Facile synthesis of bifunctional ligands using LiCH2PPh 2=NPh obtained from [PhNH-PPh3+][Br -]

Article abstract of DOI:10.1021/om100695b

The LiCH₂PPh₂=NPh derivative 2 was cleanly prepared from the aminophosphonium salt [PhNH-PPh₃⁺][Br ^-] (1) and MeLi. After formation of the iminophosphorane PPh ₃=NPh, nucleophilic displacement of one phenyl ring of the P atom by a methyl group occurred. This sequence was demonstrated to highly depend on the experimental conditions and on the substituent pattern at the nitrogen atom. Then, 2 was reacted with various electrophiles, among which phosphine chlorides, silyl chloride, stannyl chloride, and cyanophosphole, leading to bifunctional ligands. Depending on the electrophiles, the products were isolated either as the aminophosphonium salts or the iminophosphorane derivatives. All of these products were characterized by multinuclear NMR spectrocopy and in two cases by X-ray analysis. In particular, reaction of 2 with S₈ gave rise to the thiolate derivative (LiSCH₂PPh₂=NPh) (9), which was subsequently coordinated to Pd(II) and Ru(II) metal centers to give respectively [(PhNPPh₂CH₂S)Pd(PPh₃)Cl] and [(PhNPPh ₂CH₂S)Ru(p-cymene)Cl].

Full text of DOI:10.1021/om100695b

Organometallics 2010, 29, 3991–3996 3991
DOI: 10.1021/om100695b
Facile Synthesis of Bifunctional Ligands using LiCH2PPh2dNPh
þ
Obtained from [PhNH-PPh3 ][Br-]
Thi-Phuong-Anh Cao, Elina Payet, Audrey Auffrant,* Xavier F. Le Goff, and
Pascal Le Floch†
ꢀ ꢀ ꢀ ꢀ
Ecole Polytechnique, Laboratoire Heteroelements et Coordination, CNRS UMR7653,
route de Saclay, 91128 Palaiseau Cedex, France. †Deceased.
Received July 15, 2010
The LiCH2PPh2dNPh derivative 2 was cleanly prepared from the aminophosphonium salt
[PhNH-PPh3þ][Br-] (1) and MeLi. After formation of the iminophosphorane PPh3dNPh, nucleo-
philic displacement of one phenyl ring of the P atom by a methyl group occurred. This sequence was
demonstrated to highly depend on the experimental conditions and on the substituent pattern at the
nitrogen atom. Then, 2 was reacted with various electrophiles, among which phosphine chlorides,
silyl chloride, stannyl chloride, and cyanophosphole, leading to bifunctional ligands. Depending on
the electrophiles, the products were isolated either as the aminophosphonium salts or the iminopho-
sphorane derivatives. All of these products were characterized by multinuclear NMR spectrocopy
and in two cases by X-ray analysis. In particular, reaction of 2 with S8 gave rise to the thiolate
derivative (LiSCH2PPh2dNPh) (9), which was subsequently coordinated to Pd(II) and Ru(II) metal
centers to give respectively [(PhNPPh2CH2S)Pd(PPh3)Cl] and [(PhNPPh2CH2S)Ru(p-cymene)Cl].
During the past decade iminophosphorane-based ligands
have attracted the attention of different research groups, and
now their potential in coordination chemistry is well recogni-
zed.1 In addition, they have been successfully used for the
elaboration of different catalytic systems able to perform, for
example, ethylene polymerization2 or oligomerization,3 ring-
opening lactide polymerization,4 hydroamination,5 and trans-
fer hydrogenation reactions.6 Importantly, the electronic pro-
perties of the iminophosphorane (PdN) function differs greatly
from those of its carbon counterpart. In contrast to imines,
iminophosphoranes do not possess any π system and thus have
no π-accepting ability. On the other hand, as the nitrogen atom
bears two lone pairs, they behave as strong σ and π donors.
Generally these ligands are prepared by the Staudinger reac-
tion, requiring the condensation of an azide on a tertiary
phosphine.7 This methodology is very clean (N2 being the only
(2) (a) Ong, C. M.; McKarns, P.; Stephan, D. W. Organometallics
1999, 18, 4197–4204. (b) LePichon, L.; Stephan, D. W.; Gao, X. L.; Wang,
Q. Y. Organometallics 2002, 21, 1362–1366. (c) Al-Benna, S.; Sarsfield,
ꢁ
M. J.; Thornton-Pett, M.; Ormsby, D. L.; Maddox, P. J.; Bres, P.; Bochmann,
M. Dalton Trans. 2000, 4247–4257. (d) Cavell, R. G.; Aparna, K.; Babu,
R. P. K.; Wang, Q. Y. J. Mol. Catal. A: Chem. 2002, 189, 137–143.
(e) Masuda, J. B.; Wei, P.; Stephan, D. W. Dalton Trans. 2003, 3500–3505.
(f) Qi, C. H.; Zhang, S. B.; Sun, J. H. J. Organomet. Chem. 2005, 690, 3946–
3950. Qi, C. G.; Zhang, S. B. J. Organomet. Chem. 2006, 691, 1154–1158.
(g) Zhang, C.; Sun, W. H.; Wang, Z. X. Eur. J. Inorg. Chem. 2006, 4895–
4902. (h) Alhomaidan, O.; Bai, G.; Stephan, D. W. Organometallics 2008,
27, 6343–6352. (i) Beaufort, L.; Benvenuti, F.; Delaude, L.; Noels, A. F.
J. Mol. Catal. A 2008, 283, 77–82. (j) Yadav, K.; McCahill, J. S. J.; Bai, G.;
Stephan, D. W. Dalton Trans. 2009, 1636–1643. (k) Alhomaidan, O.; Welch,
G. C.; Bai, G. C.; Stephan, D. W. Can. J. Chem. 2009, 87, 1163–1172.
(l) Alhomaidan, O.; Beddie, C.; Bai, G. C.; Stephan, D. W. Dalton Trans.
2009, 1991–1998.
*To whom correspondence should be addressed. Fax: (þ33)(0)169334440.
E-mail: audrey.auffrant@polytechnique.edu.
(1) (a) Aparna, K.; Babu, R. P. K.; McDonald, R.; Cavell, R. G.
Angew. Chem., Int. Ed. 1999, 38, 1483–1484. (b) Babu, R. P. K.; McDonald,
R.; Decker, S. A.; Klobukowski, M.; Cavell, R. G. Organometallics 1999,
18, 4226–4229. (c) Cavell, R. G.; Babu, R. P. K.; Kasani, A.; McDonald, R.
J. Am. Chem. Soc. 1999, 121, 5805–5806. (d) Aparna, K.; Cavell, R. G.;
Ferguson, M. J. Am. Chem. Soc. 2000, 122, 726–727. (e) Babu, R. P. K.;
Aparna, K.; McDonald, R.; Cavell, R. G. Inorg. Chem. 2000, 39, 4981–4984.
(f) Aparna, K.; McDonald, R.; Babu, R. P. K.; Cavell, R. G. Angew. Chem.,
Int. Ed. 2001, 40, 4400–4401. (g) Cavell, R. G.; Babu, R. P. K.; Aparna, K.
J. Organomet. Chem. 2001, 617-618, 158–169. (h) Babu, R. P. K.;
McDonald, R.; Cavell, R. G. J. Chem. Soc., Dalton Trans. 2001, 2210–
2214. (i) Cadierno, V.; Diez, J.; Crochet, P.; Garcia-Garrido, S. E.; Garcia-
Granda, S.; Gimeno, J. Dalton Trans. 2002, 1465–1472. (j) Jones, N. D.;
Lin, G.; Gossage, R. A.; MacDonald, R.; Cavell, R. G. Organo-
metallics 2003, 22, 2832–2841. (k) Lin, G.; Jones, N. D.; McDonald, R.;
Cavell, R. G. Angew. Chem., Int. Ed. 2003, 42, 4054–4057. (l) Cadierno, V.;
Diez, J.; Garcia-Alvarez, J.; Gimeno, J. Chem. Commun. 2004, 1820–1821.
ꢀ
ꢀ
(3) (a) Sauthier, M.; Fornies-Camer, J.; Toupet, L.; Reau, R. Organo-
metallics 2000, 19, 553–562. (b) Buchard, A.; Auffrant, A.; Klemps, C.;
Vu-Do, L.; Boubekeur, L.; Le Goff, X. F.; Le Floch, P. Chem. Commun.
2007, 1502–1504. (c) Klemps, C.; Buchard, A.; Houdard, R.; Auffrant, A.;
Mezailles, N.; Le Goff, X. F.; Ricard, L.; Saussine, L.; Magna, L.; Le Floch, P.
New J. Chem. 2009, 33, 1748–1752.
€
(4) (a) Gamer, M. T.; Rastatter, M.; Roesky, P. W.; Steffens, A.;
€
Glanz, M. Chem. Eur. J. 2005, 11, 3165–3172. (b) Rastatter, M.; Zulys, A.;
Roesky, P. W. Chem. Commun. 2006, 874–876. (c) Liu, B.; Cui, D.; Ma, J.;
Chen, X.; Jing, X. Chem. Eur. J. 2007, 13, 334–945. (d) Gamer, M. T.;
Roesky, P. W.; Palard, I.; Le Hellaye, M.; Guillaume, S. M. Organometallics
2007, 26, 651–657. (e) Buchard, A.; Platel, R. H.; Auffrant, A.; Le Goff, X. F.;
Williams, C. K.; Le Floch, P. Organometallics 2010, 29, 2892–2900.
(5) (a) Panda, T. K.; Zulys, A.; Gamer, M. T.; Roesky, P. W.
Organometallics 2005, 24, 2197–2202. (b) Panda, T. K.; Zulys, A.; Gamer,
M. T.; Roesky, P. W. J. Organomet. Chem. 2005, 690, 5078–5089.
ꢀ
(m) Oulie, P.; Freund, C.; Saffon, N.; Martin-Vaca, B.; Maron, L.; Bourissou,
D. Organometallics 2007, 26, 6793–6804. (n) Hill, M. S.; Hitchcock, P. B.
Polyhedron 2007, 26, 1245–1250. (o) Cadierno, V.; Diez, J.; Garcia-Alvarez,
J.; Gimeno, J. Organometallics 2008, 27, 1809–1822. (p) Buchard, A.;
Komly, B.; Auffrant, A.; Le Goff, X. F.; Le Floch, P. Organometallics 2008,
27, 4380–4385. (q) Panda, T. K.; Roesky, P. W. Chem. Soc. Rev. 2009, 38,
2782–2804. (r) Buchard, A.; Auffrant, A.; Ricard, L.; Le Goff, X. F.; Platel, R.
H.; Williams, C. K.; Le Floch, P. Dalton Trans. 2009, (46), 10219–10222.
€
(c) Rastatter, M.; Zulys, A.; Roesky, P. W. Chem. Commun. 2006, 874–
876. (d) Rastatter, M.; Zulys, A.; Roesky, P. W. Chem. Eur. J. 2007, 13,
3606–3616.
r
2010 American Chemical Society
Published on Web 08/10/2010
pubs.acs.org/Organometallics

3992 Organometallics, Vol. 29, No. 17, 2010
Scheme 1. Metalation of PPh3(X) Derivatives
Cao et al.
Scheme 2. Formation of (LiCH2PPh2NPh)
Scheme 3. Electrophilic Trapping of 2
byproduct) but necessitates the handling of azides which are
usually difficult to prepare or hazardous, explaining why most
research groups employ commercially available azides. Alter-
natively, we and others prefer a methodology based on the
Kirsanov reaction,3,8 which allows the preparation of imino-
phosphorane by deprotonation of an aminophosphonium
species. These are obtained by addition of a primary amine
onto a phosphonium bromide, thus enabling an easy modifica-
tion of the substitution pattern at the nitrogen atom. We also
recently showed that selective ortho lithiation of PPh3dNR
(R = alkyl) derivatives can be another synthetic option, which
gives access after trapping with a phosphorus-based electro-
phile to bidentate (P, PN) ligands (Scheme 1a).9 This behavior
markedly differs from the reactivity of thiophosphines and
phosphine oxides toward alkyllithium or Grignard reagents
reported by Seyferth et al. in the early 1960s.10 Indeed, as
described in Scheme 1b, they have shown that such reactions
led to the formation of the diphenylphosphinylalkyl organo-
metallic reagent (MCH2)P(X)Ph2 (M = MgBr, Li; X = O, S),
which could be then reacted with chlorophosphines.11 Direct
coordination of (MCH2)P(X)Ph2 (X = O, S) anions to dif-
ferent metal centers, such as Au(I) and Hg(II), was also later
described.12 To the best of our knowledge, no such transforma-
tion has been reported for iminophosphoranes. Nevertheless,
Stuckwisch13 mentioned that a competitive reaction takes place
when performing the ortho lithiation of PPh3dNPh (Scheme 1c);
metalated diphenylalkylphosphine N-phenylimide was indeed
observed as a byproduct. Here, we wish to present a reliable and
facile preparation of LiCH2PPh2dNPh from [PhNH-PPh3þ]-
[Br-] and its trapping with different electrophiles. The coordi-
nation of LiSCH2PPh2dNPh (obtained by reaction with S8) to
Pd(II) and Ru(II) centers is also described.
Results and Discussion
The lithiation (Scheme 2) was carried out by adding
2 equiv of MeLi (1.6 M in diethyl ether) to a suspension of the
triphenylphosphonium bromide adduct 1 in THF (the first
equivalent generating the iminophosphorane). This induced a
marked color change; the white suspension disappeared to give
an orange-red solution. The 31P{1H} NMR spectrum of the
crude mixture showed a singlet at δ(THF) 24.2 ppm, which is in
the range of the chemical shift observed for ortho-lithiated
derivatives obtained from PPh3dNR (R = CH(CH3)CH-
1
(CH3)2, CH2-t-Bu, i-Pr)9,14 in diethyl ether. Nevertheless, H
NMR spectroscopy of the crude mixture in d8-THF shows a
broad singlet at δ (THF) -0.11 ppm integrating for two
protons and the presence of only two phenyl rings on the
phosphorus atom. These observations point toward the dis-
placement of one phenyl ring of the P atom by a methyl group
followed by R-metalation (performed by in situ generated
phenyllithium) leading to 2. NMR characterization was achieved
in THF, and data were similar to those described by
Davidson and Lopez-Ortiz et al., who synthesized this anion
from CH3PPh2dNPh and characterized it in solution and in
the solid state.15
Importantly, the formation of 2 from PPh3dNPh highly
depends on the reaction conditions. When n-BuLi was used
instead of MeLi in THF, two different products were ob-
tained, one coming from ortho lithiation and the other
from a phenyl displacement followed by R-metalation (see
Scheme 1c). This can be ascribed to the better nucleophilic
properties of MeLi. Moreover, the lithiation carried out with
MeLi (1.6 M in diethyl ether) in toluene leads also to a
mixture of two anions: 2 and the ortho-lithiated derivative
characterized by a singlet at δ (toluene) 16.9 ppm in 31P{1H}
(6) (a) Cadierno, V.; Crochet, P.; Garcia-Alvarez, J.; Garcia-Garrido,
S. E.; Gimeno, J. J. Organomet. Chem. 2002, 663, 32–39. (b) Cadierno, V.;
Diez, J.; Garcia-Alvarez, J.; Gimeno, J. Organometallics 2005, 24, 2801–
ꢀ
2810. (c) Boubekeur, L.; Ulmer, S.; Ricard, L.; Mezailles, N.; Le Floch, P.
Organometallics 2006, 25, 315–317. (d) Buchard, A.; Heuclin, H.; Auffrant,
A.; Le Goff, X. F.; Le Floch, P. Dalton Trans. 2009, 1659–1667.
(7) For the synthesis of iminophosphosphorane by the Staudinger
reaction, see for example: (a) Staudinger, H.; Meyer, J. Helv. Chim. Acta
1919, 2, 619–635. (b) Gololobov, Y. G.; Zhmurova, I. N.; Kasukhin, L. F.
Tetrahedron 1981, 37, 437–472. (c) Gololobov, Y. G.; Kasukhin, L. F.
Tetrahedron 1992, 48, 1353–1406. (d) Ylides and Imines of Phosphorus;
Johnson, A. W., Ed.; Wiley: New York, 1993.
(8) (a)Kirsanov,A.V.Izv. Akad. Nauk SSSR 1950, 426. (b) Boubekeur, L.;
ꢀ
Ricard, L.; Mezailles, N.; Le Floch, P. Organometallics 2005, 24, 1065–1074.
(c) Demange, M.; Boubekeur, L.; Auffrant, A.; Mezailles, N.; Ricard, L.; Le Goff,
ꢀ
X.; Le Floch, P. New J. Chem. 2006, 30, 1745–1754. (d) Cantat, T.; Mezailles, N.;
Auffrant, A.; Le Floch, P. Dalton Trans. 2008, 1957.
ꢀ
(9) Boubekeur, L.; Ricard, L.; Mezailles, N.; Demange, M.; Auffrant,
A.; Le Floch, P. Organometallics 2006, 25, 3091–3094.
(10) (a) Seyferth, D.; Heeren, J. K.; Welch, D. E. J. Am. Chem. Soc.
1963, 85, 642–643. (b) Seyferth, D.; Welch, D. E.; Heeren, J. K. J. Am.
Chem. Soc. 1964, 86, 1100–1105. (c) Seyferth, D.; Welch, D. E.
J. Organomet. Chem. 1964, 2, 1–7.
(11) Grim, S. O.; Stek, L. C.; Mitchell, J. D. Z. Naturforsch., B: Chem.
Sci. 1980, 35, 832–837.
(12) Fackler, J. P.; Galarza, E.; Garzon, G.; Mazany, A. M.; Murray,
H. H.; Omary, M. A. R.; Raptis, R.; Staples, R. J.; Van Zyl, W. E.;
Wang, S. N. Inorg. Synth. 2002, 33, 171–180 and references therein.
(13) Stuckwisch, C. G. J. Org. Chem. 1976, 41, 1173–1176.
(14) Buchard, A. Ph.D. Thesis, Ecole Polytechnique, Palaiseau,
France, 2009.
(15) Gomez, G. R.; Fernandez, I.; Ortiz, F. L.; Price, R. D.; Davidson,
M. G.;Mahon, M. F.;Howard, J. A. K. Organometallics 2007, 26, 514–518.

Article
Organometallics, Vol. 29, No. 17, 2010 3993
NMR. The latter can also be obtained as the sole product by
using n-BuLi in toluene.
Scheme 4. Trapping with S8
The course of the reaction is also very sensitive to the
nature of the nitrogen substituent. Indeed, with an alkyl
substituent at the nitrogen, whatever the nature of the base or
solvent used, only ortho lithiation was observed as we
described earlier (see Scheme 1a).9
After having determined the experimental conditions en-
abling a clean preparation of 2, this anion was trapped with
various electrophiles (Scheme 3). First, 2 was reacted with
tetrafluoroboric acid; the protonation induces a rapid fading
of the color of the solution which is accompanied by a net
shielding of the phosphorus signal (δ (THF) þ36.6 ppm).
The aminophosphonium salt 3 was isolated in 70% yield as a
white solid (Scheme 3). The presence of the methyl group
phosphole ring is a phosphine with greater accepting ability.
The formation of 8 was ascertained by NMR spectroscopy.16
The 31P{1H} NMR spectrum is very diagnostic, showing a
doublet at δ (C6D6) -23.7 ppm for the phosphole P atom and
0.8 ppm for the P(V) atom (2JP,P = 48.5 Hz).
If bidentate iminophosphorane-phosphine ligands are
well-known, the combination of iminophosphorane with
other donors based on different heteroatoms remains scarce.17
With this in mind, we achieved the synthesis of thiolate 9 and
thiol 10 (Scheme 4). Indeed, reaction with S8 in THF at room
temperature induced the precipitation of 9, which was isolated
by filtration in 55% yield. This anion could be solubilized
in pyridine and characterized by multinuclear NMR in this
is indicated by a doublet at δ (CDCl3) 2.44 ppm (2JP,H
=
1
13.5 Hz) in the H NMR spectrum. 3 was characterized by
multinuclear NMR spectroscopy, by elemental analysis, as
all other trapping products, and by X-ray crystallography
(see the Supporting Information).
1
Then, anion 2 was trapped with various chlorophosphines
to give mixed phosphine-iminophosphorane ligands. Reac-
tion with 1 equiv of PPh2Cl induced the formation of the
(P, PN) adduct, as indicated by the presence of two doublets
at δ (THF) 0.80 and -26.6 ppm (2JP,P = 51.5 Hz) in the
31P{1H} NMR of the crude mixture. After protonation the
aminophosphonium salt can be isolated. The NMR data
were identical with those we have already described.10 More
interestingly, using chlorophosphines other than diphenyl-
phosphine chloride gave rise to mixed phosphine-imino-
phosphorane ligands, in which the two phosphorus atoms
do not bear the same substituents. Such derivatives cannot
be prepared by the monobromation-Kirsanov sequence
we developed earlier. By reaction with PCy2PCl, a mixed
phosphine-iminophosphorane adduct was formed, as evi-
denced by two doublets at δ (THF) -11.2 and 27.1 ppm
(2JP,P = 101.5 Hz) in the 31P{1H} NMR spectrum of the
crude mixture. Even if the ligand could be directly isolated,
we preferred to isolate it as an aminophosphonium salt for
storage convenience. Therefore, 5 was obtained after acidic
workup. It exhibits in 31P{1H} NMR spectroscopy two
doublets at δ (CD2Cl2) -22.2 and 34.80 ppm (2JP,P = 87.5 Hz)
corresponding respectively to the P(III) and P(V) atoms. The
bridging methylene appears as a doublet at δ (CD2Cl2) 3.22
ppm (2JP,H = 16.5 Hz) and a doublet of doublets at δ (CD2Cl2)
18.7 ppm (2JP,C = 39.0 and 68.0 Hz) in the 1H and 13C NMR
spectra, respectively. In the same manner, reaction with tri-
methylsilyl chloride also proceeded cleanly, leading after acidic
workup to the aminophosphonium salt 6, which was charac-
solvent. The H NMR data reveal the coordination of one
THF molecule per ligand, which allows us to propose the
structure presented in Scheme 4. Furthermore, 9 can be proto-
nated by addition of 2.5 equiv of HBF4 in ether, yielding the
aminophosphonium salt 10, which was also fully characterized.
In the first coordination experiments, anion 9 was coordi-
nated to Pd(II) and Ru(II) centers. Due to the low solubility
of 9 in THF, reactions were carried out by addition of THF
onto a mixture of isolated 9 and the metal precursor. With
trans-PdCl2(PPh3)2, after 4 h at room temperature, the
yellow slurry had turned to an orange solution. The 31P{1H}
NMR spectrum of the crude mixture showed the presence of
1 equiv of free triphenylphosphine (δ (THF) -5.1 ppm) and
an AB signal pattern evidencing the coordination of the
ligand to the palladium center. The complex [(PhNPPh2CH2S)-
Pd(PPh3)Cl] (11) exhibited a doublet (3JPP = 6.5 Hz) at δ
(THF) 34.2 and 45.0 ppm corresponding respectively to the
coordinated triphenylphosphine and iminophosphorane func-
tions. This complex was isolated in 87% yield by evaporation of
THF and removal of lithium salt after precipitation in dichloro-
methane, followed by washing of the solid obtained after
evaporation of the solvent with n-hexanes. It was characterized
by multinuclear NMR, elemental analysis, and X-ray diffrac-
tion analysis. Single crystals were obtained by slow diffusion of
hexanes into a concentrated CH2Cl2 solution of 11. An Ortep
plot of 11 is depicted in Figure 1 together with the most relevant
metric and angular parameters. It is a neutral square-planar
complex where the iminophosphorane and the phosphine are
located trans to each other (this comes from the trans arrange-
ment of the phosphine ligands in the palladium precursor). The
deviation from planarity was found to be 16.70(9)°. The P-N
bond distance is normal at 1.597(3) A, and the P3-C1 bond is
shortened compared to the P-C bond in [(Ph2PCH2PPh2NPh)-
PdCl2] featuring a bidentate phosphine-iminophosphorane
ligand: 1.801(3) vs 1.842(2) A.8b In contrast, both the N-Pd
(2.100(2) A) and the Pd-Cl bond lengths (2.3869(7) A) are
elongated in comparison to the same reference (N-Pd =
2.076(2) A and Pd-Cl = 2.3668(5) A, 2.3035(6) A).
1
terized by multinuclear (31P, H, 13C) NMR spectroscopy as
well as X-ray analysis (see the Supporting Information).
The intermediate iminophosphosphorane can be alter-
natively, equally well, isolated (Scheme 3).
Thus, reaction of anion 2 with trimethyltin chloride gave, after
removal of lithium salt, 7as a white solid in 75% yield. In 31P{1H}
NMR spectroscopy 7 exhibited a singlet at δ (C6D6) 7.40 ppm
and satellites due to tin isotope (2JP,Sn = 60.0 Hz). In 1H NMR
the methylene protons appears as a doublet with tin satellites cen-
tered at δ (C6D6) 2.71 ppm (2JSn,H = 52.0 Hz, 2JP,H = 11.0 Hz).
Moreover, trapping 2 with 1-cyano-2,5-diphenylphosphole
gave access to 8 in 85% yield. This mixed bidentate ligand
is very promising, since it features coordination sites with
very different electronic properties. As mentioned earlier, the
iminophosphorane is a strong σ and π donor whereas the
(16) For 7 and 8, which proved to be air and moisture sensitive,
satisfactory elemental analyses could not be obtained.
(17) For an example of an iminophosphorane-thioether ligand see:
ꢀ
Alajarın, M.; Lopez-Leonardo, C.; Llamas-Lorente, P.; Bautista, D.;
´
Jones, P. G. Dalton Trans. 2003, 426–434.

3994 Organometallics, Vol. 29, No. 17, 2010
Cao et al.
phorane-phosphine, -silyl, -stannyl, or -thiolate deriva-
tives, which were often isolated as aminophosphonium
derivatives after acidic workup. All these products were
characterized by multinuclear NMR techniques and elemen-
tal analyses and in some cases by X-ray analysis. Then, the
coordination chemistry of the iminophosphorane-thiolate
anion 9 to Pd(II) and Ru(II) centers was studied, yielding
[(SCH2PPh2NPh)Pd(PPh3)Cl] (11) and [(SCH2PPh2NPh)(p-
cymene)RuCl] (12), respectively. These complexes were fully
characterized, including X-ray analysis for 11. Following
these first results, the coordination chemistry of the new
bidentate ligands, which are easily available via the described
methodology, is currently under investigation in our laboratory.
Figure 1. ORTEP view of complex 11. Hydrogen atoms have
been omitted for clarity. Thermal ellipsoids are drawn at the
50% probability level. Selected distances (A) and angles (deg):
Pd1-N1 = 2.100(2), N1-P3 = 1.597(3), P3-C1 = 1.801(3),
C1-S1 = 1.824(3), S1-Pd1 = 2.289(1), Pd1-P4 = 2.2528(8),
Pd1-Cl1 = 2.3869(7); N1-Pd1-S1 = 88.52(7), P4-Pd1-S =
189.87(3), N1-Pd1-Cl1 = 92.45(7), P4-Pd1-Cl1 = 89.73(3),
P3-C1-S1 =109.5(2), N1-P3-C1 = 104.9(2), C1-S1-Pd1 =
103.6(1), S1-Pd1-N1-Cl1 = 16.70(9).
Experimental Section
General Considerations. All experiments were performed
under an atmosphere of dry nitrogen or argon using standard
Schlenk and glovebox techniques. Solvents were freshly distilled
under dry nitrogen from Na/benzophenone (THF, diethyl ether,
petroleum ether) and from P2O5 (dichloromethane). The amino-
phosphonium compound 118 and [Ru(p-cymene)Cl2]2 were
19
Scheme 5. Coordination of the Thiolate-Iminophosphorane
Ligand to Pd(II) and Ru(II)
prepared according to literature procedures. All other reagents
and chemicals were obtained commercially and used without
further purification. Nuclear magnetic resonance spectra were
recorded on a Bruker Avance 300 spectrometer operating at
300 MHz for 1H, 75.5 MHz for 13C, and 121.5 MHz for 31P. Sol-
vent peaks were used as internal references for 1H and 13C
chemical shifts (ppm). 31P peaks were referenced to external
85% H3PO4. Coupling constants are expressed in hertz. The
following abbreviations are used: b, broad; s, singlet; d, doublet;
dd, doublet of doublets; t, triplet; m, multiplet; v, virtual. Elemental
analyses were performed by the “Service d’analyse du CNRS”, at
Gif sur Yvette, France, or at the elemental analysis service of the
London Metropolitan University (United Kingdom).
Preparation of 2. MeLi (1.6 M, 0.46 mmol, 287 μL) was added
dropwise to a suspension of 1 (0.23 mmol, 0.1 g) in THF
(2.5 mL) at -78 °C. The cold bath was removed, and stirring
was pursued at room temperature for 30 min to give an orange-
red solution. The formation of 2 was indicated by in situ NMR
data similar to those previously described.15 31P{1H} NMR (d8-
THF): δ 24.18 (s). 1H NMR (d8-THF): δ -0.11 (2H, br. s, CH2),
The iminophosphorane-thiolate anion was also easily
coordinated to a Ru(II) center. Addition of THF to a mixture
of 9 and dichloro(p-cymene)ruthenium(II) dimer in the solid
state led rapidly to a red solution. The disappearance of the
precipitated anion was a goodsign of coordination, whichwas
confirmed by 31P{1H} NMR of the crude mixture showing the
formation of a unique product exhibiting a singlet at δ (THF)
36.9 ppm. After 3 h at room temperature, the solvent was
evaporated, the lithium salt was filtered off after precipitation
in dichloromethane, and 12 was isolated as a red solid in 76%
yield. This complex was characterized by multinuclear NMR
and elemental analysis. In the 1H NMR spectrum the methyl-
ene protons appear as two doublets at 2.67 and 4.12 ppm; this
accounts for the chirality of the Ru center, which bears four
different substituents. In the same manner the protons of the
coordinated p-cymene ring are differentiated, giving three
doublets at 4.64, 4.76, and 4.90 ppm integrating respectively
for 1, 2, and 1 proton. In the aromatic area, the differentiation
of the protons of the phenyl rings on the phosphorus atom can
also be seen. In the 13C spectrum most of the carbons of both
the p-cymene and phenyl rings (on P) are differentiated. All
these data lead us to propose the structure depicted in Scheme 5
for complex 12.
6.27 (1H, t, 2JH,H = 7.5 Hz, p-CH(NPh)), 6.44 (2H, d, 3JH,H
=
3
7.5 Hz, o-CH(NPh)), 6.70 (2H, JHH = 7.5 Hz, m-CH(NPh)),
7.27 (6H, m, m-and p- CH(PPh2), 7.68 (4H, m, o- CH(PPh2)).
Electrophilic Trapping. Synthesis of 3. HBF4(Et2O)2 (0.46
mmol, 63 μL) was added to a solution of 2 (0.23 mmol, 0.1 g) in
THF, inducing a rapid fading of the initial orange solution.
After
1
/ h of stirring at room temperature, the solvent was
2
removed in vacuo, dichloromethane (5 mL) was added, and the
lithium salts were filtered off. Then evaporation of the solvent
yielded 3 as a white solid (61 mg, 70%). 31P{1H} NMR (CDCl3):
δ 36.6 (s). 1H NMR (CDCl3): δ 2.44 (3H, d, 2JP,H = 13.5 Hz,
3
CH3), 6.78 (2H, d, JH,H= 7.5 Hz, o-CH(NPh)), 6.86 (1H, d,
3
3JH,H = 7.5 Hz, p-CH(NPh)) 6.99 (2H, JH,H = 7.5 Hz,
m-CH(NPh)), 7.53 (4H, m, o- CH(PPh2), 7.68 (6H, m, m and
1
p- CH(PPh2)). 13C NMR (CDCl3): δ 12.7 (d, JP,C = 69.5 Hz,
CH3), 120.2 (d, JP,C = 6.5 Hz, o-CH(NPh)), 120.4 (d, JP,C =
3
1
100 Hz, CIV-(PPh2)), 124.0 (s, p-CH(NPh)), 129.5 (s, m-CH(NPh)),
130.1 (d, 2JP,C = 13.5 Hz, o-CH(PPh2)), 132.4 (d, 3JP,C = 11.5 Hz,
m-CH(PPh2)), 135.2 (d, JP,C = 3.0 Hz, p-CH(PPh2)), 137.5
4
(d, 2JP,C = 2.5 Hz, CIV-(NPh)). Anal. Calcd for C19H19BF4NP:
C, 60.19; H, 5.05; N, 3.69. Found: C, 59.74; H, 4.82; N, 4.03.
In conclusion, the clean preparation of LiCH2PPh2dNPh
anion from [PhNH-PPh3þ][Br-] was realized, which has
opened the way to an easy synthesis of new bidentate ligands.
First, electrophilic trapping gave access to mixed iminophos-
(18) Albright, T. A.; Freeman, W. A.; Schweizer, E. E. J. Org. Chem.
1976, 41, 2716–2720.
(19) Bennet, M. A.; Huang, T. N.; Matheson, T. W.; Smith, A. K.
Inorg. Synth. 1982, 21, 74–78.

Article
Synthesis of 5. Dicyclohexylphosphine chloride (0.58 mmol,
Organometallics, Vol. 29, No. 17, 2010 3995
o-CH(PPh2)), 7.52 (4H, dd, 3JH,H=7.0 Hz and 4JP,H=1.0 Hz,
o-CH(Phph1osphole)), 7.61 (2H, m, o-CH(NPh)). 13C NMR (C6D6): δ
128 μL) was added to a solution of 2 (0.58 mmol, 0.25 g) in THF
to give a clear yellow solution, which was stirred for 1/2 h at room
temperature. Then, the volatiles were evaporated in vacuo and
dichloromethane (12 mL) was added. The reaction mixture was
washed with 2 M aqueous HCl solution (2ꢀ7 mL); the organic
phase was then dried on Na2SO4 and filtered under N2. After
evaporation of the solvent and precipitation with hexanes,
5 was obtained as a white solid (228 mg, 75%). 31P{1H} NMR
1
24.8 (dd, JP,C = 44.0 Hz, JP,C = 37.5 Hz, PCH2), 117.6 (s,
CH(Ph)), 123.6 (s, CIV-(Phphosphole)), 123.9 (s, CH(Ph)), 126.7
(d, 3JP,C=5.0 Hz, o-CH(Phphosphole)), 127.8 (d, 3JP,C=8.0 Hz,
o-CH(NPh)), 128.8 (d, JP,C =9.0 Hz, CH(Ph)), 131.3 (s, CH-
(Ph)), 131.5 (s, CH(Ph)), 131.8 (d, JP,C=3.0 Hz, CH(Ph)), 132.3
2
2
(d, JP,C = 9.0 Hz, o-CH(PPh2)), 132.5 (d, JP,C = 9.0 Hz,
Cβ phosphole), 135.6 (dd, JP,C = 97.0 Hz and JP,C = 8.0 Hz,
1
3
(CD2Cl2): δ -22.2 (d, 2JP,P = 87.5 Hz, PCy2), 34.8 (d, 2JP,P
87.5 Hz, PvPh2). 1H NMR (CD2Cl2): δ 0.80-1.52 (22H, m, Cy),
=
CIV-(PPh2), 136.5 (d, 2JP,C=17.0 Hz, CIV-(NPh)), 152.4 (d, 1JP,C
68.0 Hz, CR phosphole).
=
2
3
3.22 (2H, d, JP,H = 16.5 Hz, PCH2), 6.82 (1H, t, JH,H
=
Synthesis of 9. S8 (0.03 mmol, 7.5 mg) was added in the
glovebox to a solution of anion 2 (0.23 mmol, 0.100 g) in THF
(3 mL) to give a yellow-orange solution from which a precipitate
formed. After the mixture was stirred for 3 h at room tempera-
ture, the precipitate was isolated by filtration, washed with
THF, and dried in vacuo to yield 9 as a white solid (447 mg,
7.5 Hz, p-CH(NPh)), 6.90 (2H, d, 3JH,H = 7.5 Hz, o-CH(NPh)),
6.99 (2H, t, 3JH,H = 7.5 Hz, m-CH(NPh)), 7.57 (6H, m, m- and
p-CH(PPh2)), 8.01 (4H, dd, 3JH,H = 8.0 Hz and 3JP,H = 12.5 Hz,
o-CH(PPh2)). 13C NMR (CD2Cl2): δ 18.7 (dd, JP,C = 39.0 Hz
1
and 1JP,C = 68.0 Hz, PCH2), 25.2 (s, CH2(Cy)), 26.2 (d, JP,C
12.0 Hz, CH2(Cy)), 28.2 (t, JP,C = 13.0 Hz, CH2(Cy)), 33.1 (dd,
=
1
55%). 31P{1H} NMR (Pyr-d5): δ 21.3 (s). H NMR (Pyr-d5):
3JP,C = 8.0 Hz and 1JP,C = 15.0 Hz, CH(Cy)), 119.3 (d, 3JP,C
=
δ 1.80 (4H, m, CH2(THF)), 3.84 (4H, m, OCH2(THF)), 4.18
(2H, d, JP,H = 7.0 Hz, PCH2), 6.89 (1H, t, JH,H = 7.0 Hz,
7.5 Hz, o-CH(NPh)), 119.7 (d, 1JP,C = 97.5 Hz, CIV-(PPh2)), 122.0
(s, p-CH(NPh)), 128.2 (s, m-CH(NPh)), 128.7 (d, 2JP,C = 13.0 Hz,
m-CH(PPh2)), 133.04 (dd, 3JP,C = 10.1 Hz and 3JP,C = 4.5 Hz,
2
3
3
p-CH(NPh)), 7.28 (2H, t, JH,H = 7.0 Hz, m-CH(NPh)), 7.40
(2H, t, 3JH,H=7.0 Hz, o-CH(NPh)), 7.54 (4H, td, 3JH,H=7.5 Hz
and JP,H =1.0 Hz, m-CH(PPh )), 7.64 (2H, t, JH,H =7.5 Hz,
4
4
3
o-CH(PPh2)), 133.8 (d, JP,C = 3.0 Hz, p-CH(PPh2)), 138.5 (d,
2
2JP,C = 3.0 Hz, CIV-(NPh)). Anal. Calcd for C31H40ClNP2: C,
71.05; H, 7.69; N, 2.67. Found: C, 71.28; H, 7.47; N, 2.36.
Synthesis of 6. 6 (0.139 g, 60%) was obtained by a procedure
similar to that used for 5, employing trimethylsilyl chloride
(0.58 mmol, 75 μL) as electrophile and HBr as acid. 31P{1H} NMR
(CDCl3): δ 37.2 (s). 1H NMR (CDCl3): δ 0.0 (9H, s, CH3), 2.71
p-CH(PPh2)), 8.22 (4H, dd, 3JHH=7.5 Hz and 3JP,H=9.5 Hz,
o-CH(PPh2)). 13C NMR (Pyr-d5): δ 28.2 (s, CH2(THF)), 31.5
(d, JP,C = 88.0 Hz, PCH2), 70.2 (s, OCH2(THF)), 119.8 (s,
1
p-CH(NPh)), 125.4 (d, 3JP,C=17.6 Hz, o-CH(NPh)), 131.1 (d,
3
3JP,C = 10.5 Hz, m-CH(PPh2)), 131.6 (d, JP,C = 1.0 Hz,
1
m-CH(NPh)), 133.6 (d, JP,C = 78.5 Hz, CIV-(PPh2)), 134.1
(d, JP,C = 2.5 Hz, p-CH(PPh2)), 135.4 (d, JP,C = 8.0 Hz, o-
2
3
4
2
(2H, d, JP,H = 18,0 Hz, PCH2), 6.86 (1H, t, JH,H = 7.0 Hz,
p-CH(NPh)), 7.03 (4H, m, 3JH,H=7.5 Hz, o- and m-CH(NPh)),
7.57 (4H, td, 3JH,H=7.5 Hz and 3JP,H=3.5 Hz, m-CH(PPh2)), 7.78
(2H, dd, 3JH,H=7.5 Hz and 4JP,H=6.0 Hz, p-CH(PPh2)), 7.91 (4H,
dd, 3JH,H=7.5 Hz and 2JP,H=13.0 Hz, o-CH(PPh2)). 13C NMR
(CDCl3): δ 0.0 (s, CH3), 14.5 (d, 1JP,C=58.5 Hz, PCH2), 120.0 (d,
CH(PPh2)), 155.8 (d, 2JP,C=5.5 Hz, CIV-(NPh)).
Synthesis of 10. To obtain 10, HBF4(Et2O)2 (0.46 mmol,
63 μL) was added to a solution of 9 (0.23 mmol, 0.100 g) in
THF to lead to a colorless solution. The solvent was removed,
CH2Cl2 (5 mL) was added, and the salts were removed by
filtration under N2. Then, evaporation of the solvent afforded
the aminophosphonium compound 10 (67 mg, 71%). 31P{1H}
3JP,C=6.0 Hz, o-CH(NPh)), 122.5 (d, 1JP,C=96.5 Hz, CIV-(PPh2)),
2
122.9 (s, p-CH(NPh)), 129.0 (s, m-CH(NPh)), 129.7 (d, JP,C
=
13.0 Hz, o-CH(PPh2)), 132.6 (d, JP,C= 11.0 Hz, m-CH(PPh2)),
3
1
NMR (CDCl3): δ 35.9 (s). H NMR (CDCl3): δ 2.00 (1H, td,
=
4
2
3
2
3JH,H =9.0 Hz and JP,H =2.0 Hz, SH), 3.85 (2H, d, JP,H
134.4 (d, JP,C =3.0 Hz, p-CH(PPh2)), 139.0 (d, JP,C =2.5 Hz,
CIV-(NPh)). Anal. Calcd for C22H27BrNPSi: C, 59.46; H, 6.12; N,
3.50. Found: C, 58.81; H, 5.93; N, 3.40.
7.5 Hz, PCH2), 6.80 (2H, d, 3JH,H=7.5 Hz, o-CH(NPh)), 6.87
(1H, t, 3JH,H=7.5 Hz, p-CH(NPh)), 7.00 (2H, t, 3JH,H=7.5 Hz,
m-CH(NPh)), 7.34(1H, d, 2JP,H=9.5 Hz, NH) 7.56 (4H, td, 3JH,H
=
Synthesis of 7. A solution of trimethyltin chloride (0.58 mmol,
0.116 g) in THF (2 mL) was added to a THF solution (12 mL) of
2 (0.58 mmol, 0.250 g) to give, after 30 min of stirring, a pale
yellow solution. Then, solvent was removed and toluene added
to filter off the lithium salts. After evaporation of toluene,
iminophosphorane 7 was obtained as a white solid (341 mg,
75%). 31P{1H} NMR (C6D6): δ -6.88 (s þ sat, 2JP,Sn=60.0 Hz).
7.5 Hz and 4JP,H=3.5 Hz, m-CH(PPh2)), 7.69 (2H, t, 3JH3,H=7.5
3
Hz, p-CH(PPh2)), 7.86 (4H, dd, JH,H = 7.5 Hz and JP,H
=
=
9.5 Hz, o-CH(PPh2)). 13C NMR (CDCl3): δ 18.7 (d, JP,C
1
69.0 Hz, PCH2), 116.8 (d, 1JP,C=99.5 Hz, CIV-(PPh2)), 119.0 (d,
3JP,C=17.6 Hz, o-CH(NPh)), 123.1 (s, p-CH(NPh)), 128.6 (s,
m-CH(NPh)), 129.2 (d, JP,C = 13.5 Hz, m-CH(PPh2)), 132.5
3
2
1H NMR (C6D6): δ 0.10 (9H, s þ sat, JSn,H = 50.0 Hz,
2
4
(d, JP,C = 10.5 Hz, o-CH(PPh2)), 134.7 (d, JP,C = 3.0 Hz,
p-CH(PPh2)), 136.3 (d, 2JP,C=3.0 Hz, CIV-(NPh)). Anal. Calcd
for C19H19BF4NPS: C, 55.50; H, 4.66; N, 3.41. Found: C, 55.21;
H, 4.94; N, 3.09.
2
2
Sn(CH3)3), 1.55 (2H, d þ sat, JP,H = 11.0 Hz, JSn,H = 52.0
Hz, CH2P), 6.76 (3H, m, p- and m-CH(NPh)), 6.99 (6H, m,
p- and m-CH(PPh2)), 7.18 (2H, m, o-CH(NPh)), 7.66 (4H, m,
o-CH(PPh2)). 13C NMR (C6D6) δ -7.4 (d þ sat, 3JP,C=1.5 Hz,
Synthesis of 11. THF (1 mL) was added to a mixture of
trans-[PdCl2(PPh3)2] (35.5 mg, 0.05 mmol) and 9 (20.0 mg,
0.05 mmol). After 4 h of stirring the yellow slurry turned into
an orange solution, from which THF was removed. Addition of
dichloromethane (4 mL) induced the precipitation of the lithium
salts, which were filtered off. After evaporation of dichloro-
methane, the obtained solid residue was washed with hexanes
(3 mL) to give 11 as an orange solid (31.7 mg, 87%). 31P{1H} NMR
(CD2Cl2): δ 33.5 (d, 3JP,P=6.5 Hz, PIII), 46.2 (d, 3JP,P=6.5 Hz, PV)
(s). 1H NMR (CDCl3): δ 3.05 (2H, d, 3JP,H=6.0 Hz, PCH2), 6.67
(1H, tt, 3JH,H=6.0 Hz, 4JH,H=2.5 Hz, p-CH(NPh)), 6.85 (2H, m,
m-CH(NPh)), 7.23-7.30 (8H, m, o-CH(NPh), m-(PPh3)), 7.36
(3H, dt, 3JH,H=7.5 Hz, 3JP,H=2.0 Hz, p-CH(PPh3)), 7.43 (4H, td,
3JH,H=7.5 Hz, 4JP,H=3.0 Hz, m-CH(PPh2)), 7.51-7.57 (8H, m,
p-CH(PPh2), o-CH(PPh3)), 7.73 (4H, m, p-CH(PPh2)). 13C NMR
(CDCl3): δ 29.5 (dd, 1JP,C=85.0 Hz, 3JP,C=4.5 Hz, PCH2), 123.3
(s, p-CH(NPh)), 128.5 (d, 1JP,C=86.0 Hz, CIV-(PPh2)), 129.0 (s,
m-CH(NPh)), 129.4 (d, 3JP,C=11.0 Hz, m-CH(PPh3)), 130.1 (dd,
1
1JSn,C =362.0 Hz, Sn(CH3)3), 12.0 (d þ sat, JP,C =75.0 Hz,
1JSn,C=296.0 Hz, CH2P), 117.1 (s, p-CH(NPh)), 123.2 (d, 3JP,C
=
20.0 Hz, m-CH(NPh)), 128.6 (d, 3JP,C=11.0 Hz, o-CH(NPh)),
129.7 (d, JP,C = 12.0 Hz, m-CH(PPh2)), 131.6 (d, JP,C =
3
2
3
9.0 Hz, o-CH(PPh2)), 133.8 (d, JP,C = 3.0 Hz, p-CH(PPh2)),
134.9 (d, JP,C = 87.0 Hz, CIV(PPh2)), 152.8 (2JP,C = 3.0 Hz,
1
C
IV-(NPh)).
Synthesis of 8. 8 (103 mg, 85%) was obtained by a procedure
similar to that employed for 7, using a solution of 1-cyano-2,5-
diphenylphosphole (0.23 mmol, 0.06 g) in THF (2 mL) and a
solution of 2 (0.23 mmol, 0.100 g) in THF (3 mL). 31P{1H} NMR
(C6D6): δ -23.7 (d, 2JP,P=48.5 Hz, PIII), 0.8 (d, 2JP,P=48.5 Hz,
PV). 1H NMR (C6D6): δ 2.75 (2H, dd, 2JP,H=10.0 Hz, 2JP,H
=
4.0 Hz, PCH2P), 6.82 (6H, td, JH,H = 7.5 Hz, JP,H =3.0 Hz,
m- and p-CH(PPh2)), 6.91 (6H, m, m and p-CH(Phphosphole)),
7.02 (6H, m, m- and p-CH(NPh)), 7.07 (2H, d, 3JP,H=8.0 Hz,
3
3
CHβ phosphole), 7.45 (4H, dd, JP,H =11.5 Hz, JH,H =7.0 Hz,

3996 Organometallics, Vol. 29, No. 17, 2010
Cao et al.
3JP,C=10.5 Hz, 4JP,C=1.0 Hz, o-CH(NPh)), 130.3 (d, 3JP,C=11.5
Hz, m-CH(PPh2)), 131.9 (d, 1JP,C=53.5 Hz, CIV-(PPh3)), 132.2 (d,
2JP,C=2.5 Hz, p-CH(PPh3)), 134.4(d, 4JP,C=2.5 Hz, p-CH(PPh2)),
134.9 (d, 2JP,C=9.0 Hz, o-CH(PPh2)), 136.5 (d, 2JP,C=11.0 Hz,
o-CH(PPh3)) 149.6 (dd, 2JP,C=3.0 Hz, 3JP,C=1.5 Hz, CIV-(NPh)).
Anal. Calcd for C37H32ClNPdP2S: C, 61.17; H, 4.44; N, 1.93.
Found: C, 61.03; H, 4.364; N, 2.02.
Table 1. Crystal Data and Structure Refinement Details for 11
mol formula
mol wt
C37H32ClNP2PdS
726.49
cryst habit
cryst dimens (mm)
cryst syst
space group
a (A)
b (A)
c (A)
R (deg)
β (deg)
orange block
0.14 ꢀ 0.12 ꢀ 0.10
monoclinic
P21/c
9.612(1)
16.430(1)
21.208(1)
90.00
102.922(1)
90.00
3264.5(4)
Synthesis of 12. THF (2 mL) was added to a mixture of
dichloro(p-cymene)ruthenium(II) dimer (23.2 mg, 0.038 mmol)
and 9 (30.0 mg, 0.076 mmol) at room temperature, immedi-
ately giving a red solution. After 2 h of stirring, THF was
removed. The residue was dissolved in dichloromethane
(3 mL), inducing the precipitation of the lithium salts, which
were filtered off. After evaporation of dichloromethane, the
obtained solid residue was washed with hexanes (3 mL) to give
12 as a red solid (34 mg, 76%). 31P{1H} NMR (d8-THF): δ
γ (deg)
V (A )
3
Z
4
1.478
1480
0.840
d (g cm-3
F(000)
)
μ (cm-1
)
max (deg)
3
36.9 (s). 1H NMR (CDCl3): δ 1.15 (6H, d, JH,H = 7.0 Hz,
3
θ
hkl ranges
27.47
-9 to þ12; -21 to þ19; -27 to þ27
CH(CH3)2), 1.99 (3H, s, CH3), 2.67 (1H, d, JH,H=13.0 Hz,
PCH2), 2.80 (1H, sept, 3JH,H=7.0 Hz, CH(CH3)2), 4.12 (1H,
vt, 3JH,H=2JP,H=13.0 Hz, PCH2), 4.64 (1H, d, 3JH,H=5.5 Hz,
CH(p-cymene)), 4.76 (2H, d, 3JH,H=5.5 Hz, CH(p-cymene)),
no. of measd/indep rflns
no. of rflns used
Rint
abs cor
no. of params refined
rflns/param
23 979/7391
4991
0.0449
multiscan; 0.8915 min, 0.9207 max
388
12
3
4.90 (1H, d, JH,H =5.5 Hz, CH(p-cymene)), 6.64 (1H, vtd,
4
3JH,H = 7.5 Hz, JH,H = 0.5 Hz, p-CH(NPh)), 6.85 (2H, t,
3JH,H=7.5 Hz, o-CH(PPh2)), 7.18 (2H, m, m-CH(PPh2)), 7.25
(1H, t, 3JH,H=7.0 Hz, p-CH(PPh2)), 7.38 (2H, d, 3JH,H=7.5
Hz, m-CH(NPh)), 7.52 (4H, td, JH,H=7.0 Hz, JP,H=11.5
R1/wR2 (I>2σ(I))
GOF
0.0405/0.0970
0.956
0.938(0.090)/-0.626(0.090)
784153
3
3
difference peak/hole (e A-3
CCDC number
)
3
Hz, o-CH(PPh2)), 7.57 (1H, d, JH,H=7.0 Hz, p-CH(PPh2)),
3
7.82 (2H, dd, JH,H=7.0 Hz, 3JP,H=10.1 Hz, m-CH(PPh2)).
13C NMR (CDCl3): δ 14.0 (s, CH3), 18.3, 18.5 (s, CH(CH3)2),
27.07 (s, CH(CH3)2), 28.8 (d, JP,C =84.0 Hz, PCH2), 73.2,
X-ray Crystallography. Data were collected at 150 K on a
Nonius Kappa CCD diffractometer using a Mo KR(λ=0.710 69 A)
X-ray source and a graphite monochromator. Experimental details
are described in Table 1. The crystal structure was solved using
SIR 9720 and Shelxl-97.21 ORTEP drawings were made using
ORTEP III for Windows.22
1
79.2, 79.3, 80.8 (s, CH(p-cymene)), 90.9, 99.0 (s, CIV-(p-
cymene)), 118.3 (d, JP,C = 2.0 Hz, p-CH(NPh)), 124.0 (d,
J
P,C=1.0 Hz, CH(NPh)), 124.4 (d, JP,C=9.0 Hz, CH(PPh2)),
124.6 (d, JP,C = 11.50 Hz, CH(PPh2)), 125.3 (d, JP,C = 7.0 Hz,
CH(NPh)), 126.1 (d, 1JP,C=89.0 Hz, CIV-(PPh2)), 127.9 (s, CH-
(PPh2)), 128.4 (s, CH(PPh2)), 129.8 (d, JP,C=9.0 Hz, CH(PPh2)),
130.1 (d, JP,C=9.0 Hz, CH(PPh2)), 151.2 (s, CIV-(NPh)). Anal.
Calcd for C29H31ClNPRuS: C, 58.72; H, 5.27; N, 2.36. Found: C,
58.61; H, 5.20; N, 2.21.
Acknowledgment. The CNRS and the Ecole Poly-
technique are thanked for financial support of this work.
Supporting Information Available: CIF files giving crystallo-
graphic data for 3, 6, and 11, figures giving ORTEP plots of 3
and 6, and tables giving crystal data and structural refinement
details for 3 and 6. This material is available free of charge via
the Internet at http://pubs.acs.org.
(20) Altomare, A.; Burla, M.; Camalli, C.; Cascarano, M. G.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.;
Spagna, R. SIR97, an integrated package of computer programs for
the solution and refinement of crystal structures using single crystal
data. J. Appl. Crystallogr. 1999, 32, 115–119.
€
€
€
(21) Sheldrick, G. M. SHELXL-97; Universitat Gottingen, Gottingen,
Germany, 1997.
(22) Farrugia, L. J. ORTEP-3; Department of Chemistry, University of
Glasgow, 2001.