6,6′ of C14H16P2), 143.95
(vt, AXX′, ΣJ (P-C) ) 20.45, C5,5′ or C4,4′ of C14H16P2), 147.45
(vt, AXX′, ΣJ (P-C) ) 70.20, C2,2′ of C14H16P2). Complex 7 did
not give reproducible elemental analysis data.
17
0.1228
0.0380
>2σ(I)
1.002
GOF
diff peak/hole (eÅ3)
3.861(0.115/
0.623(0.105)/
-0.461(0.105)
-0.934(0.115)a
X-r a y Cr ysta llogr a p h ic Stu d ies of 2 a n d 3. Crystals
suitable for X-ray diffraction were obtained by heating crude
powders in DME at 80 °C under vacuum in a sealed tube. The
tube was broken in the glovebox, crystals were protected with
paratone oil for handling and then submitted to X-ray diffrac-
tion analysis. Data were collected on a Nonius Kappa CCD
diffractometer using an Mo KR (λ ) 0.71070 Å) X-ray source
and a graphite monochromator. Experimental details are
described in Table 1. The structure of complex 3 was refined
as a racemic twin. The crystal structures were solved using
SIR 9711 and Shelxl-97.12 ORTEP drawings were made using
ORTEP III for Windows.13
a
Located approximately 0.9 Å from Ru.
Anal. Calcd for C25H34P2Ru: C, 60.35; H, 6.89. Found: C,
60.00; H, 6.83.
Syn th esis of [Ru (Cp *)(tm bp )Sn P h 3] (5). The procedure
for the synthesis of 5 is identical to that described above.
Complex 5 was obtained by addition of Ph3SnCl (0.5 mmol) to
a solution of anion 3 (0.5 mmol). Complex 5 was isolated as a
dark-red solid. Yield: 170 mg (70%). 31P NMR (CDCl3):
δ
224.15 (2J (117/119Sn-P) ) 325.60 and 340.10). 1H NMR
4
(CDCl3): δ 1.98 (t, 15H, J (P-H) ) 4.60, Me of Cp*), 2.30
(vd, AA′XX′, 6H, ΣJ (P-H) ) 3.85, Me of C14H16P2), 2.54 (s,
6H, Me of C14H16P2), 6.97-7.12 (m, 15H, SnPh3), 7.68 (vd,
AA′XX′, 2H, ΣJ (P-H) ) 19.50, H3,3′ of C14H16P2), 8.12 (vd,
AA′XX′, 2H, ΣJ (P-H)
)
24.15, H6,6′ of C14H16P2); 13C
Ack n ow led gm en t. The authors thank the CNRS
NMR (CDCl3): δ 12.55 (s, Me of Cp*), 22.85 (s, Me of C14H16P2),
25.20 (vd, AXX′, ΣJ (P-C) ) 9.80, Me of C14H16P2), 94.80
(t, 2J (P-C) ) 2.10, Cipso of Cp*), 126.90 (s, Cpara of Ph), 127.35
(s, 2J (117/119Sn-C) ) 23.70, Cortho of Ph), 128.35 (vd, AXX′,
ΣJ (P-C) ) 20.95, C5,5′ or C4,4′ of C14H16P2), 129.90 (m, AXX′,
and the Ecole Polytechnique for supporting this work.
Su p p or tin g In for m a tion Ava ila ble: Listings of atomic
coordinates, including H atoms and equivalent isotropic
displacement parameters, bond lengths, and bond angles. This
material is available free of charge via the Internet at
http://pubs.acs.org.
ΣJ (P-C)
) 28.40, C3,3′ of C14H16P2), 136.35 (m, AXX′,
3
ΣJ (P-C) ) 27.70, C6,6′ of C14H16P2), 137.70 (s, J (117/119Sn-C)
)33.70, Cmeta of Ph), 144.55 (m, AXX′, ΣJ (P-C) ) 19.50, C4,4′
or C5,5′ of C14H16P2), 146.35 (s, Cipso of Ph), 148.45 (m, AXX′,
ΣJ (P-C) ) 74.00, C2,2′ of C14H16P2. MS (m/z, rel. intensities):
833 (8, M+), 483 (100, M+ - SnPh3). Anal. Calcd for C42H46P2-
RuSn: C, 60.59; H, 5.57. Found: C, 60.80; H, 5.63.
OM0004491
(11) SIR97, an integrated package of computer programs for the
solution and refinement of crystal structures using single-crystal
data: Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.; Giaco-
vazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R.
(12) Sheldrick, G. M. SHELXL-97; Universita¨t Go¨ttingen, Go¨ttingen,
Germany, 1997.
Syn th esis of [Ru (Cp *)(tm bp )Sn Me3] (6). The procedure
for the synthesis of 6 is identical to that described above.
Complex 6 was obtained by addition of Me3SnCl (0.5 mmol)
to a solution of anion 3 (0.5 mmol). Complex 5 was isolated as
a dark-red oxygen-sensitive solid. Yield: 160 mg (50%). 31P
(13) ORTEP-3 program created by Louis J . Farrugia (Department
of Chemistry, University of Glasgow).
1
NMR (CD2Cl2): δ 226.05 (2J (117/119Sn-P) ) 296.75); H NMR