Synthesis of phospholyl-bridged heterobimetallic ruthenium hydrides in combination with zirconium and ytterbium and the crystal structure of (THF)2Yb[μ(η5,η1)-C 4Me4P]2Ru(H)2(Ph<

Article abstract of DOI:10.1021/om9602320

Heterobimetallic zirconium-ruthenium and ytterbium-ruthenium dihydrides, having bridging phospholyl ligands, have been obtained for the first time. Reaction of bis(η⁵ tetramethylphospholyl)dichlorozirconium [(TMP)₂ZrCl₂] w

Full text of DOI:10.1021/om9602320

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4178
Organometallics 1996, 15, 4178-4181
Syn th esis of P h osp h olyl-Br id ged Heter obim eta llic
Ru th en iu m Hyd r id es in Com bin a tion w ith Zir con iu m
a n d Ytter biu m a n d th e Cr ysta l Str u ctu r e of
(THF )2Yb[µ(η5,η1)-C4Me4P ]2Ru (H)2(P h 3P )2
P. Desmurs,† M. Visseaux,† D. Baudry,*,† A. Dormond,† F. Nief,*,‡ and L. Ricard‡
Laboratoire de Synthe`se et Electrosynthe`se Organome´tallique, CNRS URA 1685, Universite´ de
Dijon, BP 138, 21004 Dijon Cedex, France, and Laboratoire He´te´roe´le´ments et Coordination,
CNRS URA 1499, DCPH Ecole Polytechnique, 91128 Palaiseau Cedex, France
Received March 27, 1996X
Heterobimetallic zirconium-ruthenium and ytterbium-ruthenium dihydrides, having
bridging phospholyl ligands, have been obtained for the first time. Reaction of bis(η5-
tetramethylphospholyl)dichlorozirconium [(TMP)2ZrCl2] with RuH4(PPh3)3 gave the zirconium-
ruthenium heterobimetallic Cl2Zr[µ(η5,η1)-TMP]2 Ru(H)2(PPh3)2. This compound was trans-
formed into the hydridochloride Cl2Zr[µ(η5,η1)-TMP]2Ru(H)(Cl)(PPh3)2 by the action of CCl4.
Similarly, reaction of [(TMP)2Yb] with RuH4(PPh3)3 afforded (THF)2Yb[µ(η5,η1)-TMP]2Ru-
(H)2(PPh3)2. The structure of this compound, which has been determined by X-ray
crystallography, confirms the trans configuration of the dihydride deduced previously from
NMR data. Attempts to isolate products from the reaction of [(TMP)2UCl2] or [(TMP)2U-
(BH4)2] with RuH4(PPh3)3 were unsuccessful, but NMR data show the formation of both
heterobimetallic trans- and cis-ruthenium dihydride-uranium compounds X2U[µ(η5,η1)-
TMP]2Ru(H)2(PPh3)2 (X ) BH4, Cl) in solution.
In tr od u ction
Early-late heterobimetallic compounds are of current
pholyl ring can also be used as a bridging system
because it possesses both a 5-electron ring system,
analogous to that of a Cp ligand, and a σ2,λ3-phosphorus
atom which can act as a 2-electron donor. A bis(η5-
phospholyl) complex can thus act as a chelating ligand:
we have already prepared compounds where a diphos-
phazirconocene dichloride is linked to a metal carbonyl
residue.5 Recently, we have also prepared several
π-phospholyl complexes of the f-metals,6,7 and some
heterobimetallic ruthenium-zirconium dihydrides.8 Then,
we decided to try to link bis(η5-phospholyl)zirconium,
-ytterbium, and -uranium compounds to a ruthenium
hydride moiety. Here, we describe the synthesis of the
first f-metal-Ru hydride heterobimetallic systems.
interest. The presence, in a single molecule, of an early
transition metal, possessing hard Lewis-acid character,
and of a soft, late transition metal in a single molecule
allows the potential for cooperative behavior between
the metals which could confer unusual reactivity or
catalytic properties.1 Cyclopentadienylphosphines have
often been used to bridge metallic centers;2 the recently
described ytterbium-platinum, ytterbium-nickel,3 sa-
marium-rhodium, and uranium-molybdenum com-
pounds have incorporated the f-elements.4 The phos-
† CNRS URA 1685.
‡ CNRS URA 1499.
X Abstract published in Advance ACS Abstracts, August 15, 1996.
(1) For recent reviews and papers, see: Casey, C. P.; Audett, J . D.
Chem. Rev. 1986, 86, 339. Stephan, D. W. Coord. Chem. Rev. 1989,
95, 41. Baranger, A. M.; Bergman, R. G. J . Am. Chem. Soc. 1993, 115,
7890. Dormond, A.; Baudry, D.; Visseaux, M.; Hepie`gne, P. J . All.
Comp. 1994, 213/ 214, 1. Diamond, G. M.; Green, M. L. H.; Popham,
N. A.; Chernega, A. N. J . Chem. Soc., Chem. Commun. 1994, 727.
Baranger, A. M.; Bergman, R. G. J . Am. Chem. Soc. 1994, 116, 3822.
Nakajuma, T.; Mise, T.; Shimizu, I.; Wakatsuki, Y. Organometallics
1995, 14, 5598. Fruduch, S.; Gade, L. H.; Scowett, I. J .; Partlin, M. M.
Organometallics 1995, 14, 5344. Hanna, T. A.; Baranger, A. M.;
Bergman, R. G. J . Am. Chem. Soc. 1995, 117, 11363. Schwartz, D. J .;
Ball, G. E.; Andersen, R. A. J . Am. Chem. Soc. 1995, 117, 6027.
Amador, U.; Delgado, E.; Fornies, J .; Hernandez, E.; Lalinde, E.;
Moreno, M. T. Inorg. Chem. 1995, 34, 5279.
(2) Rausch, M. D.; Edwards, B. H.; Rogers, R. D.; Atwood, J . L. J .
Am. Chem. Soc. 1983, 105, 3882. Casey, C. P.; Nief, F. Organometallics
1985, 4, 1218. Rausch, M. D.; Spink, W.; Atwood, J . L.; Baskar, A. J .;
Bott, S. G. Organometallics 1989, 8, 2627. He, X.; Maisonnat, A.;
Dahan, F.; Poilblanc, R. Organometallics 1991, 10, 2443. Ogasa, M.;
Rausch, M. D.; Rogers, R. D. J . Organomet. Chem. 1991, 403, 279.
Bandoli, G.; Trovo, G.; Dolmella, A.; Longato, B. Inorg. Chem. 1992,
31, 45. Houlton, A.; Mingos, D. M. P.; Murphy, D. M.; Williams, D. J .;
Phang, L.-T.; Hor, T. S. A. J . Chem. Soc., Dalton Trans. 1993, 3629.
Hayashi, T.; Ohno, A.; Lu, S.; Matsumoto, Y.; Fukuyo, E.; Yanagi, K.
J . Am. Chem. Soc. 1994, 116, 4221. Brown, J . M.; Perez-Torrente, J .
J .; Alcock, N. W.; Clase, H. J . Organometallics 1995, 14, 207. Broussier,
R.; Delmas, G.; Perron, P.; Gautheron, B.; Petersen, J . L. J . Organomet.
Chem. 1996, 511, 185.
Resu lts a n d Discu ssion
Syn th esis of Zir con iu m -Ru th en iu m Com p lexes.
Previously, we have been able to obtain mixed Zr-metal
carbonyl species by using bis(η5-phospholyl)dichloro-
zirconium as a ligand.5 To use the recently prepared
bis(η5-phospholyl) f-element complexes7 as bridging
ligands in the same manner, we looked for a late
transition metal fragment such as RuH2(PPh3)2, which
should be capable of coordinating to the lone pairs of
(3) Deacon, G. B.; Forsyth, C. M.; Patalinghug, W. C.; White, A. H.;
Dietrich, A.; Schumann, H. Aust. J . Chem. 1992, 45, 567. Deacon, G.
B.; Dietrich, A.; Forsyth, C. M.; Schumann, H. Angew. Chem., Int. Ed.
Engl. 1989, 28, 1370.
(4) Visseaux, M.; Dormond, A.; Kubicki, M. M.; Mo¨ıse, C.; Baudry,
D.; Ephritikhine, M. J . Organomet. Chem. 1992, 433, 95. Baudry, D.;
Dormond, A.; Hafid, A. New J . Chim. 1993, 17, 465.
(5) Nief, F.; Mathey, F.; Ricard, L. J . Organomet. Chem. 1990, 384,
271.
(6) Baudry, D.; Ephritikhine, M.; Nief, F.; Ricard, L.; Mathey, F.
Angew. Chem., Int. Ed. Engl. 1990, 29, 1485.
(7) Nief, F.; Ricard, L.; Mathey, F. Polyhedron 1993, 12, 19.
(8) Baudry, D.; Dormond, A.; Visseaux, M.; Monnot, C.; Chardot,
H.; Lin, Y.; Bakhmutov, V. New J . Chem. 1995, 19, 921.
S0276-7333(96)00232-4 CCC: $12 00 © 1996 American Chemical Society

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Heterobimetallic Ruthenium Hydrides
Organometallics, Vol. 15, No. 20, 1996 4179
Ta ble 1. X-r a y Exp er im en ta l Da ta for 3
Sch em e 1
cryst description
deep red parallelipiped
dimens, mm
space group
a, nm
0.20 × 0.20 × 0.30
orthorhombic, P212121 (No. 19)
1.3105(1)
b, nm
1.8678(2)
c, nm
2.5477(3)
6.2363(1.9)
V, nm3
Z
4
dcalc
1.456
F(000)
2808
radiation
Mo KR (λ ) 71.073 pm)
µ, cm-1
18.7
temp, K
max 2θ, deg
no. of unique reflecns
reflens included
corr
123 ( 0.1
60
9849
2
5563 [Fo > 3σ(Fo2)]
Lorentz-polarization, abs
(DIFABS, min ) 0.842,
max ) 1.370)
R
0.041
Rw
0.045
GOF
1.03
convergence, largest shift/error
minimization function
least-squares weights
0.02
w(|Fo| - |Fc|)2, w ) 4F2/σ2(F2)
the phospholyl moiety. Initially, we chose to employ bis-
(η5-phospholyl)dichlorozirconium as a model system for
the bis(η5-phospholyl) f-element complexes because (a)
we expected good stability for Ru-Zr(IV) complexes and
(b) we had already prepared heterobimetallic ruthenium-
zirconium µ-hydrido complexes,8 wherein a flexible
cyclopentadienylphosphine was used as bridging ligand.
A red solution resulted when a mixture of bis(η5-
tetramethylphospholyl)dichlorozirconium [(TMP)2ZrCl2]
and RuH4(PPh3)3 was stirred in toluene. Investigation
of this solution by 31P NMR showed the liberation of
free PPh3 and the progressive appearance of a decep-
tively simple AB quartet which, upon closer inspection,
was shown to be an AA′XX′ system. This strongly
suggested that the expected heterobimetallic compound
had formed, that the arrangement of the phosphorus
atoms around ruthenium was planar, and that the
stereochemistry of the dihydride was trans (1, Scheme
1).
4Fo2/σ2(Fo2) σ2(F2) ) σ2(I) +
(pF2)2
instrument instability factor, p
0.05
high peak in final diff map, e‚Å-3 0.70(14)
low peak in final diff map, e‚Å-3 0.00(14)
2 was also obtained by direct reaction of Ru(H)(Cl)-
(PPh3)3 with (TMP)2ZrCl2, and 1 could be recovered by
the back-reaction of 2 with NaHBEt3.
Syn th esis of a Ytter biu m -Ru th en iu m Com p lex.
Since the attempt to link the RuH2 group to the
phosphorus atoms of (TMP)2ZrCl2 was successful, we
decided to proceed toward our goal of making a f-metal-
Ru hydride heterobimetallic complex.
When (TMP)2Yb7 and RuH4(PPh3)3 were mixed to-
gether in THF, a brown solution resulted. NMR data
were also similar to that of 1, and therefore the
structure of the product was very probably that of an
Yb-Ru analog of the Zr complex. Upon concentration
of the solution, crystals appeared, and elemental analy-
sis and a crystallographic study showed that the product
was indeed (THF)2Yb[µ(η5,η1)-TMP]2Ru(H)2(PPh3)2, 3
(Scheme 1).
This hypothesis was confirmed by proton NMR,
because the two equivalent hydrogen atoms bound to
ruthenium were found as a quintet at -5.8 ppm with
2J PH of ca. 20 Hz, which requires that both hydrogen
atoms be cis to the phosphine ligands. A red solid was
eventually isolated and fully characterized as Cl2Zr-
[µ(η5,η1)-TMP]2Ru(H)2(PPh3)2, 1, including by elemental
analysis. H2RuL4 complexes generally adopt a cis
geometry,9 but they can also be in dynamic equilibrium
with the trans form,10 which has been characterized
crystallographically in one instance.11
3 is not very stable in solution: NMR shows that a
pure C6D6 solution of the compound slowly decomposes.
Attempts to recrystallize the product after dissolution
in warm THF also resulted in decomposition.
Crystal data and data collection parameters are listed
in Table 1, and Table 2 lists selected bond lengths and
angles; Figure 1 represents an ORTEP plot of one
molecule of 3. This figure shows distorted octahedral
coordination at Ru, as is found in trans-H2Ru-
[P(OEt)2Ph]4.11 The Ru-P bonds are slightly shorter
(0.227 nm) in this complex than in 3 (0.230 nm). The
largest deviation from the ideal angle of 90° occurs for
P1-Ru-P6 (81.9°), i.e. between the P atoms belonging
to the (TMP)2Yb(THF)2 ligand and Ru. This emphasizes
the ring strain induced by the presence of the (TMP)2Yb-
(THF)2 ligand in 3, which is also reflected in the
displacement of the Ru atom from the TMP mean plane
(mean deviation ≈ 0.043 nm) and by the smaller
centroid(TMP)-Yb-centroid(TMP) angle in 3 (122°)
than in other bis(phospholyl)ytterbium complexes such
as (C4H2Ph2P)2Yb(THF)2 (129°).7 The Ru-H bond (0.18
nm) is poorly defined but falls toward the high end of
Reaction of 1 with CCl4 resulted in the smooth
replacement of one of the ruthenium-bound hydrogens
by chlorine, with the formation of Cl2Zr[µ(η5,η1)-TMP]2-
Ru(H)(Cl)(PPh3)2, 2. This compound retains a trans
arrangement of Cl and H around Ru, according to the
NMR data that are similar to those of 1 except that the
two sides of the phospholyl ligands are now inequiva-
lent. This trans stereochemistry is usual for neutral
Ru(II) hydride chloride complexes.12
(9) Seddon, E. A.; Seddon, K. The Chemistry of Ruthenium; Elsevi-
er: Amsterdam, 1984; p 532.
(10) E.g. see: Meakin, P.; Muetterties, E. L.; J esson, J . P. J . Am.
Chem. Soc. 1973, 95, 1797.
(11) Guggenberger, L. J . Inorg.Chem. 1993, 12, 1317.
(12) Seddon, E. A.; Seddon, K. The Chemistry of Ruthenium;
Elsevier: Amsterdam, 1984; p 543.

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4180 Organometallics, Vol. 15, No. 20, 1996
Desmurs et al.
Sch em e 2
F igu r e 1. ORTEP plot of one molecule of 3 with ellipsoids
scaled at the 50% probability level.
displays four peaks of equal intensity in the 31P spec-
trum at 1042 (d, J PP ) 210 Hz) and 860 ppm (P
belonging to the TMP ligand), 250 and 110 ppm (d, J PP
) 210 Hz) (PPh3 ligands). The 1H resonances corre-
sponding to this compound consist of eight peaks for the
R- and â-methyl groups and two broad resonances for
the hydride protons, one of which is very broad and is
shifted to very low field (153 ppm), and a very broad
resonance for the BH4 protons. The structure of a cis-
dihydride, such as (BH4)2U[µ(η5,η1)-TMP]2[cis-Ru(H)2-
(PPh3)2], 5, is consistent with the observed NMR data,
because (a) in such a structure one TMP ligand is trans
to a PPh3 ligand, and indeed a trans coupling constant
is detected on the spectrum,14 and (b) in contrast to the
trans isomer, there is no element of symmetry in the
molecule, which causes an inequivalence of the phos-
phorus atoms, of all the methyl groups, and of the two
hydrides (Scheme 2).
Ta ble 2. Selected Bon d Len gth s (n m ) a n d An gles
(d eg) for 3
Distances
Ru-P1
Ru-P6
Ru-P19
Ru-P38
Ru-H1
Ru-H2
Yb-P1
Yb-P6
0.2296(2)
0.2288(2)
0.2303(2)
0.2299(2)
0.18(1)
0.18(1)
0.2930(2)
0.2935(2)
Yb-C (av)
Yb-O57
Yb-O62
C2-P1
0.276
0.2418(8)
0.2448(8)
0.1765(9)
0.172(1)
0.1755(9)
0.1725(9)
C5-P1
C7-P6
C10-P6
Angles
P1-Ru-P6
P1-Ru-P19
P6-Ru-P38
P19-Ru-P38
H1-Ru-P1
H1-Ru-P19
H2-Ru-P6
81.82(9)
91.15(9)
89.16(9)
98.72(9)
89(3)
H2-Ru-P38
H1-Ru-H2
C2-P1-C5
C7-P6-C10
O-Yb-O
88(3)
175(4)
92.2(5)
91.7(4)
81.9(3)
122.2
81(3)
90(3)
Cnt-Yb-Cnt
Ru-H bond distances.13 The long distance between Yb
and Ru (0.425 nm) precludes any interaction between
the two metals. The other structural features (bond
lengths and distances within the TMP ligand and the
phenyl rings, geometry around the Yb atom) are normal.
Rea ction s of P h osp h olylu r a n iu m Der iva tives
w ith Ru H4(P P h 3)3. All attempts to isolate products
in the reactions of (TMP)2U(BH4)2 and (TMP)2UCl2 with
RuH4(PPh3)3 were unsuccessful. Nevertheless, the con-
clusions which can be drawn from the NMR spectra of
the solutions are reported below.
When equimolecular amounts of (TMP)2U(BH4)2 and
of RuH4(PPh3)3 were mixed in C6D6, the progressive
disappearance of the starting material, the liberation
of PPh3, and formation of a new complex were observed.
Two sets of signals were seen in the NMR spectra. In
the 31P spectrum, the minor compound (≈20%) displays
pseudodoublets at 178 ppm (PPh3 bonded to Ru) and
843 ppm (P atoms of the TMP ligand). The 1H TMP
resonances corresponding to this compound show two
peaks for the R- and â-methyl groups and two broad
resonances for the hydride and BH4 protons, respec-
tively. This product is probably (BH4)2U[µ(η5,η1)-TMP]2
[trans-Ru(H)2(PPh3)2], 4, because the spectra strongly
resemble those of compounds 1 and 3, once allowance
is made for the considerable shifts of the resonances due
to the paramagnetism of U(IV). The major compound
A gray solid, which was obtained from the above
solution after filtration and pentane washes, gave an
NMR spectrum in C6D6 which showed a mixture of the
desired dihydrides and numerous impurities. This solid
could not be purified further.
A single compound was observed when equimolecular
amounts of (TMP)2UCl2 and of RuH4(PPh3)3 were mixed
in C6D6. Its NMR characteristics were similar to those
of the major isomer of the reaction above; thus, it is
tentatively assigned the structure Cl2U[µ(η5,η1)-TMP]2-
[cis-Ru(H)2(PPh3)2]. The extremely low-field position of
one of the hydride resonances (+528 ppm) might
indicate an interaction of this hydride with uranium,
maybe in a bridging fashion.15
Con clu sion
We have achieved a significant advance in the field
of f-element-based heterobimetallics, having been able
to synthesize and structurally characterize a phospholyl-
bridged Yb-Ru heterobimetallic dihydride. However,
solubility problems during the isolation of the products
render the preparation of these compounds difficult. We
are currently trying to overcome these problems by
variations of the ligand environment at the f metal.
(14) No P-P cis coupling constants are detected, their typical value
being 15-40 Hz,9 i.e. smaller than the line broadening induced by the
paramagnetism of U (IV).
(15) Hydrides directly bonded to uranium are found below 200
ppm: Fagan, P. J .; Manriquez, J . M.; Maatta, E. A.; Seyam, A. M.;
Marks, T. J . J . Am. Chem. Soc. 1981, 103, 6650.
(13) A Ru-H bond of 1.84 Å has been found: Cotton, F. A.; Hunter,
D. L.; Frenz, B. A. Inorg. Chim. Acta 1975, 15, 155.

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Heterobimetallic Ruthenium Hydrides
Organometallics, Vol. 15, No. 20, 1996 4181
spectra showed the almost quantitative formation of both 4
(trans) (ca. 20%) and 5 (cis) (ca. 80%). NMR for 4: 1H δ -35
(m, BH4, W1/2 ) 240 Hz), -24 (d, MeR, 3J HP ) 13); -22 (RuH);
Exp er im en ta l Section
All reactions were performed in dry solvents under dry
oxygen-free nitrogen in a J acomex glovebox or on a vacuum
line. NMR spectra were recorded on a Bruker AC200 spec-
trometer operating at 200.13 MHz for 1H and at 81 MHz for
31P. Chemicals shifts are expressed in ppm downfield from
external TMS (1H) and external H3PO4 (31P). Coupling con-
stants are expressed in hertz. Elemental analyses were
performed by the “Service d’analyses du CNRS”, Gif-sur-
Yvette, France.
2
45.6 (s, Meâ); 31P δ 178 (d, PPh3, J PPtrans ) 210); 843 (d, PC4-
Me4, 2J PPtrans ) 210). NMR for 5: 1H (C6D6) δ -35.5, -24, -6.8,
3
-2.2 (d, MeR, J HP ) 11), 20, 19.9, 15, 13.6 (s, Meâ), 15, 153
(RuH), -48, 110 (m, BH4, W1/2 ) 240 Hz), 5.8-8 (m, RuPPh3);
2
31P (C6D6) δ 110 (d, PPh3, J PPtrans ) 210), 250 (s, PPh3), 860
2
(s, PC4Me4), 1042 (d, PC4Me4, J PPtrans ) 210).
Meth od b. In an attempted preparative-scale reaction, a
solution of (TMP)2U(BH4)2 (60 mg, 0.1 mmol) and RuH4(PPh3)3
(100 mg, 0.1 mmol) in toluene (25 mL) was stirred 20 h at
room temperature. After filtration and concentration of the
solution to 5 mL, the NMR spectra of an aliquot showed the
presence of 4 and 5 with very few impurities. The solution
was evaporated to dryness affording a gray solid. Examination
of this product by NMR indicated the presence of 4 and 5 but
also of ca. 20% of unidentified products, and the product could
not be further purified.
Cl2Zr (µ(η5,η1)-TMP )2R u H 2(P P h 3)2 (1). A solution of
16
17
(TMP)2ZrCl2 (40 mg, 0.1 mmol) and RuH4(PPh3)3 (80 mg,
0.1 mmol) in toluene (30 mL) was stirred for 6 h at room
temperature. The orange reaction mixture was concentrated,
and the product was precipitated slowly by adding pentane.
The solution was filtered yielding 20 mg (21%) of 1, as air-
sensitive red crytals. NMR: 1H (C6D6) δ -5.9 (ps quintet,
RuH, 2J HP ) 19.5 Hz), 1.8 (m, MeR, 3J HP ) 14.6), 2.06 (s, Meâ);
31P (C6D6) δ 61 (ps d, PPh3, 2J PPtrans ≈ 212), 109 (ps d, PC4Me4,
2J PPtrans ≈ 212). Anal. Calcd for C52H56Cl2P4Ru Zr: C, 58.5;
H, 5.25. Found: C, 58.2; H, 5.26.
Cl2U(µ(η5,η1)-TMP )2Ru H2(P P h 3)3 (6). In an NMR tube,
19
(TMP)2UCl2 (6 mg, 0.01 mmol) and RuH4(PPh3)3 (9 mg, 0.01
mmol) were dissolved in 0.4 mL of C6D6. After 30 mn, the
Cl2Zr (µ(η5,η1)-TMP )2R u HCl(P P h 3)2 (2). Met h od a .
A
NMR spectra showed the presence of 6 (ca. 80%). NMR: 1H
solution of (TMP)2ZrCl2 (90 mg, 0.2 mmol) and Ru(H)(Cl)-
(PPh3)3 (180 mg, 0.2 mmol) in toluene was stirred for 5 h at
room temperature. After filtration and concentration, red
crystals were formed and collected for microanalysis (ca. 45
mg, 20%). The remaining solution was concentrated and gave
a second crop of pure material (according to NMR). NMR: 1H
(C6D6) δ -60, -43, -24, -7.8 (m, MeR), -13,8, -7.8, 11.2, 15.4
2
(s, Meâ), 65, 528 (RuH); 31P (C6D6) δ 149 (d, PPh3, J PPtrans
)
2
160), 364 (s, PPh3), 656 (s, PC4Me4), 814 (d, PC4Me4, J PPtrans
) 160).
When the crude solution was pumped off and the remaining
solid dissolved for NMR analysis, the spectra revealed notice-
able decomposition.
2
(C6D6) δ -16.2 (ps quintet, RuH, J HP ) 19.5 Hz), 1.55 and
2.6 (m, MeR, 3J HP ) 13.5 Hz), 1.9 and 2.06 (s, Meâ); 31P (C6D6)
X-r ay Exper im en tal Data for 3. Crystals of 3, C60H72O2P4-
RuYb‚2C4D8O, fw ) 1367.46, were grown at room temperature
from a THF solution of the compound. Data were collected
on an Enraf-Nonius CAD4 diffractometer. The compound
crystallized in the noncentrosymmetric space group P212121
(No. 19). The crystal structure was solved and refined using
the Enraf-Nonius MOLEN software package. A Patterson
map yielded a solution for the two heavy atoms, and the model
was completed by successive difference Fourier maps. One of
the THF solvates is highly disordered, and we were unable to
locate the oxygen atom with certainty; all atoms in this ring
were consequently refined as carbon. The two hydrogen atoms
bonded to Ru were refined in the final least-squares stages;
those connected to the organic fragments were included as
fixed contributions. Anisotropic temperature factors were
assigned to all other atoms. A non-Poisson weighting scheme
was applied with a p factor equal to 0.05. The final agreement
factors were R ) 0.041, Rw ) 0.045, and GOF ) 1.03. The
2
2
δ 33 (ps d, J PPtrans ≈ 244, PPh3), 88 (ps d, PC4Me4, J PPtrans
≈
244). Anal. Calc for C52H55Cl3P4RuZr: C, 56.65; H, 5.03; Cl,
9.64. Found: C, 57.05; H, 5.11; Cl, 9.72.
Meth od b. In an NMR tube, 1 (6 mg, 0.006 mmol) was
dissolved in 0.4 mL of C6D6 and CCl4 (5.5 µl, 0.006 mmol) was
added. The NMR signals of 1 slowly decreased in intensity
whereas the signals of 2 appeared. After 2 h, only 2 was
present.
R ea ct ion of Cl2Zr (µ(η5,η1)-TMP )2R u H Cl(P P h 3)2 w it h
Na HBEt3. In an NMR tube, NaHBEt3 (5.5 µL of a 1.1 M THF
solution, 0.006 mmol) was added to a THF-d8 solution of 2 (6
mg, 0.006 mmol). After 2 h, only 1 was present in the solution.
(THF )2Yb(µ(η5,η1)-TMP )2Ru H2(P P h 3)2 (3). (TMP)2Yb-
7
(THF)2 (16 mg, 0.035 mmol) and RuH4(PPh3)3 (32 mg, 0.035
mmol) were dissolved in 2 mL of THF. After 2 days at room
temperature, 0.2 mL of benzene was added. The reaction
mixture was concentrated to 0.5 mL affording greenish brown
crystals of 3 (6 mg, 28%), only soluble in THF. NMR: 1H
(THF-d8) δ -6.1 (ps quintet, RuH, 2J PH ) 19.5), 1.7 (Meâ) MeR
enantiomeric structure yielded respectively R ) 0.065, Rw
0.078, and GOF ) 1.77.
)
masked by THF; 31P (THF-d8) δ 70 (ps d, PPh3, 2J PPtrans ≈ 220),
2
103 (ps d, PC4Me4, J PPtrans
C
≈
220). Anal. Calc for
Ack n ow led gm en t. The authors thank the CNRS,
Ecole Polytechnique, and the Universite´ de Dijon for
financial support of this work.
60H72O2P4RuYb: C, 58.91; H, 5.93. Found: C, 59.47; H, 6.06.
(BH4)2U(µ(η5,η1)-TMP )2Ru H2(P P h 3)3 [tr a n s (4) a n d cis
(5)]. Meth od a . In an NMR tube, (TMP)2U(BH4)2 (6 mg,
0.01 mmol) and RuH4(PPh3)3 (10 mg, 0.01 mmol) were dis-
solved in 0.4 mL of C6D6. After 2 h of stirring, the NMR
18
Su p p or tin g In for m a tion Ava ila ble: Text describing
X-ray procedures and tables of X-ray data, atom positional and
thermal parameters, and bond distances and angles (15 pages).
Ordering information is given on any current masthead page.
(16) Nief, F.; Mathey, F.; Ricard, L.; Robert, F. Organometallics
1988, 7, 921.
(17) Grushin, V. V.; Vymenits, A. B.; Vol’pin, M. E. J . Organomet.
Chem. 1990, 382, 185. Lin, D. E., J r.; Halpern, J . J . Am. Chem. Soc.
1987, 109, 2969.
(18) Gradoz, P.; Baudry, D.; Ephritikhine, M. J . Chem. Soc., Dalton.
Trans. 1992, 3047.
OM9602320
(19) Gradoz, P.; Baudry, D.; Ephritikhine, M.; Lance, M.; Nierlich,
M.; Vigner, J . J . Organomet. Chem. 1994, 466, 107.