Base-assisted cyclometalation and phosphorus-carbon bond cleavage in (arene)ruthenium(ii) complexes containing functionalized iminophosphorane- phosphine ligands Ph2PCH2P{=NP(=X)(OR)2}PH 2 (X = O, S; R = Et, Ph)

Article abstract of DOI:10.1021/om040033d

The bond-assisted cyclometalation and phosphorus-carbon bond cleavage in (Arene)ruthenium(II) complexes are discussed. The complexes contain functionalized iminophosphorane-phosphine ligands Ph₂PCH ₂P{=NP(=X)(OR)₂}Ph₂ (X = O, S; R = Et, Ph). It is found that the functionalized iminophosphorane-phosphines act as versatile ligands upon coordination to a (η⁶-arene)-ruthenium(II) fragment. The results show that the ligands are used as templates for the construction and stabilization of unusual organometallic ruthenium(II) complexes.

Full text of DOI:10.1021/om040033d

Organometallics 2004, 23, 3425-3436
3425
Ba se-Assisted Cyclom eta la tion a n d P h osp h or u s-Ca r bon
Bon d Clea va ge in (Ar en e)r u th en iu m (II) Com p lexes
Con ta in in g F u n ction a lized
Im in op h osp h or a n e-P h osp h in e Liga n d s
P h 2P CH2P {dNP (dX)(OR)2}P h 2 (X ) O, S; R ) Et, P h )
Victorio Cadierno,*,† J osefina D´ıez, J oaqu´ın Garc´ıa-AÄ lvarez, and J ose´ Gimeno*,‡
Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto Universitario de Qu´ımica
Organometa´lica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Qu´ımica,
Universidad de Oviedo, E-33071 Oviedo, Spain
Received March 12, 2004
Complexes [RuCl(η6-p-cymene)(κ2-P,X-Ph2PCH2P{dNP(dX)(OR)2}Ph2)][SbF6] (X ) O, R
) Et (1a ), Ph (1b); X ) S, R ) Et (2a ), Ph (2b)) react with a stoichiometric amount of NaH,
in THF at rt, to generate the neutral cyclometalated compounds [RuCl(κ2-P,C-Ph2PCHP-
{dNP(dX)(OR)2}Ph2)(η6-p-cymene)] (X ) O, R ) Et (3a ), Ph (3b); X ) S, R ) Et (4a ), Ph
(4b)), via selective deprotonation of the methylenic backbone of the coordinated iminophos-
phorane-phosphine ligands. Treatment of 3-4a ,b with AgSbF6, in CH2Cl2 at rt, affords the
corresponding cationic species [Ru(κ3-P,C,X-Ph2PCHP{dNP(dX)(OR)2}Ph2)(η6-p-cymene)]-
[SbF6] (X ) O, R ) Et (7a ), Ph (7b); X ) S, R ) Et (8a ), Ph (8b)) through the intramolecular
O- or S-coordination of the free -Ph2PdNP(dX)(OR)2 fragment. Complexes 7-8a ,b can also
be prepared by reaction of the dicationic derivatives [Ru(η6-p-cymene)(κ3-P,N,X-Ph2PCH2P-
{dNP(dX)(OR)2}Ph2)][SbF6]2 (5-6a ,b) with 1 equiv of NaH. Formation of complexes 3-4a ,b
and 7-8a ,b proceeds, in all cases, in a diastereoselective manner. Phosphorus-carbon bond
splitting has been observed upon treatment of complexes 1-2a ,b, 3-4a ,b, or 7-8a ,b with
an excess of NaH, in wet THF at rt, affording the novel phosphinito derivatives [Ru(κ2-C,X-
CH2P{dNP(dX)(OR)2}Ph2){κ1-P-P(dO)Ph2}(η6-p-cymene)] (X ) O, R ) Et (10a ); X ) S, R )
Et (11a ), Ph (11b)). Protonation and methylation of 10-11a ,b generates the cationic species
[Ru(κ2-C,X-CH2P{dNP(dX)(OR)2}Ph2){κ1-P-P(OH)Ph2}(η6-p-cymene)][BF4] (X ) O, R ) Et
(12a ); X ) S, R ) Et (13a ), Ph (13b)) and [Ru(κ2-C,X-CH2P{dNP(dX)(OR)2}Ph2){κ1-P-
P(OMe)Ph2}(η6-p-cymene)][CF3SO3] (X ) O, R ) Et (14a ); X ) S, R ) Et (15a ), Ph (15b)),
respectively, via selective electrophilic addition at the Ph2PdO group. The structure of
compounds [RuCl(κ2-P,C-Ph2PCHP{dNP(dO)(OPh)2}Ph2)(η6-p-cymene)] (3b) and [Ru(κ2-C,S-
CH2P{dNP(dS)(OEt)2}Ph2){κ1-P-P(dO)Ph2}(η6-C6H6)] (11a ′) has been determined by X-ray
crystallography.
In tr od u ction
taining iminophosphorane-phosphine ligands,4a,6f we
have recently reported the preparation of the heterot-
rifunctional systems Ph2PCH2P{dNP(dX)(OR)2}Ph2 (X
) O, S; R ) Et, Ph), via single-stage oxidation of bis-
The selective monoimination of bis-phosphines with
azides, via the Staudinger reaction,1,2 has been success-
fully applied to the preparation of several bidentate
iminophosphorane-phosphine ligands R2P-X-P(dNR′)-
R2 (X ) divalent bridging group).3 Nevertheless, despite
its great potential as hemilabile ligands4 and anticipated
diversity, the coordination chemistry5 and catalytic
applications6 of these heterodifunctional ligands still
remain scarcely explored when compared to their bis-
phosphine-monoxide counterparts R2P-X-P(dO)R2.7
As part of our ongoing work dealing with the synthe-
sis and catalytic activity of ruthenium complexes con-
(3) See for example: (a) Gilyarov, V. A.; Kovtum, V. Y.; Kabachmich,
M. I. Izv. Akad. Nauk SSSR, Ser. Khim. 1967, 5, 1159. (b) Katti K. V.;
Cavell, R. G. Inorg. Chem. 1989, 28, 413. (c) Katti, K. V.; Batchelor,
R. J .; Einstein F. W. B.; Cavell, R. G. Inorg. Chem. 1990, 29, 808. (d)
Cavell, R. G.; Reed, R. W.; Katti, K. V.; Balakrishna, M. S.; Collins, P.
W.; Mozol V.; Bartz, I. Phosphorus, Sulfur, Silicon 1993, 76, 9. (e)
Saravanamuthu, A.; Ho, D. M.; Kerr, M. E.; Fitzgerald, C.; Bruce, M.
R. M.; Bruce, A. E. Inorg. Chem. 1993, 32, 2202. (f) Balakrishna, M.
S.; Santarsiero B. D.; Cavell, R. G. Inorg. Chem. 1994, 33, 3079. (g)
Reed, R. W.; Santarsiero, B.; Cavell, R. G. Inorg. Chem. 1996, 35, 4292.
(h) Avis, M. W.; Goosen, M.; Elsevier, C. J .; Veldman, N.; Kooijman,
H.; Spek, A. L. Inorg. Chim. Acta 1997, 264, 43. (i) Molina, P.; Arques,
A.; Garc´ıa, A.; Ram´ırez de Arellano, M. C. Tetrahedron Lett. 1997, 38,
7613. (j) Molina, P.; Arques, A.; Garc´ıa, A.; Ram´ırez de Arellano, M.
C. Eur. J . Inorg. Chem. 1998, 1359. (k) Pandurangi, R. S.; Katti, K.
V.; Stillwell, L.; Barnes, C. L. J . Am. Chem. Soc. 1998, 120, 11364. (l)
Alajar´ın, M.; Lo´pez-Leonardo, C.; Llamas-Lorente, P.; Bautista, D.
Synthesis 2000, 2085. (m) Arques, A.; Molina, P.; Aun˜on, D.; Vilaplana,
M. J .; Desamparados Velasco, M.; Mart´ınez, F.; Bautista, D.; Lahoz,
F. J . J . Organomet. Chem. 2000, 598, 329. (n) Balakrishna, M. S.;
Teipel, S.; Pinkerton A. A.; Cavell, R. G. Inorg. Chem. 2001, 40, 1802.
† E-mail: vcm@fq.uniovi.es.
‡ E-mail: jgh@fq.uniovi.es.
(1) Staudinger, H.; Meyer, J . Helv. Chim. Acta 1919, 2, 635.
(2) For reviews on the Staudinger reaction see: (a) Gololobov, Y.
G.; Zhamurova, I. N.; Kasukhin, L. F. Tetrahedron 1981, 37, 437. (b)
Gololobov, Y. G.; Kasukhin, L. F. Tetrahedron 1992, 48, 1353. (c)
J ohnson, A. W. In Ylides and Imines of Phosphorus; Wiley: New York,
1993; p 403.
10.1021/om040033d CCC: $27.50 © 2004 American Chemical Society
Publication on Web 06/02/2004

3426 Organometallics, Vol. 23, No. 14, 2004
Cadierno et al.
Ch a r t 1
Ch a r t 2
(diphenylphosphino)methane (dppm) with the corre-
sponding phosphorylated or thiophosphorylated azide
(RO)2P(dX)N3 (X ) O, S; R ) Et, Ph).8 The attachment
of these functionalities at one of the phosphorus atoms
of dppm generates a new class of versatile polydentate
ligands with ability to adopt κ1-P- (I), κ2-P,N- (II), κ2-
P,X- (III), and κ3-P,N,X-coordination modes (IV) (see
Chart 1).8,9 In a series of reactivity studies we have also
proved the utility of these ligands to design valuable
precursors for the preparation of a host of novel ruthe-
nium(II) derivatives.8
obtained via base-induced phosphorus-carbon bond
splitting in complexes A and B, and (iii) cationic
complexes [Ru(κ2-C,X-CH2P{dNP(dX)(OR)2}Ph2){κ1-P-
P(OE)Ph2}(η6-p-cymene)]+ (D), generated by selective
protonation or methylation at the phosphinito Ph2PdO
group of complexes C.
We now report further examples of the synthetic
utility of these complexes. In particular, we describe the
role of the coordinated iminophosphorane-phosphines
Ph2PCH2P{dNP(dX)(OR)2}Ph2 (X ) O, S; R ) Et, Ph)
in the generation of novel ruthenium(II) complexes
bearing metal-carbon bonds, including (see Chart 2)
(i) cyclometalated complexes [RuCl(κ2-P,C-Ph2PCHP-
{dNP(dX)(OR)2}Ph2)(η6-p-cymene)] (A) and [Ru(κ3-
P,C,X-Ph2PCHP{dNP(dX)(OR)2}Ph2)(η6-p-cymene)]+ (B),
(ii) neutral phosphinito derivatives [Ru(κ2-C,X-CH2P-
{dNP(dX)(OR)2}Ph2){κ1-P-P(dO)Ph2}(η6-p-cymene)] (C),
Resu lts a n d Discu ssion
Syn th esis a n d Ch a r a cter iza tion of Cyclom eta -
la t ed Com p ou n d s [R u Cl(K2-P ,C-P h 2P CH P {dNP -
(dX)(OR)2}P h 2)(η6-p-cym en e)] (X ) O, R ) Et (3a ),
P h (3b); X ) S, R ) Et (4a ), P h (4b)) a n d [Ru (K3-
P ,C,X-P h 2P CHP {dNP (dX)(OR)2}P h 2)(η6-p-cym en e)]-
[SbF 6] (X ) O, R ) Et (7a ), P h (7b); X ) S, R ) Et
(8a ), P h (8b)). Complexes [RuCl(η6-p-cymene)(κ2-P,X-
Ph2PCH2P{dNP(dX)(OR)2}Ph2)][SbF6] (1-2a ,b)8,10 re-
act with a stoichiometric amount of NaH, in THF at
room temperature, to generate cyclometalated com-
pounds [RuCl(κ2-P,C-Ph2PCHP{dNP(dX)(OR)2}Ph2)(η6-
p-cymene)] (X ) O, R ) Et (3a ), Ph (3b); X ) S, R ) Et
(4a ), Ph (4b); 67-99% yield), via selective deprotonation
of the methylenic backbone and concomitant decoordi-
nation of the (RO)2PdX group of the iminophosphorane-
phosphine ligands (Scheme 1). 31P{1H} and 1H NMR
spectra of the crude reaction mixtures show no forma-
tion of a ruthenium-hydride bond.
Complexes 3-4a ,b have been characterized by means
of standard spectroscopic techniques (IR and 31P{1H},
1H, and 13C{1H} NMR) as well as elemental analyses
(details are given in the Experimental Section and the
Supporting Information). In particular, the NMR spec-
tra clearly indicate the diastereoselective formation of
a three-membered Ru-P-C metallacycle (two stereo-
genic centers are present, i.e., the ruthenium atom and
the PCHP carbon). The most significant features are the
following: (i) (1H NMR) a doublet of doublets signal at
2.07-2.22 ppm (2J HP(III) ) 2J HP(V) ) 6.7-7.8 Hz) for the
methine PCHP proton, (ii) (13C{1H} NMR) a character-
istic high-field doublet of doublets of doublets resonance
in the range 7.06-10.04 ppm (1J CP(V) ) 102.8-104.5 Hz;
(4) Hemilabile behavior of iminophosphorane-phosphine ligands has
been reported in: (a) Cadierno, V.; D´ıez, J .; Garc´ıa-Garrido, S. E.;
Garc´ıa-Granda, S.; Gimeno, J . J . Chem. Soc., Dalton Trans. 2002, 1465.
For a general review on hemilabile functionalized phosphine ligands
see: (b) Slone, C. S.; Weinberger, D. A.; Mirkin, C. A. Prog. Inorg.
Chem. 1999, 48, 233.
(5) For overviews on the coordination chemistry of R2P-X-P(dNR′)-
R2 ligands see: (a) Katti, K. V.; Cavell, R. G. Comments Inorg. Chem.
1990, 10, 53. (b) Cavell, R. G. Curr. Sci. 2000, 78, 440.
(6) Hydrogenation of olefins (Rh and Ir complexes): (a) Law, D. J .;
Cavell, R. G. J . Mol. Catal. 1994, 91, 175. (b) Cavell, R. G.; Law, D. J .;
Reed, R. W. U.S. Pat. Appl. US 887014, 1994. Methanol carbonylation
(Rh, Ni, and Co complexes): (c) Cavell, R. G.; Katti, K. V. U.S. Pat.
Appl. US 752348, 1994. Olefin oligomerization (Ni complexes): (d)
Cavell, R. G.; Creed, B.; Gelmini, L.; Law, D. J .; McDonald, R.; Sanger,
A. R.; Somogyvary, A. Inorg. Chem. 1998, 37, 757. (e) Cavell, R. G.;
Creed, B.; Law, D. J .; Nicola, A. P.; Sanger, A. R.; Somogyvary, A. U.S.
Pat. Appl. US 447887, 1996. Transfer hydrogenation of ketones (Ru
complexes): (f) Cadierno, V.; Crochet, P.; Garc´ıa-AÄ lvarez, J .; Garc´ıa-
Garrido, S. E.; Gimeno, J . J . Organomet. Chem. 2002, 663, 32. Cross-
coupling of secondary amines with aryl halides (Pd complexes): see
ref 3i.
(7) (a) Grushin, V. V. Organometallics 2001, 20, 3950, and references
therein. (b) Grushin, V. V. Chem. Rev. 2004, 104, 1629, and references
therein.
(8) X ) O: (a) Cadierno, V.; Crochet, P.; D´ıez, J .; Garc´ıa-AÄ lvarez,
J .; Garc´ıa-Garrido, S. E.; Gimeno, J .; Garc´ıa-Granda, S.; Rodr´ıguez,
M. A. Inorg. Chem. 2003, 42, 3293. X ) S: (b) Cadierno, V.; Crochet,
P.; D´ıez, J .; Garc´ıa-AÄ lvarez, J .; Garc´ıa-Garrido, S. E.; Garc´ıa-Granda,
S.; Gimeno, J .; Rodr´ıguez, M. A. Dalton Trans. 2003, 3240.
(9) Although theoretical calculations (DFT level) on the model
complexes
[Ru(η6-C6H6)Cl(κ2-P,N-H2PCH2P{dNP(dX)(OH)2}H2)]+
(10) We note that complex [Ru(η6-p-cymene)Cl(κ2-P,O-Ph2PCH2P-
{dNP(dO)(OEt)2}Ph2)][SbF6] (1a ) is always obtained as an equilibrium
mixture along with its κ2-P,N-isomer [Ru(η6-p-cymene)Cl(κ2-P,N-Ph2-
PCH2P{dNP(dO)(OEt)2}Ph2)][SbF6]. See ref 8a. For clarity, and in
order to save space, in this paper we will refer to this mixture as
complex 1a exclusively.
(X ) O, S) and [Ru(η6-C6H6)Cl(κ2-P,X-H2PCH2P{dNP(dX)(OH)2}H2)]+
(X ) O, S) predicted that the κ2-P,N-isomers II are more stable than
their κ2-P,X-counterparts III, a marked preference for the bidentate
κ2-P,X-coordination, probably due to steric reasons, was experimentally
observed.

Cyclometalation in (Arene)ruthenium(II) Complexes
Organometallics, Vol. 23, No. 14, 2004 3427
Sch em e 1
1J CP(III) ) 19.0-21.6 Hz; 3J CP(V) ) 8.5-12.2 Hz) assigned
to the metal-bonded carbon of the PCHP unit, and (iii)
(31P{1H} NMR) the presence of three well-separated
F igu r e 1. ORTEP-type view of the structure of [RuCl(κ2-
P,C-Ph2PCHP{dNP(dO)(OPh)2}Ph2)(η6-p-cymene)] (3b )
showing the crystallographic labeling scheme. Phenyl
groups and hydrogen atoms (except that on C(11)) have
been omitted for clarity. Thermal ellipsoids are drawn at
20% probability level. Selected bond distances (Å) and
angles (deg): Ru-Cl(1) ) 2.417(1); Ru-P(1) ) 2.244(1);
Ru-C(11) ) 2.204(4); Ru-C* ) 1.717(2); P(1)-C(11) )
1.759(4); C(11)-P(2) ) 1.758(4); P(2)-N(1) ) 1.581(4);
N(1)-P(3) ) 1.582(4); P(3)-O(1) ) 1.469(3); P(3)-O(2) )
1.605(3); P(3)-O(3) ) 1.611(3); C*-Ru-Cl(1) ) 124.81(1);
C*-Ru-P(1) ) 139.63(1); C*-Ru-C(11) ) 142.64(1); Cl-
(1)-Ru-P(1) ) 91.43(4); Cl(1)-Ru-C(11) ) 83.12(11);
P(1)-Ru-C(11) ) 46.57(10); Ru-C(11)-P(1) ) 67.93(14);
Ru-P(1)-C(11) ) 65.50(13); Ru-C(11)-P(2) ) 125.6(2);
P(1)-C(11)-P(2) ) 134.3(3); C(11)-P(2)-N(1) ) 114.3(2);
P(2)-N(1)-P(3) ) 132.4(2); N(1)-P(3)-O(1) ) 120.14(19);
signals with equal relative intensities (δ 6.26-7.18 (d,
2
2J PP ) 24.4-25.3 Hz; Ph2P), 18.61-24.00 (dd, J PP
)
24.4-25.3 and 11.3-34.4 Hz; Ph2PdN), and -9.93-1.53
(d, 2J PP ) 29.3-34.4 Hz; (RO)2PdO) or 48.73-58.13 (d,
2J PP ) 11.3-12.6 Hz; (RO)2PdS) ppm), the chemical
shifts observed being in accord with the presence of
uncoordinated Ph2PdN-P(dX)(OR)2 moieties8 and the
incorporation of the diphenylphosphino group into a
strained three-membered chelate ring.11,12
The X-ray crystal structure of [RuCl(κ2-P,C-Ph2PCHP-
{dNP(dO)(OPh)2}Ph2)(η6-p-cymene)] (3b) unambigu-
ously confirmed the proposed structure. As the ORTEP-
type drawing (Figure 1) reveals,13 the ruthenium atom
is coordinated by the p-cymene ring, one chloride, and
the P,C-bonded phosphinomethanide ligand. As ex-
pected, the P(1)-Ru-C(11) bond angle (46.57(10)°) is
significantly smaller than the Cl(1)-Ru-P(1) and Cl-
(1)-Ru-C(11) angles (91.43(4)° and 83.12(11)°, respec-
tively). In addition, the bond distances within the three-
membered Ru-P-C metallacycle (Ru-P(1) ) 2.244(1)
Å, Ru-C(11) ) 2.204(4) Å, and P(1)-C(11) ) 1.759(4)
Å) compare well with those found in the related (η6-
arene)-ruthenium(II) complexes [RuCl{κ2-P,C-iPr2PCH-
(CO2Me)}(η6-1,3,5-C6H3Me3)] (E) (Ru-P ) 2.2694(8) Å,
Ru-C ) 2.201(2) Å, P-C ) 1.761(2) Å),14a [Ru(κ3-P,C,O-
iPrP{CH(CO2Me)}C(H)dCO2Me)(η6-1,3,5-C6H3Me3)] (F )
(Ru-P ) 2.301(2) Å, Ru-C ) 2.217(4) Å, P-C )
N(1)-P(3)-O(2)
)
105.74(18); N(1)-P(3)-O(3)
)
105.17(17); O(1)-P(3)-O(2) ) 112.52(17); O(1)-P(3)-O(3)
) 112.67(17); O(2)-P(3)-O(3) ) 98.06(16). C* ) centroid
of the p-cymene ring (C(1), C(2), C(3), C(4), C(5), and C(6)).
Ch a r t 3
(11) An important shielding is observed in the Ph2P phosphorus
resonances when moving from 1-2a ,b (22.97-26.36 ppm) to 3-4a ,b
(6.26-7.18 ppm). This fact is in agreement with the formation of a
smaller chelate ring: Garrou, P. E. Chem. Rev. 1981, 81, 229.
(12) The diphenylphosphino group in ruthenium(II) complexes
containing Ru(κ2-P,C-Ph2PCHR) units usually resonate, in 31P NMR,
at δ 4-9 ppm. See for example: (a) Demerseman, B.; Guilbert, B.;
Renouard, C.; Gonzalez, M.; Dixneuf, P. H.; Masi, D.; Mealli, C.
Organometallics 1993, 12, 3906. (b) Crochet, P.; Demerseman, B.;
Rocaboy, C.; Schleyer, D. Organometallics 1996, 15, 3048, and refer-
ences therein.
(13) As expected, the two enantiomers are present in the unit cell
displaying SRuSC and RRuRC configurations. For brevity, only the
molecular structure of the SRuSC enantiomer is depicted in Figure 1
(selected bond distances and angles listed in the caption refer to this
enantiomer).
1.727(4) Å),14b and [Ru(κ3-P,C,O-Ph2PCH{C(Ph)dC(H)C-
(dO)tBu})(η6-1,3,5-C6H3Me3)][BF4] (G) (Ru-P
)
2.243(2) Å, Ru-C ) 2.211(8) Å, P-C ) 1.761(4) Å)12a
(see Chart 3). P-N and P-O bond lengths are also
similar to those found in other species containing
-R2PdNP(dX)(OR′)2 units (X ) O, S).3f,8,15 Cyclometa-
lations leading to the formation of a strained three-
membered M-P-C ring are well documented,12,14,16 but
(14) (a) Henig, G.; Schulz, M.; Windmu¨ller, B.; Werner, H. Dalton
Trans. 2003, 441. (b) Werner, H.; Bank, J .; Windmu¨ller, B.; Gevert,
O.; Wolfsberger, W. Helv. Chim. Acta 2001, 84, 3162.

3428 Organometallics, Vol. 23, No. 14, 2004
Cadierno et al.
Ch a r t 4
Ch a r t 5
no example is known in the chemistry of iminophos-
phorane-phosphine ligands R2PCH2P(dNR′)R2.5
It is apparent that the bidentate κ2-P,C-coordination
mode of the anions [Ph2PCHP{dNP(dX)(OR)2}Ph2]- (A
in Chart 2) is preferred versus the κ2-P,N- or κ2-P,X-
coordination isomers (see Chart 4). It is worth noting
the favorable formation of a relatively strained Ru-P-C
ring versus the more relaxed five- (κ2-P,N) or seven-
membered (κ2-P,X) chelates. In fact, it has been recently
reported the selective formation of five-membered κ2-
P,N-rings, i.e., complexes [PdL2{κ2-P,N-Ph2PCHdC(Ph)-
N(2,6-C6H3Me2)}] (see Chart 4), by deprotonation of the
methylenic unit in compounds [PdL2{κ2-P,N-Ph2PCH2C-
(Ph)dN(2,6-C6H3Me2)}] containing a related iminophos-
phine ligand.17
Analogous deprotonations also occur starting from the
dicationic complexes [Ru(η6-p-cymene)(κ3-P,N,X-Ph2-
PCH2P{dNP(dX)(OR)2}Ph2)][SbF6]2 (X ) O, R ) Et
(5a ), Ph (5b); X ) S, R ) Et (6a ), Ph (6b)).8 Thus, the
treatment of complexes 5-6a ,b with a stoichiometric
amount of NaH, in THF at room temperature, affords
the cyclometalated complexes [Ru(κ3-P,C,X-Ph2PCHP-
{dNP(dX)(OR)2}Ph2)(η6-p-cymene)][SbF6] (X ) O, R )
Et (7a ), Ph (7b); X ) S, R ) Et (8a ), Ph (8b)) via PCH2P
deprotonation and selective decoordination of the labile
iminophosphorane Ph2PdN unit (Scheme 1). Com-
pounds 7-8a ,b have been isolated as air-stable micro-
crystalline solids in 79-93% yield. As expected, 7-8a ,b
can also be prepared in similar yields by reaction of the
neutral complexes [RuCl(κ2-P,C-Ph2PCHP{dNP(dX)-
(OR)2}Ph2)(η6-p-cymene)] (X ) O, R ) Et (3a ), Ph (3b);
X ) S, R ) Et (4a ), Ph (4b)) with 1 equiv of AgSbF6, in
dichloromethane at room temperature, via diastereo-
selective intramolecular O- or S-coordination of the free
-Ph2PdNP(dX)(OR)2 fragment (see Scheme 1).
Complexes 7-8a ,b have been characterized by el-
emental analyses, conductance measurements (1:1 elec-
trolytes; ΛM ) 111-120 Ω-1 cm2 mol-1), and IR and
NMR spectroscopy (see the Experimental Section and
the Supporting Information for details), the latter
supporting its diastereoselective formation. Character-
istic spectroscopic features are (i) (1H NMR) the me-
thinic PCHP proton resonance at 1.89-2.07 ppm which,
in contrast to 3-4a ,b, appears as doublet due to the
exclusive coupling with the phosphorus atom of the
Ph2PdN unit (2J HP ) 6.1-6.4 Hz), (ii) (13C{1H} NMR)
the ddd signal for the PCHP carbon (δ from -8.69 to
-6.22 ppm; 1J CP(V) ) 67.6-69.2 Hz; 1J CP(III) ) 11.5-15.5
(15) See for example: (a) Larre´, C.; Donnadieu, B.; Caminade, A.
M.; Majoral, J . P. Eur. J . Inorg. Chem. 1999, 601. (b) Balakrishna, M.
S.; Abhyankar, R. M.; Walawalker, M. G. Tetrahedron Lett. 2001, 42,
2733. (c) Longlet, J . J .; Bodige, S. G.; Watson, W. H.; Nielson, R. H.
Inorg. Chem. 2002, 41, 6507. (d) Maraval, V.; Laurent, R.; Donnadieu,
B.; Caminade, A. M.; Majoral, J . P. Synthesis 2003, 389.
3
Hz; J CP(V) ) 7.8-11.5 Hz) which is ca. 16 ppm high-
field shifted when compared to that of their neutral
precursors 3-4a ,b, and (iii) (31P{1H} NMR) the typical
signals for the Ph2P (δ 4.34-9.87 (d or dd, 2J PP ) 15.9-
(16) Cyclometalation of coordinated tertiary alkyl-phosphines is a
widely occurring phenomenon. See for example: (a) Rathke, J . W.;
Muetterties, E. L. J . Am. Chem. Soc. 1975, 97, 3272. (b) Karsch, H.
H.; Klein, H.-F.; Schmidbaur, H. Angew. Chem. 1975, 87, 630. (c) Al-
J ibori, S.; Crocker, C.; McDonald, W. S.; Shaw, B. L. J . Chem. Soc.,
Dalton Trans. 1981, 1572. (d) Karsch, H. H.; Neugebauer, D. Angew.
Chem., Int. Ed. Engl. 1982, 21, 312. (e) Karsch, H. H. Angew. Chem.,
Int. Ed. Engl. 1982, 21, 921. (f) Karsch, H. H. Chem. Ber. 1984, 117,
783. (g) Karsch, H. H. Chem. Ber. 1984, 117, 3123. (h) Mainz, V. V.;
Andersen, R. A. Organometallics 1984, 3, 675. (i) Gotzig, J .; Werner,
R.; Werner, H. J . Organomet. Chem. 1985, 285, 99. (j) Baker, M. V.;
Field, L. D. Organometallics 1986, 5, 821. (k) Bryndza, H. E.; Fong, L.
K.; Paciello, R. A.; Tam, W.; Bercaw, J . E. J . Am. Chem. Soc. 1987,
109, 1444. (l) Shinomoto, R. S.; Desrosiers, P. J .; Harper, T. G. P.; Flood,
T. C. J . Am. Chem. Soc. 1990, 112, 704. (m) Dahlenburg, L.; Kerstan,
S.; Werner, D. J . Organomet. Chem. 1991, 411, 457. (n) Werner, H.;
Henig, G.; Wecker, U.; Mahr, N.; Peters, K.; von Schnering, H. G.
Chem. Ber. 1995, 128, 1175. (o) Holland, A. W.; Bergman, R. G.
Organometallics 2002, 21, 2149. (p) J anak, K. E.; Tanski, J . M.;
Churchill, D. G.; Parkin, G. J . Am. Chem. Soc. 2002, 124, 4182. (q)
Liu, S. H.; Lo. S. T.; Wen, T. B.; Williams, I. D.; Zhou, Z. Y.; Lau, C.
P.; J ia, G. Inorg. Chim. Acta 2002, 334, 122.
3
22.6 Hz, J PP ) 0-4.5 Hz)) and (RO)2PdO (δ -0.28-
2
8.85 (d, J PP ) 16.2-17.1 Hz)) or (RO)2PdS (δ 40.94-
2
3
47.75 (d or dd, J PP ) 7.2-9.0 Hz, J PP ) 0-4.5 Hz))
units. The chemical shifts found for the Ph2PdN phos-
phorus nuclei (δ 23.32-31.29 (dd, 2J PP ) 15.9-22.6 and
7.2-17.1 Hz)) strongly support the κ3-P,C,X-coordina-
tion of the ligands versus the potential κ3-P,C,N-
coordination isomers (Chart 5). We note that Ph2PdN
phosphorus resonances in the related species H, I, and
J (see Chart 5) are observed at 60-70 ppm.18 The
preference for the κ3-P,C,X- versus κ3-P,C,N-coordina-
tion mode observed in complexes 7-8a ,b could probably
be due to the higher steric strain associated with the
presence of an unfavorable three- and four-membered
fused metalla-bicycle in the latter.
Protonation of complexes [RuCl(κ2-P,C-Ph2PCHP-
{dNP(dO)(OPh)2}Ph2)(η6-p-cymene)] (3b) and [Ru(κ3-
(17) (a) Coleman, K. S.; Green, M. L. H.; Pascu, S. I.; Rees, N. H.;
Cowley, A. R.; Rees, L. H. J . Chem. Soc., Dalton Trans. 2001, 3384.
Imine-enamine tautomerism has been also observed for this type of
P,N-ligands in solution: (b) Liu, X.; Mok, K. F.; Leung, P.-H. Orga-
nometallics 2001, 20, 3918. (c) Masuda, J . D.; Wei, P.; Stephan, D. W.
Dalton Trans. 2003, 3500.
(18) Cadierno, V.; D´ıez, J .; Garc´ıa-AÄ lvarez, J .; Gimeno, J .; Calhorda,
M. J .; Veiros, L. F. Organometallics 2004, 23, 2421.

Cyclometalation in (Arene)ruthenium(II) Complexes
Organometallics, Vol. 23, No. 14, 2004 3429
Sch em e 2
Sch em e 3
P,C,X-Ph2PCHP{dNP(dO)(OPh)2}Ph2)(η6-p-cymene)]-
[SbF6] (7b) shows the reversibility of the processes
depicted in Scheme 1 (see Scheme 2). Thus, we have
found that, while the treatment of 3b with an equimolar
amount of HBF4 regenerates complex 1b (as the tet-
rafluoroborate salt) quantitatively, the use of HCl (1
equiv) results in the selective formation of the previously
reported neutral complex [RuCl2(κ1-P-Ph2PCH2P{dNP-
(dO)(OPh)2}Ph2)(η6-p-cymene)] (9) via competitive chlo-
ride coordination.8a Similar results were obtained start-
ing from 7b, which can be selectively transformed into
5b or 1b depending on the protic acid used.
of a ruthenium-carbon bond, we speculated the pos-
sibility to generate ruthenium-carbene complexes via
subsequent deprotonation of the remaining C-H bond.
We have recently reported the synthesis of unusual
ruthenium-carbene derivatives [Ru(κ2-C,N-C[P{dNP-
(dO)(OR)2}Ph2]2)(η6-p-cymene)] (R ) Ph, Et) (J in Chart
5) from complexes containing bis(iminophosphorano)-
methanide groups of the type H and I (Chart 5).18
However, the treatment of complexes 3a and 4a ,b with
a 10-fold excess of NaH in THF at room temperature
leads instead to the formation of diphenylphosphinito-
ruthenium(II) derivatives [Ru(κ2-C,X-CH2P{dNP(dX)-
(OR)2}Ph2){κ1-P-P(dO)Ph2}(η6-p-cymene)] (X ) O, R )
Et (10a ); X ) S, R ) Et (11a ), Ph (11b)) (Scheme 3). It
is interesting to note that the reaction proceeds faster
(ca. 6 h) when undistilled THF (wet) was used as solvent
(versus ca. 48 h with predistilled THF). Complexes 10a
and 11a ,b can also be obtained (74-91% yield), under
the same reaction conditions, starting from the cationic
species [Ru(κ3-P,C,X-Ph2PCHP{dNP(dX)(OR)2}Ph2)(η6-
Syn th esis a n d Ch a r a cter iza tion of P h osp h in ito
Der iva tives [Ru (K2-C,X-CH2P {dNP (dX)(OR)2}P h 2)-
{K1-P -P (dO)P h 2}(η6-p-cym en e)] (X ) O, R ) Et
(10a ); X ) S, R ) Et (11a ), P h (11b)) a n d [Ru (K2-
C,S-CH2P {dNP (dS)(OEt)2}P h 2){K1-P -P (dO)P h 2}(η6-
C6H6)] (11a ′). Providing that the methylenic carbon-
hydrogen bonds are activated in the iminophosphorane
complexes 1-2a ,b and 5-6a ,b promoting the formation

3430 Organometallics, Vol. 23, No. 14, 2004
Cadierno et al.
F igu r e 2. ORTEP-type view of the structure of [Ru(κ2-C,S-CH2P{dNP(dS)(OEt)2}Ph2){κ1-P-P(dO)Ph2}(η6-C6H6)] (11a ′)
showing the crystallographic labeling scheme. Phenyl groups and hydrogen atoms have been omitted for clarity. Thermal
ellipsoids are drawn at 10% probability level. Selected bond distances (Å) and angles (deg): Ru-C(7) ) 2.158(7); Ru-P(3)
) 2.338(2); Ru-S(1) ) 2.405(2); Ru-C* ) 1.7384(9); C(7)-P(1) ) 1.756(7); P(1)-N(1) ) 1.590(6); N(1)-P(2) ) 1.556(6);
P(2)-S(1) ) 1.982(3); P(2)-O(1) ) 1.577(6); P(2)-O(2) ) 1.563(6); P(3)-O(3) ) 1.519(5); C*-Ru-C(7) ) 130.8(2); C*-
Ru-P(3) ) 123.85(6); C*-Ru-S(1) ) 127.00(7); C(7)-Ru-P(3) ) 82.7(2); C(7)-Ru-S(1) ) 87.3(2); P(3)-Ru-S(1) )
91.50(8); Ru-P(3)-O(3) ) 113.1(2); Ru-P(3)-C(24) ) 118.2(2); Ru-P(3)-C(30) ) 111.7(3); O(3)-P(3)-C(24) ) 106.1(3);
O(3)-P(3)-C(30) ) 106.4(3); C(24)-P(3)-C(30) ) 100.2(3); Ru-C(7)-P(1) ) 116.4(4); C(7)-P(1)-N(1) ) 115.8(4); P(1)-
N(1)-P(2) ) 133.1(4); N(1)-P(2)-O(1) ) 109.7(4); N(1)-P(2)-O(2) ) 111.0(4); N(1)-P(2)-S(1) ) 118.8(3); O(1)-P(2)-
O(2) ) 100.2(4); O(1)-P(2)-S(1) ) 107.4(3); O(2)-P(2)-S(1) ) 108.1(3); P(2)-S(1)-Ru ) 105.25(11). C* ) centroid of the
benzene ring (C(1), C(2), C(3), C(4), C(5), and C(6)).
p-cymene)][SbF6] (X ) O, R ) Et (7a ); X ) S, R ) Et
(8a ), Ph (8b)) or [RuCl(η6-p-cymene)(κ2-P,X-Ph2PCH2P-
{dNP(dX)(OR)2}Ph2)][SbF6] (X ) O, R ) Et (1a ); X )
S, R ) Et (2a ), Ph (2b)) (Scheme 3).19,20 Compounds 10a
and 11a ,b formally arise from an OH--promoted phos-
phorus-carbon bond splitting with concomitant forma-
tion of PdO and C-H bonds.21 All attempts to avoid
the P-C cleavage have failed.
Complexes 10a and 11a ,b have been isolated as air-
stable yellow solids. They have been characterized by
elemental analyses and IR and NMR spectroscopy
(details are given in the Experimental Section and the
Supporting Information), which are fully consistent with
the structural proposal. In particular, (i) the presence
of a coordinated Ph2P(dO) ligand is strongly supported
by the 31P{1H} NMR spectra, which show a downfield
doublet (10a ) or doublet of doublets signal (11a ,b) at δ
70.92-73.75 ppm (3J PP ) 14.8-19.0 Hz). These chemical
shifts fit well with those reported in the literature for
related diphenylphosphinito-ruthenium(II) complexes.20c
(ii) Typical Ru-CH2 carbon resonances appear in the
13C{1H} NMR spectra as a high-field doublet of doublet
of doublets signal in the range from -2.74 to 0.30 ppm
(1J CP ) 38.1-41.1 Hz; 2J CP ) 13.7-16.1 Hz; 3J CP ) 8.3-
11.7 Hz).
X-ray diffraction studies on the related η6-benzene
derivative [Ru(κ2-C,S-CH2P{dNP(dS)(OEt)2}Ph2){κ1-P-
P(dO)Ph2}(η6-C6H6)] (11a ′) unequivocally confirmed the
molecular structure proposed for complexes 10-11a ,b.22
An ORTEP plot is shown in Figure 2; selected bond
distances and angles are listed in the caption. The
coordination sphere around ruthenium consists of the
η6-benzene fragment, the phosphorus atom of the diphe-
nylphosphinito unit, and the carbon and sulfur atoms
of the novel anionic ligand [CH2P{dNP(dS)(OEt)2}Ph2]-,
which forms along with the metal a six-membered ring
with chair conformation. The P(1)-N(1) and N(1)-P(2)
distances within this six-membered ring are quite
similar (1.590(6) and 1.556(6) Å, respectively), indicat-
ing, as observed in 3b, that electronic delocalization of
the nitrogen lone pair is also present.3f,8,15 The P(3)-
O(3) bond length (1.519(5) Å) is in good agreement with
(19) Treatment of complex 1b, 3b, or 7b with 10 equiv of NaH in
wet THF generates also the corresponding phosphinito derivative [Ru-
(κ2-C,O-CH2P{dNP(dO)(OPh)2}Ph2){κ1-P-P(dO)Ph2}(η6-p-cymene)]
(10b), as clearly assessed by 31P{1H} NMR spectroscopy (δP 7.72 (d,
2
3
2J PP ) 17.1 Hz, (PhO)2PdO), 27.77 (dd, J PP ) 17.1 Hz, J PP ) 12.2
3
Hz, Ph2PdN), 80.89 (d, J PP ) 12.2 Hz, Ph2PdO)), along with several
unidentified species, which prevented its isolation in pure form.
(20) Mononuclear phosphinito-ruthenium(II) and osmium(II) com-
plexes [M]-{PR2(dO)} are known. For recent references see: (a)
Esteruelas, M. A.; Lo´pez, A. M.; Tolosa, J . I.; Vela, N. Organometallics
2000, 19, 4650. (b) Geldbach, T. J .; Pregosin, P. S.; Bassetti, M.
Organometallics 2001, 20, 2990. (c) Geldbach, T. J .; den Reijer, C. J .;
Wo¨rle, M.; Pregosin, P. S. Inorg. Chim. Acta 2002, 330, 155.
(21) Scission of phosphorus-cabon bonds in ruthenium-coordinated
phosphine ligands is known to occur in both basic and acidic media.
See for example ref 12b and: Geldbach, T. J .; Pregosin, P. S. Eur. J .
Inorg. Chem. 2002, 1907, and references therein.
(22) All attempts to obtain crystals of compounds 10-11a ,b suitable
for X-ray diffraction studies failed. Complex 11a ′ was prepared in 77%
yield, as described for 10-11a ,b, starting from [RuCl(η6-C6H6)(κ2-P,S-
Ph2PCH2P{dNP(dS)(OEt)2}Ph2)][SbF6] (2a ′). Synthetic details and
characterization data for 2a ′, 11a ′, and the precursor species [RuCl2-
(η6-C6H6)(κ1-P-Ph2PCH2P{dNP(dS)(OEt)2}Ph2)] are given in the Ex-
perimental Section.

Cyclometalation in (Arene)ruthenium(II) Complexes
Organometallics, Vol. 23, No. 14, 2004 3431
absorption band at 3230-3280 cm-1 for 12-13a ,b, (ii)
(1H NMR) a low-field broad singlet (12-13a ,b) or a
high-field doublet (14-15a ,b) signal corresponding to
the OH (δ 8.91-11.60 ppm) and OMe (δ 3.40-3.51 ppm;
Sch em e 4
3
ca. J HP ) 11 Hz) protons, respectively, and (iii) (31P-
{1H} NMR) a doublet of doublets signal (δ 112.34-
3
117.61 ppm; J PP ) 4.4-24.4 Hz) for the Ph2POH
phosphorus nucleus, the low-field chemical shifts ob-
served being in accord with those observed in other
hydroxydiphenylphosphine-ruthenium(II) complexes (for
14-15a ,b the signal of the Ph2POMe ligand appears
at δ 130.31-135.81 ppm).25 NMR spectra also show the
resonances arising from the presence of the bidentate
ligands κ2-C,X-CH2P{dNP(dX)(OR)2}Ph2. Since they
show no significant differences with respect to those of
the precursor complexes 10-11a ,b, no further comment
is deserved.
literature P-O distances for phosphine oxides,23 and the
Ru-C(7) and Ru-P(3) lengths (2.158(7) and 2.338(2) Å,
respectively) show also the expected values for ruthe-
nium-carbon and ruthenium-phosphorus single bonds.24
A mechanistic proposal for the formation of complexes
10-11a ,b is depicted in Scheme 4. We assume that a
nuclephilic attack of OH- (generated in situ from NaH
and the water present in the undistilled solvent) at the
phosphorus atom of the three-membered metallacycle
takes place in the first step, giving rise to the cleavage
of the P-C bond to form intermediate species I. A
subsequent H-migration from oxygen to the resulting
nucleophilic carbon atom gives the final product. In the
case of 3-4a ,b the concomitant chloride abstraction
leaves a free coordination site, allowing the attachment
of the phosphoryl or thiophosphoryl unit. We note that
such P-C bond cleavage has no precedent in the
chemistry of the three-membered metallacyclic com-
pounds of the type [M]-(κ2-P,C-R2PCHR).12,14,16
Syn th esis a n d Ch a r a cter iza tion of [Ru (K2-C,X-
CH 2P {dNP (dX)(OR )2}P h 2){K1-P -P (OH )P h 2}(η6-p -
cym en e)][BF 4] (X ) O, R ) Et (12a ); X ) S, R ) Et
(13a ), P h (13b )) a n d [R u (K2-C,X-CH 2P {dNP (dX)-
(OR )2}P h 2){K1-P -P (OMe)P h 2}(η6-p -cym en e)][CF 3-
SO3] (X ) O, R ) Et (14a ); X ) S, R ) Et (15a ), P h
(15b)). In agreement with the presence of the phos-
phinito Ph2PdO group, complexes 10-11a ,b are prone
to add electrophiles at the oxygen atom. Thus, the
treatment of dichloromethane solutions of 10-11a ,b
with 1 equiv of HBF4 generates the novel hydroxydi-
phenylphosphine-ruthenium(II) derivatives [Ru(κ2-C,X-
CH 2P {dNP (dX)(OR)2}P h 2){κ1-P -P (OH )P h 2}(η6-p-
cymene)][BF4] (X ) O, R ) Et (12a ); X ) S, R ) Et
(13a ), Ph (13b)) (60-75% yield) (Scheme 5). Similarly,
complexes [Ru(κ2-C,X-CH2P{dNP(dX)(OR)2}Ph2){κ1-P-
P(OMe)Ph2}(η6-p-cymene)][CF3SO3] (X ) O, R ) Et
(14a ); X ) S, R ) Et (15a ), Ph (15b)) have been
prepared (70-78% yield) via methylation reactions with
MeOSO2CF3 (Scheme 5). Analogous transformations of
coordinated phosphinito ligands into hydroxy- or alkoxy-
phosphines have been described.20a
Con clu sion
In this paper we have shown that the functionalized
iminophosphorane-phosphines Ph2PCH2P{dNP(dX)-
(OR)2}Ph2 (X ) O, S; R ) Et, Ph) act as versatile ligands
upon coordination to a (η6-arene)-ruthenium(II) frag-
ment, generating through selective transformations
unusual systems containing ruthenium-carbon bonds.
These are generated by the formation of two novel
anionic ligands of the type (i) [Ph2PCHP{dNP(dX)-
(OR)2}Ph2]- (I) obtained by deprotonation of the meth-
ylenic backbone of the iminophosphorane-phosphine
ligands in complexes 1-2a ,b and 5-6a ,b, and (ii)
[CH2P{dNP(dX)(OR)2}Ph2]- (II) via base-assisted P-C
bond splitting in the latter complexes in which ligands
I show κ2-P,C (complexes 3-4a ,b) and κ3-P,C,X (com-
plexes 7-8a ,b) coordination modes. The coordination
ability of the anionic polydentate ligands of the type I
in complexes 7-8a ,b is remarkable, adopting selectively
the rare case of a κ3-P,C,X-coordination mode in which
two fused three- and six-membered metallacycles are
stabilized.
It is also worth noting that the closely related ligands
bis(diphenylphosphino)methanide monochalcogenides
[Ph2PCHP(dX)Ph2]- (X ) O, S, Se) show in contrast a
marked preference for the κ2-P,X- versus κ2-P,C-
coordination mode, leading to less strained five-mem-
bered chelates.26,27 In summary, the results reported
here, which have no precedents in the chemistry of
iminophosphorane-phosphine ligands Ph2PCH2P(dNR)-
Ph2,5 represent a clear example of the usefulness of
these ligands as templates for the construction and
stabilization of unusual organometallic ruthenium(II)
complexes.
Complexes 12-13a ,b and 14-15a ,b have been iso-
lated as yellow air-stable tetrafluoroborate or tri-
flouromethanesulfonate salts, respectively, and charac-
terized by elemental analysis, conductance masure-
ments (1:1 electrolytes; ΛM ) 116-132 Ω-1 cm2 mol-1),
and IR and NMR spectroscopy. The presence of the
hydroxy- and methoxy-phosphine ligands Ph2POR (R )
H, Me) is fully suported by IR and NMR spectroscopy.
Particular features are (i) (IR) a characteristic ν(OH)
(25) See for example: (a) den Reijer, C. J .; Wo¨rle, M.; Pregosin, P.
S. Organometallics 2000, 19, 309. (b) Geldbach, T. J .; Drago, D.;
Pregosin, P. S. J . Organomet. Chem. 2002, 643-644, 214. (c) Geldbach,
T. J .; Pregosin, P. S.; Albinati, A. Organometallics 2003, 22, 1443.
(26) See for example: (a) Berry, D. E.; Browning, J .; Dixon, K. R.;
Hilts, R. W. Can. J . Chem. 1988, 66, 1272. (b) Browning, J .; Dixon, K.
R.; Hilts, R. W. Organometallics 1989, 8, 552. (c) Uso´n, R.; Laguna,
A.; Laguna, M.; Nieves Fraile, M.; J ones, P. G.; Freire Erdbru¨gger, C.
J . Chem. Soc., Dalton Trans. 1989, 73. (d) Browning, J .; Bushnell, G.
W.; Dixon, K. R.; Hilts, R. W. J . Organomet. Chem. 1993, 452, 205.
(27) The dinuclear complex [Pd2{µ:κ2-P,C-Ph2PCHP(dO)Ph2}(CN-
2,6-C6H3Me2)2(µ-dppm)2], in which the Pd-Pd unit is bridged by a κ2-
P,C-[Ph2PCHP(dO)Ph2]- ligand, is known: Rashidi, M.; Vittal, J . J .;
Puddephatt, R. J . J . Chem. Soc., Dalton Trans. 1994, 1283.
(23) See for example: Allen, F. H.; Kennard, O.; Watson, D. G.;
Orpen, A. G.; Brammer, L.; Taylor, R. J . Chem. Soc., Perkin Trans. 2
1987, S1.
(24) See for example: Seddon, E. A.; Seddon, K. R. In The Chemistry
of Ruthenium; Elsevier: Amsterdam, 1984, and references therein.

3432 Organometallics, Vol. 23, No. 14, 2004
Cadierno et al.
Sch em e 5
3J HH ) 6.9 Hz, CH(CH3)2), 1.94 (s, 3H, CH3), 2.07 (dd, 1H, 2J HP
) 6.7 and 6.7 Hz, PCHP), 2.20 (m, 1H, CH(CH3)2), 4.86 and
Exp er im en ta l Section
The manipulations were performed under an atmosphere
of dry nitrogen using vacuum-line and standard Schlenk
techniques. Solvents were dried by standard methods and
distilled under nitrogen before use. All reagents were obtained
from commercial suppliers and used without further purifica-
tion with the exception of compounds [RuCl(η6-p-cymene)(κ2-
P,X-Ph2PCH2P{dNP(dX)(OR)2}Ph2)][SbF6] (X ) O, R ) Et
(1a ), Ph (1b); X ) S, R ) Et (2a ), Ph (2b)),8 [Ru(η6-p-cymene)-
(κ3-P,N,X-Ph2PCH2P{dNP(dX)(OR)2}Ph2)][SbF6]2 (X ) O, R )
Et (5a ), Ph (5b); X ) S, R ) Et (6a ), Ph (6b)),8 Ph2PCH2P{d
NP(dS)(OEt)2}Ph2,8b and [{Ru(η6-C6H6)(µ-Cl)Cl}2],28 which
were prepared by following the methods described in the
literature. Infrared spectra were recorded on a Perkin-Elmer
1720-XFT spectrometer. The conductivities were measured at
room temperature, in ca. 10-3 mol dm-3 acetone solutions, with
a J enway PCM3 conductimeter. The C, H, and N analyses
were carried out with a Perkin-Elmer 2400 microanalyzer.
NMR spectra were recorded on a Bruker DPX300 instrument
at 300 MHz (1H), 121.5 MHz (31P), or 75.4 MHz (13C) using
SiMe4 or 85% H3PO4 as standard. DEPT experiments have
been carried out for all the compounds reported in this paper.
Syn th esis of [Ru Cl(K2-P ,C-P h 2P CHP {dNP (dX)(OR)2}-
P h 2)(η6-p-cym en e)] (X ) O, R ) Et (3a ), P h (3b); X ) S, R
) Et (4a ), P h (4b)). A solution of the corresponding complex
[RuCl(η6-p-cymene)(κ2-P,X-Ph2PCH2P{dNP(dX)(OR)2}Ph2)]-
[SbF6] (1-2a ,b) (0.2 mmol) in 30 mL of THF was treated, at
room temperature, with NaH (0.005 g, 0.21 mmol) for 30 min.
After removing the solvent under reduced presure, the solid
residue was extracted with dichloromethane and filtered over
Kieselguhr. The resulting solution was then concentrated to
ca. 2 mL, and 50 mL of hexanes was added, yielding a
microcrystalline yellow solid, which was washed with hexanes
(3 × 10 mL) and vaccum-dried. 3a : Yield 99% (0.159 g). Anal.
Calcd for RuC39H45O3P3ClN: C, 58.17; H, 5.63; N, 1.74.
Found: C, 57.90; H, 5.46; N, 1.63. 31P{1H} NMR (C6D6): δ 1.53
(d, 2J PP ) 34.4 Hz, (EtO)2PdO), 7.18 (d, 2J PP ) 25.1 Hz, Ph2P),
3
6.05 (d, 1H each, J HH ) 5.7 Hz, CH of p-cymene), 5.17 and
3
5.75 (d, 1H each, J HH ) 6.0 Hz, CH of p-cymene), 6.79-8.54
1
(m, 30H, Ph) ppm. 13C{1H} NMR (CD2Cl2): δ 8.71 (ddd, J CP
3
) 102.8 and 21.0 Hz, J CP ) 11.7 Hz, PCHP), 18.93 (s, CH3),
22.91 and 24.43 (s, CH(CH3)2), 31.35 (s, CH(CH3)2), 79.83,
2
84.87, 85.11 and 91.50 (s, CH of p-cymene), 99.59 (d, J CP
)
2
7.6 Hz, C of p-cymene), 109.87 (d, J CP ) 4.1 Hz, C of
p-cymene), 120.47-147.68 (m, Ph), 153.56 (d, J CP ) 6.4 Hz,
Cipso of OPh), 153.66 (d, J CP ) 7.0 Hz, Cipso of OPh) ppm. 4a :
2
2
Yield 67% (0.110 g). Anal. Calcd for RuC39H45P3O2ClNS‚1/
4CH2Cl2: C, 55.95; H, 5.44; N, 1.66. Found: C, 56.09; H, 5.29;
N, 1.56. 31P{1H} NMR (C6D6): δ 7.04 (d, 2J PP ) 24.4 Hz, Ph2P),
2
2
18.61 (dd, J PP ) 24.4 and 12.6 Hz, Ph2PdN), 58.13 (d, J PP
)
12.6 Hz, (EtO)2PdS) ppm. 1H NMR (C6D6): δ 1.15 (t, 3H, 3J HH
3
) 7.2 Hz, OCH2CH3), 1.18 and 1.20 (d, 3H each, J HH ) 6.8
Hz, CH(CH3)2), 1.25 (t, 3H, 3J HH ) 7.0 Hz, OCH2CH3), 2.13 (s,
2
3H, CH3), 2.14 (dd, 1H, J HP ) 7.0 and 7.0 Hz, PCHP), 2.40
(m, 1H, CH(CH3)2), 4.28 (m, 4H, OCH2CH3), 5.09 and 6.43 (d,
3
1H each, J HH ) 5.7 Hz, CH of p-cymene), 5.34 and 6.01 (d,
1H each, 3J HH ) 6.0 Hz, CH of p-cymene), 6.98-8.67 (m, 20H,
Ph) ppm. 13C{1H} NMR (CD2Cl2): δ 7.06 (ddd, J CP ) 104.3
1
3
3
and 19.0 Hz, J CP ) 8.5 Hz, PCHP), 16.96 (d, J CP ) 8.6 Hz,
OCH2CH3), 17.11 (d, 3J CP ) 7.1 Hz, OCH2CH3), 19.68 (s, CH3),
23.63 and 25.05 (s, CH(CH3)2), 31.98 (s, CH(CH3)2), 62.80 (d,
2J CP ) 4.2 Hz, OCH2CH3), 63.54 (d, 2J CP ) 4.8 Hz, OCH2CH3),
80.95, 85.66, and 85.94 (s, CH of p-cymene), 91.13 (d, J CP
3.0 Hz, CH of p-cymene), 100.61 (d, J CP ) 7.5 Hz, C of
p-cymene), 110.52 (d, J CP ) 4.1 Hz, C of p-cymene), 120.05-
136.58 (m, Ph) ppm. 4b: Yield 91% (0.167 g). Anal. Calcd for
2
)
2
2
RuC47H45P3O2ClNS: C, 61.53; H, 4.94; N, 1.53. Found: C,
61.60; H, 4.97; N, 1.48. 31P{1H} NMR (C6D6): δ 6.70 (d, 2J PP
)
2
25.3 Hz, Ph2P), 22.80 (dd, J PP ) 25.3 and 11.3 Hz, Ph2PdN),
48.73 (d, 2J PP ) 11.3 Hz, (PhO)2PdS) ppm. 1H NMR (C6D6): δ
2
1.16 (br, 6H, CH(CH3)2), 2.10 (s, 3H, CH3), 2.16 (dd, 1H, J HP
) 7.8 and 7.8 Hz, PCHP), 2.36 (m, 1H, CH(CH3)2), 5.06 and
3
6.25 (d, 1H each, J HH ) 5.6 Hz, CH of p-cymene), 5.29 and
2
1
19.53 (dd, J PP ) 34.4 and 25.1 Hz, Ph2PdN) ppm. H NMR
3
5.95 (d, 1H each, J HH ) 6.0 Hz, CH of p-cymene), 6.97-8.72
(C6D6): δ 1.17 and 1.26 (d, 3H each, 3J HH ) 6.9 Hz, CH(CH3)2),
1
(m, 30H, Ph) ppm. 13C{1H} NMR (CD2Cl2): δ 10.04 (ddd, J CP
3
3
1.22 (t, 3H, J HH ) 7.3 Hz, OCH2CH3), 1.31 (t, 3H, J HH ) 7.0
Hz, OCH2CH3), 2.08 (s, 3H, CH3), 2.22 (dd, 1H, 2J HP ) 7.0 and
7.0 Hz, PCHP), 2.38 (m, 1H, CH(CH3)2), 4.26 (m, 4H, OCH2-
3
) 104.5 and 21.6 Hz, J CP ) 12.2 Hz, PCHP), 18.93 (s, CH3),
22.84 and 24.35 (s, CH(CH3)2), 31.26 (s, CH(CH3)2), 80.11,
2
84.55, 85.61, and 91.56 (s, CH of p-cymene), 99.38 (d, J CP
)
3
CH3), 5.02 and 6.37 (d, 1H each, J HH ) 5.3 Hz, CH of
2
7.6 Hz, C of p-cymene), 109.97 (d, J CP ) 4.1 Hz, C of
p-cymene), 120.33-136.73 (m, Ph), 153.20 and 153.31 (br, Cipso
of OPh) ppm.
3
p-cymene), 5.33 and 5.99 (d, 1H each, J HH ) 5.7 Hz, CH of
p-cymene), 7.02-8.71 (m, 20H, Ph) ppm. 13C{1H} NMR (CD2-
1
3
Cl2): δ 9.23 (ddd, J CP ) 104.4 and 19.8 Hz, J CP ) 11.1 Hz,
Syn th esis of [Ru (K3-P ,C,X-P h 2P CHP {dNP (dX)(OR)2}-
P h 2)(η6-p-cym en e)][SbF 6] (X ) O, R ) Et (7a ), P h (7b); X
) S, R ) Et (8a ), P h (8b)). Meth od A. A solution of the
corresponding neutral complex [RuCl(κ2-P,C-Ph2PCHP{dNP-
(dX)(OR)2}Ph2)(η6-p-cymene)] (3-4a ,b) (0.2 mmol) in 40 mL
of CH2Cl2 was treated, at room temperature and in the absence
of light, with AgSbF6 (0.072 g, 0.21 mmol) for 1 h. The AgCl
formed was then filtered off (Kieselghur) and the resulting
solution concentrated to ca. 2 mL. Addition of hexanes (ca. 30
mL) gave a yellow microcrystalline solid, which was filtered,
washed with hexanes (3 × 20 mL), and vacuum-dried. 7a :
Yield 93% (0.187 g). Anal. Calcd for RuC39H45F6O3P3NSb: C,
46.59; H, 4.51; N, 1.39. Found: C, 46.88; H, 4.39; N, 1.37.
3
PCHP), 16.84 and 16.94 (d, J CP ) 7.6 Hz, OCH2CH3), 18.99
(s, CH3), 22.95 and 24.44 (s, CH(CH3)2), 31.38 (s, CH(CH3)2),
2
2
61.24 (d, J CP ) 5.2 Hz, OCH2CH3), 61.31 (d, J CP ) 5.8 Hz,
OCH2CH3), 80.16, 84.82, 85.34, and 91.13 (s, CH of p-cymene),
2
2
99.80 (d, J CP ) 7.6 Hz, C of p-cymene), 110.12 (d, J CP ) 4.1
Hz, C of p-cymene), 126.45-135.84 (m, Ph) ppm. 3b: Yield
92% (0.166 g). Anal. Calcd for RuC47H45O3P3ClN: C, 62.63;
H, 5.03; N, 1.55. Found: C, 62.92; H, 5.01; N, 1.43. 31P{1H}
2
NMR (C6D6): δ -9.93 (d, J PP ) 29.3 Hz, (PhO)2PdO), 6.26
2
2
(d, J PP ) 24.4 Hz, Ph2P), 24.00 (dd, J PP ) 29.3 and 24.4 Hz,
1
Ph2PdN) ppm. H NMR (C6D6): δ 1.04 and 1.06 (d, 3H each,
(28) Bennett, M. A.; Smith, A. K. J . Chem. Soc., Dalton Trans. 1974,
233.
Conductivity (acetone, 20 °C): 117 Ω-1 cm2 mol-1 31P{1H}
.

Cyclometalation in (Arene)ruthenium(II) Complexes
Organometallics, Vol. 23, No. 14, 2004 3433
NMR ((CD3)2CO): δ 8.85 (d, 2J PP ) 16.2 Hz, (EtO)2PdO), 9.87
(d, J PP ) 15.9 Hz, Ph2P), 23.32 (dd, J PP ) 16.2 and 15.9 Hz,
136.08 (m, Ph), 151.77 (d, 2J CP ) 10.4 Hz, Cipso of OPh), 152.49
2
2
2
(d, J CP ) 8.7 Hz, Cipso of OPh) ppm.
1
3
Ph2PdN) ppm. H NMR ((CD3)2CO): δ 1.00 (t, 3H, J HH ) 6.7
Met h od B. A solution of the corresponding complex
[Ru (η6-p-cym en e)(κ3-P ,N,X-P h 2P CH 2P {dNP (dX)(OR)2}-
Ph2)][SbF6]2 (5-6a ,b) (0.2 mmol) in 30 mL of THF was treated,
at room temperature, with NaH (0.005 g, 0.21 mmol) for 30
min. The reaction mixture was then evaporated to dryness and
the solid residue extracted with dichloromethane and filtered
off (Kieselguhr). Concentration of the resulting solution (ca. 2
mL) followed by the addition of hexanes (ca. 30 mL) gave a
yellow microcrystalline solid, which was washed with hexanes
(3 × 20 mL) and vacuum-dried. 7a : Yield 80% (0.176 g). 7b:
Yield 88% (0.177 g). 8a : Yield 93% (0.208 g). 8b: Yield 79%
(0.161 g).
Hz, OCH2CH3), 1.23 (d, 6H, 3J HH ) 7.0 Hz, CH(CH3)2), 1.27 (t,
3
3H, J HH ) 7.1 Hz, OCH2CH3), 1.69 (s, 3H, CH3), 1.89 (d, 1H,
2J HP ) 6.1 Hz, PCHP), 2.51 (m, 1H, CH(CH3)2), 3.96 (m, 4H,
3
OCH2CH3), 4.73 and 5.69 (d, 1H each, J HH ) 5.4 Hz, CH of
3
p-cymene), 5.21 and 5.62 (d, 1H each, J HH ) 5.7 Hz, CH of
p-cymene), 7.05-8.38 (m, 20H, Ph) ppm. 13C{1H} NMR ((CD3)2-
1
3
CO): δ -7.34 (ddd, J CP ) 68.5 and 14.0 Hz, J CP ) 8.0 Hz,
PCHP), 16.30 (d, J CP ) 7.6 Hz, OCH2CH3), 16.51 (d, J CP
8.2 Hz, OCH2CH3), 18.67 (s, CH3), 23.32 and 23.90 (s, CH-
3
3
)
2
(CH3)2), 32.11 (s, CH(CH3)2), 63.09 (d, J CP ) 2.9 Hz, OCH2-
2
CH3), 63.17 (d, J CP ) 4.0 Hz, OCH2CH3), 79.20 and 80.57 (s,
2
Syn th esis of [Ru (K2-C,X-CH2P {dNP (dX)(OR)2}P h 2){K1-
P -P (dO)P h 2}(η6-p-cym en e)] (X ) O, R ) Et (10a ); X ) S,
R ) Et (11a ), P h (11b)). Meth od A. A solution of the
corresponding cationic complex [RuCl(η6-p-cymene)(κ2-P,X-Ph2-
PCH2P{dNP(dX)(OR)2}Ph2)][SbF6] (1-2a ,b) (0.2 mmol) in 30
mL of undistilled THF was treated, at room temperature, with
NaH (0.05 g, 2.1 mmol) for 6 h. After removing the solvent
under reduced presure, the solid residue was extracted with
dichloromethane and filtered over Kieselguhr. The resulting
solution was then concentrated to ca. 2 mL, and 50 mL of
hexanes was added, yielding a microcrystalline yellow solid,
which was washed with hexanes (3 × 10 mL) and vaccum-
CH of p-cymene), 89.69 (d, J CP ) 1.7 Hz, CH of p-cymene),
2
2
89.99 (d, J CP ) 5.2 Hz, CH of p-cymene), 98.67 (d, J CP ) 3.5
Hz, C of p-cymene), 113.18 (s, C of p-cymene), 122.16-137.48
(m, Ph) ppm. 7b: Yield 82% (0.181 g). Anal. Calcd for
RuC47H45F6O3P3NSb‚1/4CH2Cl2: C, 50.54; H, 4.08; N, 1.25.
Found: C, 50.62; H, 4.14; N, 1.17. Conductivity (acetone, 20
°C): 111 Ω-1 cm2 mol-1
.
31P{1H} NMR ((CD3)2CO): δ -0.28
(d, 2J PP ) 17.1 Hz, (PhO)2PdO), 8.37 (d, 2J PP ) 17.1 Hz, Ph2P),
2
1
26.08 (dd, J PP ) 17.1 and 17.1 Hz, Ph2PdN) ppm. H NMR
((CD3)2CO): δ 0.89 (d, 3H, J HH ) 6.6 Hz, CH(CH3)2), 1.22 (d,
3
3
3H, J HH ) 6.9 Hz, CH(CH3)2), 1.63 (s, 3H, CH3), 1.91 (d, 1H,
2J HP ) 6.4 Hz, PCHP), 2.46 (m, 1H, CH(CH3)2), 4.27 and 5.21
(d, 1H each, 3J HH ) 6.5 Hz, CH of p-cymene), 5.57 (br, 2H, CH
of p-cymene), 7.12-8.35 (m, 30H, Ph) ppm. 13C{1H} NMR
((CD3)2CO): δ -6.22 (ddd, 1J CP ) 67.6 and 15.5 Hz, 3J CP ) 7.8
Hz, PCHP), 18.66 (s, CH3), 23.30 and 24.10 (s, CH(CH3)2),
32.30 (s, CH(CH3)2), 76.73 and 81.64 (s, CH of p-cymene), 89.93
dried. 10a : Yield 83% (0.130 g). Anal. Calcd for RuC39
-
H
46O4P3N: C, 59.54; H, 5.89; N, 1.78. Found: C, 59.56; H, 5.91;
2
N, 1.58. 31P{1H} NMR (C6D6): δ 12.50 (d, J PP ) 17.8 Hz,
(EtO)2PdO), 36.63 (dd, 2J PP ) 17.8 Hz, 3J PP ) 14.8 Hz, Ph2Pd
3
1
N), 70.92 (d, J PP ) 14.8 Hz, Ph2PdO) ppm. H NMR (C6D6):
2
2
3
3
(d, J CP ) 5.8 Hz, CH of p-cymene), 92.07 (d, J CP ) 3.2 Hz,
CH of p-cymene), 97.63 and 113.71 (s, C of p-cymene), 120.34-
137.31 (m, Ph), 151.85 and 152.54 (d, J CP ) 7.8 Hz, Cipso of
OPh) ppm. 8a : Yield 92% (0.188 g). Anal. Calcd for RuC39H45
δ 0.82 (t, 3H, J HH ) 7.1 Hz, OCH2CH3), 0.96 (d, 3H, J HH
)
6.7 Hz, CH(CH3)2), 1.15 (d, 3H, 3J HH ) 6.9 Hz, CH(CH3)2), 1.17
2
3
(t, 3H, J HH ) 7.0 Hz, OCH2CH3), 1.71 (s, 3H, CH3), 2.42 (m,
1H, CH(CH3)2), 3.40 and 3.94 (m, 1H each, RuCH2P), 4.06 (m,
-
3
F6P3O2NSSb: C, 45.85; H, 4.44; N, 1.37. Found: C, 46.11; H,
4H, OCH2CH3), 4.63 and 4.69 (d, 1H each, J HH ) 5.8 Hz, CH
4.58; N, 1.51. Conductivity (acetone, 20 °C): 118 Ω-1 cm2 mol-1
.
3
of p-cymene), 5.07 and 5.10 (d, 1H each, J HH ) 6.0 Hz, CH of
2
31P{1H} NMR ((CD3)2CO): δ 4.34 (d, J PP ) 22.3 Hz, Ph2P),
p-cymene), 6.92-8.62 (m, 20H, Ph) ppm. 13C{1H} NMR
(C6D6): δ 0.30 (ddd, 1J CP ) 38.1 Hz, 2J CP ) 16.1 Hz, 3J CP ) 8.3
2
2
30.76 (dd, J PP ) 22.3 and 7.2 Hz, Ph2PdN), 47.75 (d, J PP
)
1
3
7.2 Hz, (EtO)2PdS) ppm. H NMR ((CD3)2CO): δ 0.94 (t, 3H,
Hz, RuCH2P), 15.97 and 16.48 (d, J CP ) 8.4 Hz, OCH2CH3),
17.41 (s, CH3), 21.96 and 22.87 (s, CH(CH3)2), 30.38 (s, CH-
(CH3)2), 62.06 (d, J CP ) 6.0 Hz, OCH2CH3), 62.26 (d, J CP
7.2 Hz, OCH2CH3), 83.67 (d, J CP ) 7.7 Hz, CH of p-cymene),
86.24 and 89.24 (s, CH of p-cymene), 89.20 and 104.48 (s, C of
p-cymene), 93.23 (d, 2J CP ) 4.8 Hz, CH of p-cymene), 127.70-
145.63 (m, Ph) ppm. 11a : Yield 91% (0.146 g). Anal. Calcd
for RuC39H46O3P3NS: C, 58.34; H, 5.78; N, 1.74. Found: C,
58.26; H, 5.66; N, 1.52. 31P{1H} NMR (C6D6): δ 39.85 (dd, 2J PP
3J HH ) 7.0 Hz, OCH2CH3), 1.18 (d, 6H, J HH ) 6.8 Hz, CH-
3
3
2
2
(CH3)2), 1.31 (t, 3H, J HH ) 7.1 Hz, OCH2CH3), 1.69 (s, 3H,
)
2
2
CH3), 2.07 (d, 1H, J HP ) 6.4 Hz, PCHP), 2.44 (m, 1H,
CH(CH3)2), 4.04 (m, 4H, OCH2CH3), 5.19 and 5.53 (d, 1H each,
3J HH ) 5.5 Hz, CH of p-cymene), 5.32 and 5.73 (d, 1H each,
3J HH ) 6.0 Hz, CH of p-cymene), 7.18-8.40 (m, 20H, Ph) ppm.
13C{1H} NMR ((CD3)2CO): δ -7.42 (ddd, 1J CP ) 68.2 and 13.7
Hz, 3J CP ) 9.1 Hz, PCHP), 15.56 (d, 3J CP ) 8.0 Hz, OCH2CH3),
3
3
2
15.69 (d, J CP ) 10.6 Hz, OCH2CH3), 18.07 (s, CH3), 23.01 (s,
) 26.6 Hz, J PP ) 18.8 Hz, Ph2PdN), 55.73 (dd, J PP ) 26.6
2
3
3
2C, CH(CH3)2), 31.18 (s, CH(CH3)2), 62.52 (d, J CP ) 6.9 Hz,
Hz, J PP ) 16.8 Hz, (EtO)2PdS), 73.75 (dd, J PP ) 18.8 and
16.8 Hz, Ph2PdO) ppm. 1H NMR (C6D6): δ 0.73 (t, 3H, 3J HH
7.0 Hz, OCH2CH3), 1.06 (d, 3H, 3J HH ) 6.6 Hz, CH(CH3)2), 1.15
OCH2CH3), 63.84 (d, 2J CP ) 7.4 Hz, OCH2CH3), 85.04 and 85.16
(s, CH of p-cymene), 90.31 (d, 2J CP ) 2.7 Hz, CH of p-cymene),
90.95 (d, 2J CP ) 4.8 Hz, CH of p-cymene), 102.09 (d, 2J CP ) 4.2
)
3
3
(d, 3H, J HH ) 6.8 Hz, CH(CH3)2), 1.20 (t, 3H, J HH ) 7.3 Hz,
OCH2CH3), 1.92 (s, 3H, CH3), 2.13 (m, 1H, CH(CH3)2), 3.07
and 3.28 (m, 1H each, RuCH2P), 4.12 (m, 4H, OCH2CH3), 4.47
2
Hz, C of p-cymene), 113.28 (d, J CP ) 2.6 Hz, C of p-cymene),
121.40-135.99 (m, Ph) ppm. 8b: Yield 90% (0.201 g). Anal.
Calcd for RuC47H45F6P3O2NSSb‚1/2CH2Cl2: C, 49.17; H, 3.99;
N, 1.21. Found: C, 49.22; H, 3.94; N, 1.23. Conductivity
.
(acetone, 20 °C): 120 Ω-1 cm2 mol-1 31P{1H} NMR ((CD3)2-
3
and 5.23 (d, 1H each, J HH ) 5.7 Hz, CH of p-cymene), 4.70
3
and 5.36 (d, 1H each, J HH ) 5.4 Hz, CH of p-cymene), 6.88-
8.53 (m, 20H, Ph) ppm. 13C{1H} NMR (C6D6): δ -2.74 (ddd,
1J CP ) 41.1 Hz, 2J CP ) 14.9 Hz, 3J CP ) 11.7 Hz, RuCH2P), 15.64
2
3
CO): δ 5.44 (dd, J PP ) 22.6 Hz, J PP ) 4.5 Hz, Ph2P), 31.29
2
2
3
3
(dd, J PP ) 22.6 and 9.0 Hz, Ph2PdN), 40.94 (dd, J PP ) 9.0
(d, J CP ) 8.2 Hz, OCH2CH3), 16.26 (d, J CP ) 8.7 Hz,
OCH2CH3), 17.90 (s, CH3), 20.69 and 24.21 (s, CH(CH3)2), 30.34
3
1
Hz, J PP ) 4.5 Hz, (PhO)2PdS) ppm. H NMR ((CD3)2CO): δ
1.06 (d, 3H, 3J HH ) 6.0 Hz, CH(CH3)2), 1.15 (d, 3H, 3J HH ) 5.8
Hz, CH(CH3)2), 1.58 (s, 3H, CH3), 1.98 (br, 1H, PCHP), 2.27
(m, 1H, CH(CH3)2), 4.73 (br, 1H, CH of p-cymene), 5.16 (d, 1H,
3J HH ) 4.7 Hz, CH of p-cymene), 5.63 (m, 2H, CH of p-cymene),
6.71-8.34 (m, 30H, Ph) ppm. 13C{1H} NMR ((CD3)2CO): δ
-8.69 (ddd, J CP ) 69.2 and 11.5 Hz, J CP ) 11.5 Hz, PCHP),
18.57 (s, CH3), 22.62 and 24.00 (s, CH(CH3)2), 31.39 (s, CH-
(CH3)2), 84.76 and 85.16 (s, CH of p-cymene), 90.82 (d, J CP
5.2 Hz, CH of p-cymene), 93.00 (d, J CP ) 3.5 Hz, CH of
p-cymene), 101.88 and 113.54 (s, C of p-cymene), 121.05-
2
(s, CH(CH3)2), 62.17 (d, J CP ) 5.2 Hz, OCH2CH3), 62.47 (d,
2J CP ) 7.0 Hz, OCH2CH3), 86.88 (d, J CP ) 7.6 Hz, CH of
2
p-cymene), 87.27 (s, CH of p-cymene), 90.46 (d, 2J CP ) 3.5 Hz,
2
CH of p-cymene), 92.83 (d, J CP ) 2.9 Hz, CH of p-cymene),
94.00 and 110.48 (s, C of p-cymene), 126.54-151.31 (m, Ph)
ppm. 11b: Yield 78% (0.140 g). Anal. Calcd for RuC47H46O3P3-
NS: C, 62.80; H, 5.16; N, 1.56. Found: C, 62.60; H, 5.26; N,
1
3
2
2
3
)
1.52. 31P{1H} NMR (C6D6): δ 42.46 (dd, J PP ) 20.8 Hz, J PP
2
2
3
) 19.0 Hz, Ph2PdN), 47.79 (dd, J PP ) 20.8 Hz, J PP ) 19.0
Hz, (PhO)2PdS), 71.44 (dd, 3J PP ) 19.0 and 19.0 Hz, Ph2PdO)

3434 Organometallics, Vol. 23, No. 14, 2004
Cadierno et al.
ppm. 1H NMR (C6D6): δ 1.12 (d, 3H, 3J HH ) 6.6 Hz, CH(CH3)2),
yellow solid, was prepared as described for complexes 10-
11a ,b (method A) starting from [RuCl(η6-C6H6)(κ2-P,S-Ph2-
PCH2P{dNP(dS)(OEt)2}Ph2)][SbF6] (2a ′) (0.200 g, 0.2 mmol)
and NaH (0.048 g, 2 mmol). Yield: 77% (0.115 g). Anal. Calcd
for RuC35H38O3P3NS: C, 56.29; H, 5.13; N, 1.88. Found: C,
56.54; H, 5.15; N, 1.95. 31P{1H} NMR (C6D6): δ 40.40 (dd, 2J PP
3
1.24 (d, 3H, J HH ) 6.9 Hz, CH(CH3)2), 1.99 (s, 3H, CH3), 2.32
(m, 2H, CH(CH3)2 and RuCH2P), 2.75 (m, 1H, RuCH2P), 4.52
3
and 5.44 (d, 1H each, J HH ) 5.8 Hz, CH of p-cymene), 4.81
3
and 5.53 (d, 1H each, J HH ) 5.6 Hz, CH of p-cymene), 6.71-
8.51 (m, 30H, Ph) ppm. 13C{1H} NMR (C6D6): δ -2.17 (ddd,
1J CP ) 40.5 Hz, 2J CP ) 13.7 Hz, 3J CP ) 11.2 Hz, RuCH2P), 17.85
(s, CH3), 20.47 and 24.60 (s, CH(CH3)2), 30.39 (s, CH(CH3)2),
3
2
) 26.3 Hz, J PP ) 19.1 Hz, Ph2PdN), 54.42 (dd, J PP ) 26.3
3
3
Hz, J PP ) 16.0 Hz, (EtO)2PdS), 74.70 (dd, J PP ) 19.1 and
2
1
86.95 (d, J CP ) 7.6 Hz, CH of p-cymene), 87.79, 91.22, and
16.0 Hz, Ph2PdO) ppm. H NMR (C6D6): δ 0.80 and 1.18 (t,
3H each, 3J HH ) 7.0 Hz, OCH2CH3), 3.30 and 3.49 (m, 1H each,
RuCH2P), 4.07 (m, 4H, OCH2CH3), 5.13 (s, 6H, C6H6), 6.91-
8.54 (m, 20H, Ph) ppm. 13C{1H} NMR (C6D6): δ -4.37 (ddd,
1J CP ) 41.1 Hz, 2J CP ) 14.6 Hz, 3J CP ) 11.5 Hz, RuCH2P), 15.70
93.58 (s, CH of p-cymene), 92.70 and 111.90 (s, C of p-cymene),
120.85-144.51 (m, Ph), 151.78 (d, 2J CP ) 8.5 Hz, Cipso of OPh),
2
153.27 (d, J CP ) 12.3 Hz, Cipso of OPh) ppm.
Meth od B. A solution of the corresponding neutral complex
[RuCl(κ2-P,C-Ph2PCHP{dNP(dX)(OR)2}Ph2)(η6-p-cymene)]
(3-4a ,b) (0.2 mmol) in 30 mL of undistilled THF was treated,
at room temperature, with NaH (0.05 g, 2.1 mmol) for 6 h.
Workup as described in method A allows the isolation of
complexes 10a and 11a ,b in 80% (0.126 g), 85% (0.136 g), and
79% (0.142 g) yield, respectively.
Meth od C. A solution of the corresponding cationic complex
[Ru(κ3-P,C,X-Ph2PCHP{dNP(dX)(OR)2}Ph2)(η6-p-cymene)][S-
bF6] (7-8a ,b) (0.2 mmol) in 30 mL of undistilled THF was
treated, at room temperature, with NaH (0.05 g, 2.1 mmol)
for 6 h. Workup as described in method A allows the isolation
of complexes 10a and 11a ,b in 82% (0.129 g), 87% (0.140 g),
and 74% (0.133 g) yield, respectively.
3
3
(d, J CP ) 7.5 Hz, OCH2CH3), 16.23 (d, J CP ) 8.4 Hz,
2
2
OCH2CH3), 62.41 (d, J CP ) 5.8 Hz, OCH2CH3), 62.68 (d, J CP
2
) 6.6 Hz, OCH2CH3), 89.32 (d, J CP ) 2.7 Hz, C6H6), 126.55-
151.30 (m, Ph) ppm.
Syn th esis of [Ru (K2-C,X-CH2P {dNP (dX)(OR)2}P h 2){K1-
P -P (OH)P h 2}(η6-p-cym en e)][BF 4] (X ) O, R ) Et (12a ); X
) S, R ) Et (13a ), P h (13b)). A solution of the corresponding
neutral complex [Ru(κ2-C,X-CH2P{dNP(dX)(OR)2}Ph2){κ1-P-
P(dO)Ph2}(η6-p-cymene)] (10-11a ,b) (0.2 mmol) in 30 mL of
dichloromethane was treated, at room temperature, with a
solution of HBF4 in diethyl ether (0.14 mL of a 1.6 M solution,
0.22 mmol) for 30 min. Concentration of the resulting solution
(ca. 2 mL) followed by the addition of hexanes (ca. 30 mL) gave
a yellow microcrystalline solid, which was washed with hex-
anes (3 × 20 mL) and vacuum-dried. 12a : Yield 75% (0.131
g). Anal. Calcd for RuC39H47F4O4P3BN: C, 53.56; H, 5.42; N,
1.60. Found: C, 53.51; H, 5.45; N, 1.85. Conductivity (acetone,
Syn t h esis of [R u Cl2(η6-C6H 6)(K1-P -P h 2P CH2P {dNP -
(dS)(OEt)2}P h 2)]. A solution of [{Ru(η6-C6H6)(µ-Cl)Cl}2] (0.250
g, 0.5 mmol) and the iminophosphorane-phosphine ligand Ph2-
PCH2P{dNP(dS)(OEt)2}Ph2 (0.552 g, 1 mmol) in 50 mL of
CH2Cl2 was stirred at room temperature for 1 h. The solution
was then concentrated (ca. 5 mL) and diethyl ether (ca. 30 mL)
was added, yielding an orange solid, which was washed with
diethyl ether (3 × 10 mL) and vacuum-dried. Yield: 65% (0.521
g). Anal. Calcd for RuC35H38P3Cl2O2NS: C, 52.44; H, 4.78; N,
1.75. Found: C, 52.62; H, 4.45; N, 1.59. 31P{1H} NMR (CD2-
Cl2): δ 11.09 (dd, 2J PP ) 39.1 and 24.4 Hz, Ph2PdN), 23.53 (d,
20 °C): 121 Ω-1 cm2 mol-1
.
31P{1H} NMR ((CD3)2CO): δ 9.90
2
3
3
(dd, J PP ) 6.6 Hz, J PP ) 4.4 Hz, (EtO)2PdO), 57.41 (dd, J PP
2
3
) 10.8 Hz, J PP ) 6.6 Hz, Ph2PdN), 112.34 (dd, J PP ) 10.8
1
and 4.4 Hz, Ph2POH) ppm. H NMR ((CD3)2CO): δ 0.73 and
3
1.51 (t, 3H each, J HH ) 6.8 Hz, OCH2CH3), 0.99 and 1.51 (d,
3
3H each, J HH ) 6.8 Hz, CH(CH3)2), 1.95 (s, 3H, CH3), 2.68
(m, 2H, CH(CH3)2 and RuCH2P), 3.70 (m, 1H, RuCH2P), 4.21
2
2J PP ) 39.1 Hz, Ph2P), 59.18 (d, J PP ) 24.4 Hz, (EtO)2PdS)
3
(m, 4H, OCH2CH3), 4.79 and 5.37 (d, 1H each, J HH ) 5.1 Hz,
3
ppm. 1H NMR (CD2Cl2): δ 1.05 (t, 6H, J HH ) 6.9 Hz,
3
CH of p-cymene), 5.06 and 5.58 (d, 1H each, J HH ) 5.6 Hz,
OCH2CH3), 3.50 (m, 4H, OCH2CH3), 3.91 (dd, 2H, 2J HP ) 10.1
and 10.1 Hz, PCH2P), 5.29 (s, 6H, C6H6), 7.25-8.08 (m, 20H,
CH of p-cymene), 6.75-8.21 (m, 20H, Ph), 11.60 (br, 1H, POH)
ppm. 13C{1H} NMR ((CD3)2CO): δ -12.86 (ddd, J CP ) 64.1
1
3
Ph) ppm. 13C{1H} NMR (CD2Cl2): δ 16.23 (d, J CP ) 8.9 Hz,
Hz, 2J CP ) 12.8 Hz, 3J CP ) 12.8 Hz, RuCH2P), 17.46 (d, 3J CP
)
1
3
3
OCH2CH3), 22.61 (ddd, J CP ) 76.9 and 19.2 Hz, J CP ) 6.7
Hz, PCH2P), 61.63 (d, 2J CP ) 6.3 Hz, OCH2CH3), 88.68 (d, 2J CP
) 3.4 Hz, C6H6), 128.35-134.38 (m, Ph) ppm.
6.4 Hz, OCH2CH3), 18.09 (d, J CP ) 7.6 Hz, OCH2CH3), 20.33
(s, CH3), 23.41 and 25.47 (s, CH(CH3)2), 31.20 (s, CH(CH3)2),
65.47 and 66.25 (d, 2J CP ) 5.8 Hz, OCH2CH3), 84.71 and 88.92
(s, CH of p-cymene), 91.58 (d, 2J CP ) 3.5 Hz, CH of p-cymene),
95.07 (d, 2J CP ) 8.7 Hz, CH of p-cymene), 110.64 (d, 2J CP ) 3.5
Hz, C of p-cymene), 118.47 (s, C of p-cymene), 129.94-144.56
(m, Ph) ppm. 13a : Yield 60% (0.107 g). Anal. Calcd for
RuC39H47F4P3O3BNS‚1/4CH2Cl2: C, 51.70; H, 5.25; N, 1.53.
Found: C, 51.72; H, 5.17; N, 1.23. Conductivity (acetone, 20
Syn t h esis of [R u Cl(η6-C6H 6)(K2-P ,S-P h 2P CH2P {dNP -
(dS)(OEt)2}P h 2)][SbF 6] (2a ′). A solution of the neutral
complex [RuCl2(η6-C6H6)(κ1-P-Ph2PCH2P{dNP(dS)(OEt)2}-
Ph2)] (0.400 g, 0.5 mmol) in 50 mL of dichloromethane was
treated, at room temperature and in the absence of light, with
AgSbF6 (0.172 g, 0.5 mmol) for 1 h. After the AgCl formed was
filtered off (Kieselguhr), the solution was concentrated to ca.
2 mL, and 50 mL of diethyl ether was then added, yielding an
orange microcrystalline solid, which was washed with diethyl
ether (3 × 20 mL) and vacuum-dried. Yield: 88% (0.441 g).
Anal. Calcd for RuC35H38F6P3O2ClNSSb: C, 41.96; H, 3.82; N,
1.40. Found: C, 41.63; H, 3.54; N, 1.66. Conductivity (acetone,
°C): 114 Ω-1 cm2 mol-1
.
31P{1H} NMR ((CD3)2CO): δ 40.00
2
3
2
(dd, J PP ) 26.4 Hz, J PP ) 19.3 Hz, Ph2PdN), 53.48 (dd, J PP
) 26.4 Hz, 3J PP ) 22.7 Hz, (EtO)2PdS), 117.61 (dd, 3J PP ) 22.7
and 19.3 Hz, Ph2POH) ppm. 1H NMR ((CD3)2CO): δ 0.91 (t,
3
3
3H, J HH ) 6.8 Hz, OCH2CH3), 1.02 (d, 3H, J HH ) 6.8 Hz,
CH(CH3)2), 1.12 (d, 3H, 3J HH ) 6.9 Hz, CH(CH3)2), 1.49 (t, 3H,
3J HH ) 7.0 Hz, OCH2CH3), 2.00 (s, 3H, CH3), 2.06 and 2.55
(m, 1H each, RuCH2P), 2.45 (m, 1H, CH(CH3)2), 4.37 (m, 4H,
20 °C): 111 Ω-1 cm2 mol-1
.
31P{1H} NMR (CD2Cl2): δ 17.16
2
3
(dd, J PP ) 28.7 and 3.8 Hz, Ph2PdN), 26.85 (dd, J PP ) 12.1
2
2
3
3
Hz, J PP ) 3.8 Hz, Ph2P), 54.30 (dd, J PP ) 28.7 Hz, J PP
)
OCH2CH3), 5.10 (d, 2H, J HH ) 6.0 Hz, CH of p-cymene), 5.42
12.1 Hz, (EtO)2PdS) ppm. 1H NMR (CD2Cl2): δ 1.09 (t, 3H,
3
and 5.47 (d, 1H each, J HH ) 5.6 Hz, CH of p-cymene), 7.10-
3J HH ) 6.9 Hz, OCH2CH3), 1.59 (t, 3H, J HH ) 7.0 Hz,
3
8.35 (m, 20H, Ph), 8.91 (br, 1H, POH) ppm. 13C{1H} NMR
((CD3)2CO): δ -2.45 (ddd, 1J CP ) 42.9 Hz, 2J CP ) 14.7 Hz, 3J CP
OCH2CH3), 3.29 and 4.62 (m, 1H each, PCH2P), 4.10 (m, 4H,
OCH2CH3), 5.74 (s, 6H, C6H6), 7.10-7.62 (m, 20H, Ph) ppm.
13C{1H} NMR (CD2Cl2): δ 15.95 (d, 3J CP ) 7.7 Hz, OCH2CH3),
16.48 (d, 3J CP ) 8.3 Hz, OCH2CH3), 25.52 (dd, 1J CP ) 59.2 and
3
) 11.3 Hz, RuCH2P), 16.46 and 17.13 (d, J CP ) 8.3 Hz,
OCH2CH3), 18.58 (s, CH3), 21.73 and 23.94 (s, CH(CH3)2), 30.93
2
(s, CH(CH3)2), 63.97 (d, J CP ) 5.8 Hz, OCH2CH3), 64.75 (d,
2
2J CP ) 8.3 Hz, OCH2CH3), 90.04 (d, J CP ) 6.2 Hz, CH of
2
17.7 Hz, PCH2P), 64.88 (d, J CP ) 10.2 Hz, OCH2CH3), 65.01
2
2
p-cymene), 91.53 (d, 2J CP ) 5.0 Hz, CH of p-cymene), 91.78 (d,
2J CP ) 2.5 Hz, CH of p-cymene), 95.70 (d, 2J CP ) 3.7 Hz, CH of
p-cymene), 102.16 and 114.23 (s, C of p-cymene), 129.30-
141.40 (m, Ph) ppm. 13b: Yield 64% (0.126 g). Anal. Calcd
(d, J CP ) 7.2 Hz, OCH2CH3), 91.36 (d, J CP ) 2.8 Hz, C6H6),
124.84-138.31 (m, Ph) ppm.
Syn th esis of [Ru (K2-C,S-CH2P {dNP (dS)(OEt)2}P h 2){K1-
P -P (dO)P h 2}(η6-C6H6)] (11a ′). Complex 11a ′, isolated as a

Cyclometalation in (Arene)ruthenium(II) Complexes
Organometallics, Vol. 23, No. 14, 2004 3435
Ta ble 1. Cr ysta l Da ta a n d Str u ctu r e Refin em en t
for 3b a n d 11a ’
for RuC47H46F4O3P3BNS‚1/4CH2Cl2: C, 56.36; H, 4.65; N, 1.39.
Found: C, 56.40; H, 4.94; N, 1.39. Conductivity (acetone, 20
°C): 116 Ω-1 cm2 mol-1
.
31P{1H} NMR ((CD3)2CO): δ 43.34
3b
11a ′
2
3
3
(dd, J PP ) 22.6 Hz, J PP ) 19.9 Hz, Ph2PdN), 47.00 (dd, J PP
chemical formula
RuC47H45O3P3NCl
RuC35H38O3P3NS‚
H2O
2
3
) 24.4 Hz, J PP ) 22.6 Hz, (PhO)2PdS), 115.70 (dd, J PP
)
24.4 and 19.9 Hz, Ph2POH) ppm. 1H NMR ((CD3)2CO): δ 0.99
fw
901.27
764.72
3
3
(d, 3H, J HH ) 6.6 Hz, CH(CH3)2), 1.09 (d, 3H, J HH ) 6.5 Hz,
CH(CH3)2), 1.95 (s, 3H, CH3), 2.06 and 2.44 (m, 1H each,
RuCH2P), 2.37 (m, 1H, CH(CH3)2), 5.01 and 5.55 (d, 1H each,
3J HH ) 5.9 Hz, CH of p-cymene), 5.14 and 5.42 (d, 1H each,
3J HH ) 4.8 Hz, CH of p-cymene), 6.76-8.04 (m, 30H, Ph), 9.00
(br, 1H, POH) ppm. 13C{1H} NMR ((CD3)2CO): δ -3.07 (ddd,
1J CP ) 41.3 Hz, 2J CP ) 15.5 Hz, 3J CP ) 12.2 Hz, RuCH2P), 18.44
(s, CH3), 20.81 and 24.19 (s, CH(CH3)2), 30.82 (s, CH(CH3)2),
T (K)
120(2)
293(2)
1.71073
triclinic
P1h (No. 2)
wavelength (Å)
cryst syst
space group
cryst size, mm
a, Å
1.54180
triclinic
P1h (No. 2)
0.10 × 0.05 × 0.025 0.26 × 0.16 × 0.13
10.3434(5)
12.6084(7)
16.4528(9)
84.595(3)
76.211(3)
82.999(3)
2
10.859(4)
12.174(2)
15.189(4)
69.71(3)
87.735(19)
69.09(2)
2
1751.2(8)
1.450
0.683
b, Å
c, Å
R, deg
2
2
88.58 (d, J CP ) 7.6 Hz, CH of p-cymene), 90.28 (d, J CP ) 2.3
Hz, CH of p-cymene), 91.15 (s, CH of p-cymene), 96.05 (d, 2J CP
) 4.1 Hz, CH of p-cymene), 98.80 and 116.21 (s, C of p-cymene),
121.11-142.88 (m, Ph), 151.72 (d, 2J CP ) 8.7 Hz, Cipso of OPh),
â, deg
γ, deg
Z
V, Å3
2063.6(2)
1.450
5.110
F
calcd, g cm-3
2
152.98 (d, J CP ) 12.2 Hz, Cipso of OPh) ppm.
µ, mm-1
Syn th esis of [Ru (K2-C,X-CH2P {dNP (dX)(OR)2}P h 2){K1-
P -P (OMe)P h 2}(η6-p-cym en e)][CF 3SO3] (X ) O, R ) Et
(14a ); X ) S, R ) Et (15a ), P h (15b)). A solution of the
corresponding neutral complex [Ru(κ2-C,X-CH2P{dNP(dX)-
(OR)2}Ph2){κ1-P-P(dO)Ph2}(η6-p-cymene)] (10-11a,b) (0.2 mmol)
in 30 mL of dichloromethane was treated, at room tempera-
ture, with MeOSO2CF3 (0.025 mL, 0.22 mmol) for 30 min.
Concentration of the resulting solution (ca. 2 mL) followed by
the addition of hexanes (ca. 30 mL) gave a yellow microcrys-
talline solid, which was washed with hexanes (3 × 20 mL) and
vacuum-dried. 14a : Yield 70% (0.133 g). Anal. Calcd for
RuC41H49O7F3P3NS: C, 51.79; H, 5.19; N, 1.47. Found: C,
F(000)
928
788
θ range, deg
index ranges
2.77 to 69.53
-11 e h e 12
-14 e k e 14
0 e l e 19
1.44 to 25.98
-13 e h e 13
-14 e k e 14
-18 e l e 18
100.0%
completeness to θmax 95.2%
no. of data coll
no. of unique data
no. of params/
restraints
33 680
14 408
7370 (Rint ) 0.029) 6860 (Rint ) 0.1202)
505/0
414/2
goodness of fit on F2 1.038
1.005
0.0597, 0.9784
0.0587
0.1171
0.2021
0.1632
0.697 and -0.988
weight function (a, b) 0.0270, 0.0000
R1a [I > 2σ(I)]
wR2a [I > 2σ(I)]
R1 (all data)
0.0428
0.1041
0.0628
0.1120
51.57; H, 4.96; N, 1.36. Conductivity (acetone, 20 °C): 132 Ω-1
2
cm2 mol-1
.
31P{1H} NMR ((CD3)2CO): δ 10.24 (d, J PP ) 20.3
2
3
wR2 (all data)
largest diff peak
and hole, e Å-3
Hz, (EtO)2PdO), 35.13 (dd, J PP ) 20.3 Hz, J PP ) 12.2 Hz,
Ph2PdN), 130.31 (d, 3J PP ) 12.2 Hz, Ph2POMe) ppm. 1H NMR
((CD3)2CO): δ 0.87 (d, 6H, 3J HH ) 6.7 Hz, CH(CH3)2), 1.06 and
1.48 (t, 3H each, 3J HH ) 6.6 Hz, OCH2CH3), 1.73 (s, 3H, CH3),
2.38 (m, 1H, CH(CH3)2), 2.81 and 4.20 (m, 1H each, RuCH2P),
3.40 (d, 3H, 3J HP ) 11.0 Hz, POCH3), 3.76 (m, 4H, OCH2CH3),
5.02 (br, 1H, CH of p-cymene), 5.13 (d, 1H, 3J HH ) 5.7 Hz, CH
of p-cymene), 5.21 (m, 2H, CH of p-cymene), 7.10-8.32 (m,
0.600 and -0.716
R1 ) ∑(|Fo| - |Fc|)/∑|Fo|; wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]}1/2
.
a
CH of p-cymene), 102.57 and 112.63 (s, C of p-cymene),
129.41-137.33 (m, Ph) ppm. 15b: Yield 78% (0.166 g). Anal.
Calcd for RuC49H49O6F3P3S2N: C, 55.36; H, 4.65; N, 1.32.
Found: C, 55.44; H, 4.93; N, 1.18. Conductivity (acetone, 20
1
20H, Ph) ppm. 13C{1H} NMR ((CD3)2CO): δ -1.62 (ddd, J CP
2
3
°C): 119 Ω-1 cm2 mol-1
.
31P{1H} NMR ((CD3)2CO): δ 42.36
) 40.6 Hz, J CP ) 17.1 Hz, J CP ) 8.6 Hz, RuCH2P), 16.13 (d,
3J CP ) 7.8 Hz, OCH2CH3), 16.52 (d, 3J CP ) 8.2 Hz, OCH2CH3),
17.18 (s, CH3), 21.07 and 22.23 (s, CH(CH3)2), 30.70 (s, CH-
(CH3)2), 55.00 (d, 2J CP ) 12.3 Hz, POCH3), 62.63 (d, 2J CP ) 6.0
2
3
3
(dd, J PP ) 22.6 Hz, J PP ) 17.7 Hz, Ph2PdN), 45.67 (dd, J PP
2
3
) 24.4 Hz, J PP ) 22.6 Hz, (EtO)2PdS), 134.24 (d, J PP ) 24.4
1
and 17.7 Hz, Ph2POMe) ppm. H NMR ((CD3)2CO): δ 0.80 (d,
2
3H, 3J HH ) 6.9 Hz, CH(CH3)2), 0.99 (d, 3H, 3J HH ) 7.0 Hz, CH-
(CH3)2), 1.93 (s, 3H, CH3), 2.25 (m, 1H, CH(CH3)2), 2.37 and
Hz, OCH2CH3), 63.53 (d, J CP ) 6.7 Hz, OCH2CH3), 85.73 (d,
2J CP ) 7.5 Hz, CH of p-cymene), 86.17 and 91.79 (s, CH of
2
3
p-cymene), 94.12 and 110.66 (s, C of p-cymene), 95.11 (d, J CP
3.50 (m, 1H each, RuCH2P), 3.46 (d, 3H, J HP ) 11.4 Hz,
3
) 5.6 Hz, CH of p-cymene), 128.68-136.01 (m, Ph) ppm. 15a :
Yield 73% (0.141 g). Anal. Calcd for RuC41H49O6F3P3S2N: C,
50.93; H, 5.11; N, 1.45. Found: C, 50.54; H, 5.47; N, 1.35.
POCH3), 5.19 and 5.36 (d, 1H each, J HH ) 5.9 Hz, CH of
3
p-cymene), 5.27 and 5.49 (d, 1H each, J HH ) 6.5 Hz, CH of
p-cymene), 6.93-8.09 (m, 30H, Ph) ppm. 13C{1H} NMR ((CD3)2-
Conductivity (acetone, 20 °C): 128 Ω-1 cm2 mol-1 31P{1H}
.
1
2
3
CO): δ -2.76 (ddd, J CP ) 42.4 Hz, J CP ) 15.1 Hz, J CP
)
NMR ((CD3)2CO): δ 39.24 (dd, 2J PP ) 26.2 Hz, 3J PP ) 18.1 Hz,
11.4 Hz, RuCH2P), 18.46 (s, CH3), 21.30 and 23.86 (s, CH-
2
3
(CH3)2), 31.23 (s, CH(CH3)2), 56.91 (d, 2J CP ) 13.2 Hz, POCH3),
Ph2PdN), 52.64 (dd, J PP ) 26.2 Hz, J PP ) 23.5 Hz, (EtO)2-
3
1
2
PdS), 135.81 (d, J PP ) 23.5 and 18.1 Hz, Ph2POMe) ppm. H
NMR ((CD3)2CO): δ 0.91 (d, 3H, J HH ) 6.6 Hz, CH(CH3)2),
1.01 (t, 3H, J HH ) 6.9 Hz, OCH2CH3), 1.07 (d, 3H, J HH ) 6.8
Hz, CH(CH3)2), 1.50 (t, 3H, 3J HH ) 6.8 Hz, OCH2CH3), 2.02 (s,
3H, CH3), 2.45 (m, 1H, CH(CH3)2), 2.94 and 3.63 (m, 1H each,
90.60 (d, J CP ) 7.2 Hz, CH of p-cymene), 92.18 and 92.27 (s,
3
2
CH of p-cymene), 95.36 (d, J CP ) 4.2 Hz, CH of p-cymene),
3
3
101.89 and 114.34 (s, C of p-cymene), 122.00-134.42 (m, Ph),
2
2
152.06 (d, J CP ) 9.0 Hz, Cipso of OPh), 153.18 (d, J CP ) 10.9
Hz, Cipso of OPh) ppm.
3
RuCH2P), 3.51 (d, 3H, J HP ) 11.2 Hz, POCH3), 4.36 (m, 4H,
X-r a y Cr ysta l Str u ctu r e Deter m in a tion of Com p lexes
3b a n d 11a ′. Crystals suitable for X-ray diffraction analysis
were obtained by cooling a saturated toluene solution of 3b at
0 °C or by slow diffusion of hexane into a saturated solution
of 11a ′ in toluene. 11a ′ was obtained as solvated crystals that
contained one water molecule per molecular unit. The most
relevant crystal and refinement data are collected in Table 1.
F or 3b: diffraction data were recorded at 120(2) K on a
Nonius KappaCCD single-crystal diffractometer using Cu KR
radiation. The crystal-detector distance was fixed at 29 mm,
and a total of 1120 frames were collected using the oscillation
3
OCH2CH3), 5.23 (d, 1H, J HH ) 5.5 Hz, CH of p-cymene), 5.43
3
(br, 2H, CH of p-cymene), 5.53 (d, 1H, J HH ) 5.3 Hz, CH of
p-cymene), 7.10-8.18 (m, 20H, Ph) ppm. 13C{1H} NMR ((CD3)2-
CO): δ -2.21 (ddd, 1J CP ) 34.7 Hz, J CP ) 10.8 Hz, J CP ) 6.4
2
3
3
Hz, RuCH2P), 15.97 (d, J CP ) 7.8 Hz, OCH2CH3), 16.61 (d,
3J CP ) 8.4 Hz, OCH2CH3), 18.03 (s, CH3), 21.49 and 23.01 (s,
2
CH(CH3)2), 30.81 (s, CH(CH3)2), 56.37 (d, J CP ) 13.8 Hz,
2
2
POCH3), 63.53 (d, J CP ) 6.0 Hz, OCH2CH3), 64.21 (d, J CP
)
2
8.4 Hz, OCH2CH3), 89.98 (d, J CP ) 6.0 Hz, CH of p-cymene),
2
91.71 (d, J CP ) 3.6 Hz, CH of p-cymene), 91.82 and 94.29 (s,

3436 Organometallics, Vol. 23, No. 14, 2004
Cadierno et al.
method, with 2° oscillations and 40 s exposure time per frame.
Data collection strategy was calculated with the program
Collect.29 Data reduction and cell refinement were performed
using the programs HKL Denzo and Scalepack.30 Unit cell
dimensions were determined from 6275 reflections. Absorption
correction was applied by means of SORTAV.31
F or 11a ′: diffraction data were recorded at 293(2) K on a
Nonius CAD4 single-crystal diffractometer using Mo KR
radiation. The unit-cell parameters were obtained from the
least-squares fit of 25 reflections (with θ between 5° and 13°).
Data were collected with the ω-2θ scan technique and a
variable scan rate, with a maximum scan time of 60 s per
reflection. The intensity of the primary beam was checked
throughout the data collection by monitoring three standard
reflections every 60 min. On all reflections, profile analysis
was performed.32,33 Some double measured reflections were
averaged, and Lorentz and polarization corrections were
applied. Absorption correction was applied by means of
XABS2.34
the anisotropic temperature factors of all the non-H atoms
were refined. Hydrogen atoms were geometrically placed and
isotropically refined with a common thermal parameter, riding
on their parent atoms (except the H atoms of the H2O molecule
in 11a ′, which were located by difference Fourier maps and
2
refined isotropically). The function minimized was [∑w(Fo
-
Fc2)/∑w(Fo2)]1/2 where w ) 1/[σ2(Fo2) + (aP)2 + bP] (a and b
values are shown in Table 1) with σ2(Fo2) from counting
statistics and P ) (max (Fo2,0) + 2Fc2)/3. Atomic scattering
factors were taken from International Tables for X-ray Crys-
tallography.38 Geometrical calculations were made with
PARST.39 The crystallographic plots were made with PLA-
TON.40
Ack n ow led gm en t. This work was supported by the
Ministerio de Ciencia y Tecnolog´ıa (MCyT) of Spain
(Projects BQU2000-0227 and BQU2003-00255), the
Gobierno del Principado de Asturias (Project PR-01-GE-
6), and the EU (COST Project D24/0014/02). V.C. thanks
the MCyT for a Ramo´n y Cajal contract.
The software package WINGX was used for space group
determination, structure solution, and refinement.35 All the
structures were solved by Patterson interpretation and phase
expansion using DIRDIF.36 Isotropic least-squares refinement
on F2 using SHELXL97 was performed.37 During the final
stages of the refinements, all the positional parameters and
Su p p or tin g In for m a tion Ava ila ble: IR data for all the
complexes reported in this paper. X-ray crystallographic files,
in CIF format, for the structure determinations of complexes
3b and 11a ′. This material is available free of charge via the
Internet at http://pubs.acs.org.
(29) Collect; Nonius BV: Delft, The Netherlands, 1997-2000.
(30) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307.
(31) Blessing, R. H. Acta Crystallogr. Sect. A 1995, 51, 33.
(32) Grant, D. F.; Gabe, E. J . J . Appl. Crystallogr. 1978, 11, 114.
(33) Lehman, M. S.; Larsen, F. K. Acta Crystallogr., Sect. A 1974,
30, 580.
OM040033D
(37) Sheldrick, G. M. SHELXL97: Program for the Refinement of
Crystal Structures; University of Go¨ttingen: Go¨ttingen, Germany,
1997.
(34) Parkin, S.; Moezzi, B.; Hope, H. J . Appl. Crystallogr. 1995, 28,
53.
(35) Farrugia, L. J . J . Appl. Crystallogr. 1999, 32, 837.
(36) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garc´ıa-Granda, S.; Gould, R. O.; Smits, J . M. M.; Smykalla, C. The
DIRDIF Program System; Technical Report of the Crystallographic
Laboratory; University of Nijmegen: Nijmegen, The Netherlands,
1999.
(38) International Tables for X-ray Crystallography; Kynoch Press:
Birmingham, U.K., 1974; Vol. IV (Present distributor: Kluwer Aca-
demic Publishers: Dordrecht, The Netherlands).
(39) Nardelli, M. Comput. Chem. 1983, 7, 95.
(40) Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;
University of Utrecht: The Netherlands, 2000.