Palladium (II) complexes with mono-oxide 1,1′-bis(diphenylphosphino) metallocene ligands [Fe(η5-C5Me4PPh 2)(η5-C5Me4P{O}Ph2)] and [Os(η5-C5H4PPh2) (η5-C5H4P{O}Ph2)]

Article abstract of DOI:10.1016/j.jorganchem.2005.01.025

The monoxides [Fe(η⁵-C₅Me₄PPh ₂)(η⁵-C₅Me₄P{O}Ph₂)] (1) and [Os(η⁵-C₅H₄PPh₂) (η⁵-C₅H₄P{O}Ph₂)] (2) have been prepared by treatment of the corresponding diphosphines with CCl₄ and methanol. These ligands react with [Pd(PhCN)₂Cl₂] to give dichloride complexes of different structure. The dimeric complex [{Os(η⁵-C₅H₄PPh₂) (η⁵-C₅H₄P{O}Ph₂)}PdCl(μ-Cl)] ₂ (4) contains the monodentate P-coordinated osmocene ligand with the free P{O}Ph₂ group, while the octamethylferrocene ligand gives the chelate k²-P,O complex [{Fe(η⁵-C₅Me ₄PPh₂)(η⁵-C₅Me ₄P{O}Ph₂)}PdCl₂] (3). The structures of 3 and 4 have been determined crystallographically. Treatment of 3 and 4 with silver salts in CH₂Cl₂ or acetonitrile leads to the corresponding dicationic complexes[{M(η⁵-C₅R₄PPh ₂)(η⁵-C₅R₄P{O}Ph ₂)}Pd(MeCN)_x]²⁺ (5, M = Fe, R = Me; 6, M = Os, R = H). Complex 5 decomposes upon isolation, in contrast 6 is rather stable, probably due to Os-Pd bonding. The dichlorides 3 and 4 catalyze catalytic amination of p-bromotoluene with N-(4-tolyl)morpholine with lower activity than (dppf)PdCl₂, however they perform comparable to (dppf)PdCl ₂ activity in coupling of p-bromotoluene with p-methoxyphenyl boronic acid.

Full text of DOI:10.1016/j.jorganchem.2005.01.025

Journal of Organometallic Chemistry 690 (2005) 1710–1717
www.elsevier.com/locate/jorganchem
Palladium (II) complexes with mono-oxide
1,10-bis(diphenylphosphino)metallocene ligands [Fe(g5-C5Me4PPh2)-
(g5-C5Me4P{O}Ph2)] and [Os(g5-C5H4PPh2)(g5-C5H4P{O}Ph2)]
a,
a
a
a
Oleg V. Gusev *, Tatꢀyana A. Peganova , Alexander M. Kalsin , Nikolai V. Vologdin ,
Pavel V. Petrovskii , Konstantin A. Lyssenko , Aleksei V. Tsvetkov ,
a
a
b
b
Irina P. Beletskaya
a
A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilov St. 28, 119991 Moscow, Russian Federation
b
Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory, 119899 Moscow, Russian Federation
Received 17 December 2004; accepted 17 January 2005
Available online 25 February 2005
Abstract
The monoxides [Fe(g5-C5Me4PPh2)(g5-C5Me4P{O}Ph2)] (1) and [Os(g5-C5H4PPh2)(g5-C5H4P{O}Ph2)] (2) have been prepared
by treatment of the corresponding diphosphines with CCl4 and methanol.These ligands react with [Pd(PhCN)2Cl2] to give dichloride
complexes of different structure.The dimeric complex [{Os(g5-C5H4PPh2)(g5-C5H4P{O}Ph2)}PdCl(l-Cl)]2 (4) contains the monod-
entate P-coordinated osmocene ligand with the free P{O}Ph2 group, while the octamethylferrocene ligand gives the chelate k2-P,O
complex [{Fe(g5-C5Me4PPh2)(g5-C5Me4P{O}Ph2)}PdCl2] (3).The structures of 3 and 4 have been determined crystallographi-
cally.Treatment of 3 and 4 with silver salts in CH2Cl2 or acetonitrile leads to the corresponding dicationic complexes [{M(g5-
C5R4PPh2)(g5-C5R4P{O}Ph2)}Pd(MeCN)x]2+ (5, M = Fe, R = Me; 6, M = Os, R = H). Complex 5 decomposes upon isolation,
in contrast 6 is rather stable, probably due to Os–Pd bonding. The dichlorides 3 and 4 catalyze catalytic amination of p-bromotol-
uene with N-(4-tolyl)morpholine with lower activity than (dppf)PdCl2, however they perform comparable to (dppf)PdCl2 activity in
coupling of p-bromotoluene with p-methoxyphenyl boronic acid.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Palladium; 1,10-Bis(diphenylphosphino)metallocene monoxides; Amination; Cross-coupling
1. Introduction
{O}Ph2)2PdCl2] (X = CH2, (CH2)2, (CH2)3, (CH2)4,
[Fe(g5-C5H4)2]) with two ligands coordinated by phos-
phino group merely [2a]. However the equimolar
interaction of [Fe(g5-C5H4PPh2)(g5-C5H4P{O}Ph2)]-
(dppfO) with palladium salts to form the P,O-chelated
palladium complex has not been reported yet. Though
the chelate palladium complex can be obtained from
the corresponding dioxide [Fe(g5-C5H4P{O}Ph2)2] [3].
Attempts to synthesize the dicationic palladium complex
by treating [(dppfO)2PdCl2] with silver salts resulted in
the mixture of unidentified products [2a]. It has to be
noted that the P,O-bidentate coordination favored over
the P-monodentate mode only in the case of the BINAP
In recent years a strong attention to the transition
metal complexes with chelating diphosphine monoxide
ligands has been attracted due to their possibility to be
applied as catalysts for various processes [1]. Complexa-
tion of diphosphine monoxides to palladium has been
recently investigated [2a,2b]. In particular, the reaction
of sodium tetrachloropalladate with two equivalents of
diphosphine monoxide gave the complexes [(Ph2PXP-
*
Corresponding author. Tel.: +70951359337; fax: +70951355085.
E-mail address: gusev@ineos.ac.ru (O.V. Gusev).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.01.025

O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
1711
monoxide [2b] to give the chelated palladium complex.
Interaction of the monoxides
1
and
2
with
The steric hindrance of the BINAP monoxide backbone
arisen from its rigidity has been assumed to be responsi-
ble for the equilibrium observed.
Here, we report about the synthesis of palladium
complexes with [Fe(g5-C5Me4PPh2)(g5-C5Me4P{O}Ph2)]
(1) and [Os(g5-C5H4PPh2)(g5-C5H4P{O}Ph2)] (2).
[Pd(PhCN)2Cl2] were supposed to give j2-P,O chelated
dichloride complexes [{M(g5-C5R4PPh2)(g5-C5R4P{O}-
Ph2)}PdCl2] (3, M = Fe, R = Me; 4, M = Os, R = H)
while unexpectedly proceeded in diverse ways. In both
reactions, 1 and 2 led to complexes which elemental
analyses were consistent with the proposed dichlorides
1
3 and 4. The H and 13C{1H} NMR spectra showed
two different types of Cp and Ph rings for both com-
plexes 3 and 4. Although in the 31P{1H} NMR spectra
3 and 4 differed significantly. Thus, in 31P{1H} NMR
complex 4 showed signals at d 28.27, 30.25, while com-
plex 3 – at d 17.75, 44.94. The upfield shifted signals cor-
responding to free ligands 1, 2 dissapeared and instead
new signals at d 17.75 and d 30.25 arose due to coordi-
nation of the PPh2 group in complexes 3 and 4. The
downfield shift of the P{O}Ph2 group from d 30.65 in
1 to d 44.94 in 3 may imply its coordination to palla-
dium to form the chelated j2-P,O complex. On the other
hand the chemical shifts of the P{O}Ph2 group in 2 and
4 differ insignificantly, and the phosphinoxide group in 4
appeared to not coordinate to palladium to give the di-
meric complex with bridging chlorides and monodentate
j1-P bonded diphosphine oxides [{Os(g5-C5H4PPh2)-
(g5-C5H4P{O}Ph2)}PdCl(l-Cl)]2 (Scheme 2).
2. Results and discussion
The monoxide of 1,10-bis(diphenylphosphino)ferro-
cene has been earlier prepared either by catalytic oxida-
tion [1,4] or by oxidation with the mixture of CCl4 and
benzophenone [5]. The latter method has been previ-
ously utilized for synthesis of [Fe(g5-C5Me4PPh2)(g5-
C5Me4P{O}Ph2)] (1) [5], though the low yields of less
than 30% and necessity to purify 1 from the side organic
products were disadvantages of this method. It has been
found that methanol being used instead of benzophe-
none results in higher yields of 1, up to 55%, and allows
us easy work up of the reaction mixture (Scheme 1).
The 1,10-bis(diphenylphosphino)osmocene gave in
this reaction unknown earlier monoxide [Os(g5-
C5H4PPh2)(g5-C5H4P{O}Ph2)] (2).
The new monoxide 2 has been characterized spectro-
scopically and by elemental analysis. In the 31P{1H}
NMR spectrum of 2 two signals at d ꢀ13.80, 28.95 arose
from phosphine PPh2 and phosphinoxide P{O}Ph2
groups, correspondingly. In the 1H NMR spectrum of 2
the Cp protons were observed as four singlets at d 4.56,
4.69, 4.76 and 4.92, and the phenyl protons – as multiplets
at d 7.1–7.7. In its 13C{1H} NMR spectrum, six signals of
the Cp carbons were in the region d 67–76 and eight sig-
nals from two types of the phenyl rings were at d 127–139.
The structures of 3 (Fig. 1) and 4 (Fig. 2) were deter-
mined by means of X-ray diffraction investigation
(Table 1). Each of the palladium atoms in the dimeric
complex 4 has slightly distorted square-planar configu-
ration and coordinated to three chlorines and one phos-
phorus. The angle Cl(2)–Pd(1)–Cl(2A) is 83.23(9)° and
similar to analogous complexes with other phosphines
bearing two phenyl substituents [6a,6b]. The phosphine
ligands are trans to each other with the bond lengths
˚
Pd(1)–P(2) of 2.229(2) A. The dihedral angle between
the plane Pd(1)Cl(2)Pd(1A)Cl(2A) and the Cp plane
C(1)C(2)C(3)C(4)C(5) is 58°, and the osmocene moieties
are situated up and under the plane Pd(1)Cl(2)Pd(1A)-
O
R
R
R
R
PPh2
PPh2
PPh2
˚
Cl(2A). The bond length P@O is 1.495(7) A and typical
R
R
R
R
R
MeOH
CCl4
for the uncoordinated P@O bond. The P@O group is
nearly in the plane of the Cp ring with the torsion angle
O(1)P(1)C(1)C(5) of 18.3°. The analysis of crystal pack-
ing revealed that the P@O group participate in the C–
M
M
R
R
R
R
PPh2
R
R
R
1, M = Fe, R = Me
2, M = Os, R = H
˚
Hꢁ ꢁ ꢁO contacts (the distance Hꢁ ꢁ ꢁO is 1.98–2.09 A, the
angle C–Hꢁ ꢁ ꢁO is 154–164°) with solvate CHCl3
Scheme 1.
molecules.
R
R
O
O
R
Cl
PPh2
PPh2
PPh2
Ph2P
Pd
Cl
Cl
[Pd(PhCN)2Cl2]
M = Fe, R = Me
R
R
R
[Pd(PhCN)2Cl2]
M = Os, R = H
O
Fe
M
Os
Os
Pd
PPh2
PdCl2
R
PPh2
PPh2
Ph2P
O
R
Cl
3
4
Scheme 2.

1712
O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
˚
planar configuration. The P@O bond (1.479(9) A) is
slightly smaller than that for the coordinated (the length
of the P@O bond in [{Fe(g5-C5H4P{O}Ph2)2}PdCl2] is
˚
1.495 A [3]) and even the uncoordinated phosphinoxide
˚
group (the P@O length in 4 is 1.495(7) A). The angle
P(1)–O(1)–Pd(1) is 171° and significantly larger than
the analogous angle for [{Fe(g5-C5H4P{O}Ph2)2}PdCl2]
(158.3°) [3] and [{Fe(g5-C5H4PPh2)(g5-C5H4P{O}Ph2)}-
W(CO)3I] (160.2°) [7]. The coordination of the palla-
dium to the oxygen of the phosphinoxide group
occurred in expense of strong distortion of the ferrocene
moiety. Thus, the phosphorus atom P(1) is inclined from
˚
the Cp plane outward the palladium on 0.0192 A, while
˚
analogous value for the P(2) is much higher (0.5792 A).
Moreover the bond C(10)–P(2) is significantly bent out
to the methyl C(18) with the angle C(10)–Cpcenter(2)–
P(2) of 11.0°, the analogous angle C(1)–Cpcenter(1)–
P(1) is only 2.0°. The distortions described result in
the Cp rings to be fixed in unusual for the complexes
with 1,10-bis(diphenylphosphino)octamethylferrocene
staggered conformation with the twisting angle C(1)–
Cpcenter(1)–Cpcenter(2)–C(10) of 36.8°. The differences
observed between the structures 3 and 4 are probably
due to the presence of four a-methyls in the Cp rings
in 3 that can hamper the dimerisation.
Fig. 1. The general view of 3.
The reaction of the octamethylferrocene complex 3
with silver salts in the presence of water or acetonitrile
led to partial oxidation of the ferrocene moiety resulting
in mixture of unstable paramagnetic cationic complexes.
The alternative approach that is the reaction of the free
The palladium atom in 3 is coordinated with two ter-
minal chlorides, phosphorus and oxygen (the Pd–O
˚
length is 1.998(9) A) to give slightly distorted square-
Fig. 2. The general view of 4.

O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
1713
Table 1
Selected geometrical parameters for the complexes 3 and 4
ing material, instead new complex 5 having singlets at d
32.70 and 53.77 formed. In the H NMR spectrum of 5
1
3
4
methyls of the ferrocene moiety were presented by four
singlets at d 1.55, 1.76, 1.79 and 1.86, the signal corre-
sponded to the coordinated acetonitrile arose at 2.00
and the multiplets at d 7.3–7.8 were assigned to the phe-
nyl protons. These spectral data allowed us to propose
the chelated structure for [{Fe(g5-C5Me4PPh2)(g5-C5-
Me4P{O}Ph2)}Pd(MeCN)2]2+(BF4ꢀ)2 (5), cf. Scheme 3.
The complex 5 is unstable without solvent. Evapora-
tion of the reaction mixture following with dissolution
of the residue in CD3CN resulted in arising new signals
in 31P{1H} NMR spectrum at d 30.11, 34.35 50.12 and
51.50 of unidentified products together with the signals
of 5.
M = Fe
2.03(1)–2.08(1)
1.669
M = Os
2.16(1)–2.209(9)
1.811
˚
M–CCp (A)
M–X(1)a (A)
˚
M–X(2)b (A)
1.656
2.264(3)
1.998(9)
1.822
2.229(3)
˚
˚
Pd(1)–P(2) (A)
˚
Pd(1)–O(1) (A)
˚
Pd(1)–Cl(1) (A)
˚
Pd(1)–Cl(1) (A)
2.259(4)
2.362(3)
2.283(2)
2.326(2)
2.428(2)
1.495(7)
˚
Pd(1)–Cl(2) (A)
˚
Pd(1)–Cl(2A) (A)
˚
P(1)–O(1) (A)
1.479(9)
171.1(9)
95.1(2)
90.8(1)
Pd(1)O(1)P(1) (°)
O(1)Pd(1)P(1) (°)
Cl(1)Pd(1)Cl(2) (°)
Cl(2)Pd(1)Cl(2A) (°)
83.23(9)
1.77(1)
1.794(9)
0.0
Treating the osmocene complex 4 with silver tosylate
gave relatively stable dicationic aqua complex 6a. Anal-
ogously, reaction of 4 with silver tetrafluoroborate in the
presence of acetonitrile gave complex 6b (Scheme 4).
Complexes 6a,b were characterized by elemental
analysis and spectroscopically. The 31P{1H} NMR spec-
tra of 6a,b are similar, and each consisted of two signals
at d 13.70, 48.98 (6a) and d 16.59, 53.47 (6b) of the coor-
dinated phosphinoxide and phosphino groups, corre-
˚
P(1)–CCp (A)
1.78(1)
1.82(1)
0.0192
0.570
2.9
˚
P(2)–CCp (A)
c
˚
dP(1) (A)
c
˚
dP(2) (A)
ꢀ0.02
3.6
15.8
Cp/Cpd (°)
he (°)
36.8
a
Centroid of the C(1)–C(5) Cp ring.
Centroid of the C(10)–C(15) Cp-ring in 3 and of C(6)–C(7) one in
b
4.
c
Deviation of the phosphorus atom from the Cp plane ring, a
negative value meaning the P(1)/P(2) is closer to Os/Fe.
1
spondingly. In their H NMR spectra the Cp protons
d
are presented at d 4.88, 5.79, 6.08, 6.88 (6a) and d
5.16, 5.61, 5.79, 6.73 (6b). Such a large difference of
chemical shifts in 1H NMR of 1,10-bis(phosphino)metal-
locene complexes between a- and b-Cp protons is indic-
ative for the presence of M–Pd bonding [8]. Complex 6b
contains one molecule of acetonitrile according to inte-
gral intensity of the signal in 1H NMR that confirms for-
mation of the Os–Pd bond as well; otherwise it should
contain two solvate ligands. Both the relatively large dif-
ference between the signals of a- and b-carbons of the
The dihedral angle between the two Cp rings.
The torsion angle CCp(1)X(1)X(2)CCp(2), where X is the centroid of
the corresponding Cp ring.
e
monoxide 1 with [Pd(MeCN)4](BF4)2 allowed us to ob-
tain the diamagnetic dication, which still underwent
decomposition after removing the solvent in vacuum.
The 31P{1H} NMR spectrum registered in 30 min. after
addition of a solution [Pd(MeCN)4](BF4)2 in CD3CN to
a solution of 1 in CD2Cl2 showed no signals of the start-
2+
PPh2
PPh2
[Pd(MeCN)4](BF4)2
O
O
-
Fe
Fe
Pd(NCMe)2 (BF4 )2
PPh2
PPh2
5
Scheme 3.
2+
PPh2
Cl
Pd
PPh2
O
O
4AgX / L
(X-)2
Os
Os
Pd(L)
2
Cl
PPh2
PPh2
2
6a, L = H2O, X = OTs
6b, L = MeCN, X = BF4
Scheme 4.

1714
O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
Cp rings (d 74.49, 78.24, 78.34, 79.93 for 6a and d 74.94,
78.42, 78.94, 80.79 for 6b) and significant upfield shift of
the ipso-carbons of the Cp rings (d 60.74 for 6a and d
59.80 for 6b) in the 13C{1H} NMR spectrum can also
be evident for the metal–metal bonding. The transfor-
mation of the bidentate osmocene ligand to the triden-
tate is probably responsible for the stabilization of the
dicationic complexes 6a,b in comparison to 5.
The dichloride complexes 3 and 4 were tested in cat-
alytic amination (Scheme 5) and Suzuki type reaction
(Scheme 6) of p-bromotoluene. The amination of p-
bromotoluene catalyzed by 3 and 4 gave lower yields
comparing to 1,10-bis(diphenylphosphino)ferrocene
(Table 2). Though, the precursor 3 stabilized with
octamethylferrocene ligand performed comparable
activity to 1,10-bis(diphenylphosphino)ferrocene in the
reaction of p-bromotoluene with p-methoxyphenyl
boronic acid to give 4-methoxy-40-methylbiphenyl
(Table 3), cf. Schemes 5 and 6.
3. Experimental
3.1. General procedures
All experiments were performed under argon in sol-
1
vents purified by standard methods. H, 31P{1H} and
13C{1H} NMR spectra were recorded on Bruker AMX
400 and Varian VXR 400 spectrometers. Chemical shifts
are reported in ppm (d) with reference to TMS as an
internal standard (1H and 13C{1H} NMR spectra),
and 85% H3PO4 for 31P{1H} NMR spectra as an exter-
nal standards. Microanalyses were performed at the
A.N. Nesmeyanov Institute of Organoelement Com-
pounds. The following compounds were synthesized
according to published procedures: [Pd(PhCN)2Cl2] [9],
[Fe(g5-C5Me4PPh2)2] [5], [Os(g5-C5H4PPh2)2] [8].
3.2. Synthesis of [Fe(g5-C5Me4PPh2)(g5-C5Me4P{O}-
Ph2)] (1)
To
a
solution of [Fe(g5-C5Me4PPh2)2] (1.00 g,
t-BuONa
O
dioxane
1.5 mmol) in benzene (50 mL) methanol (0.5 mL) and
CCl4 (7 mL) were added. The mixture was heated at
50 °C for 1.5 h. The solution was then cooled to room
temperature and passed through a bed of silica (5 cm).
The unreacted diphosphine [Fe(g5-C5Me4PPh2)2]
(0.28 g) was eluted first with benzene, then the monoxide
1 was eluted with the mixture Et2O/benzene (2:1). Yield
of 1: 0.54 g (53%). Anal. Calcd. for C42H44FeOP2: C,
N
O
+
1 mol % Pd
N
H
Br
Scheme 5.
OMe
K2CO3 /H2O
dioxane
1
73.90; H, 6.50. Found: C, 73.91; H, 6.61%. H NMR
(CDCl3): d 1.38 (s, 3H, C5Me4); 1.39 (s, 3H, C5Me4);
1.84 (s, 3H, C5Me4); 1.97 (s, 3H, C5Me4); 7.1–7.4 (m,
OMe
+
1 mol % Pd
3
16H, Ph); 7.52 (dd, 4H, o-H(Ph), JHH = 7.3,
Br
B(OH)2
3JHP = 11.6 Hz). 31P{1H} NMR (CDCl3): d ꢀ21.59 (s,
Scheme 6.
PPh2); 30.65 (s, P{O}Ph2).
Table 2
The catalytic amination of p-bromotoluene with N-(4-tolyl)-morphol-
ine catalyzed by 3 and 4
3.3. Synthesis of [Os(g5-C5H4PPh2)(g5-C5H4P{O}-
Ph2)] (2)
Run
Catalyst
Yield of N-(4-tolyl)-morpholine (%)
To
a
solution of [Os(g5-C5H4PPh2)2] (0.78 g,
1
2
3
(dppf)PdCl2
42
25
21
1.13 mmol) in benzene (50 mL) methanol (0.3 mL) and
CCl4 (5 mL) were added. The mixture was heated at
40 °C for 40 min. The solution was cooled to room tem-
perature and then passed through a bed of silica (5 cm).
The unreacted [Os(g5-C5H4PPh2)2] (0.47 g) was eluted
with benzene, the monoxide 2 – with the mixture ace-
tone/CH2Cl2 (1:1). Yield of 2: 0.26 g (33%). Anal. Calcd.
for C34H28OOsP2: C, 57.94; H, 4.00. Found: C, 58.15;
H, 4.31%. 1H NMR (CDCl3): d 4.56 (s, 2H, C5H4);
4.69 (s, 2H, C5H4); 4.76 (s, 2H, C5H4); 4.92 (s, 2H,
C5H4); 7.26 (m, 10H, Ph); 7.40 (m, 4H, Ph); 7.48 (t,
3
4
Conditions: 4-Bromotoluene (1 eq), morpholine (1.25 eq), t-BuONa
(1.25 eq), catalyst (0.01 eq), dioxane (2.5 ml), T = 100 °C, t = 20 min.
Table 3
The catalytic reaction of p-bromotoluene with p-methoxyphenyl
boronic acid catalyzed by 3 and 4
Run
Catalyst
Yield of 4-methoxy-40-methylbiphenyl (%)
1
2
3
(dppf)PdCl2
60
71
38
3
4
3
2H, p-H(Ph), JHH = 7.6 Hz); 7.61 (dd, 4H, o-H(Ph),
3
3JHH = 7.2, JHP = 12.2 Hz). 13C{1H} NMR (CDCl3):
Conditions: 4-Bromotoluene (1 eq), 4-methoxyphenylboronic acid
(1.32 eq), K2CO3 (3 eq), catalyst (0.01 eq), dioxane (1.5 ml), water
(0.5 ml), T = 100 °C, t = 10 min.
2
d 67.49 (d, a-C(C5H4); JCP = 12.6 Hz); 68.85 (d, b-
C(C5H4); 3JCP = 9.6 Hz); 69.82 (d, b-C(C5H4);

O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
1715
3JCP = 3.3 Hz); 70.74 (d, ipso-C(C5H4); 1JCP
=
7.37–7.60 (m, 12H, Ph); 7.66 (dd, 4H, o-H(Ph),
3
2
114.5 Hz); 70.98 (d, a-C(C5H4); JCP = 15.6 Hz); 75.37
(d, ipso-C(C5H4); JCP = 9.9 Hz); 127.85 (d, o-C(Ph),
3JHH = 7.5, JHP = 11.8 Hz).13C{1H} NMR (CDCl3): d
1
1
66.10 (d, ipso-C(C5H4); JCP = 67.5 Hz); 69.76 (d, a-
2JCP = 7.0 Hz); 127.88 (s, p-C(Ph)); 128.22 (d, m-
C(C5H4); 2JCP = 12.2 Hz); 71.13 (d, b-C(C5H4);
3
C(Ph), JCP = 18.1 Hz); 131.32 (d, m-C(Ph), JCP
3
2
=
9.9 Hz); 131.38 (s, p-C(Ph)); 133.45 (d, o-C(Ph),
3JCP = 5.5 Hz); 71.76 (d, a-C(C5H4); JCP = 11.0 Hz);
1
72.98 (d, ipso-C(C5H4); JCP = 117.6 Hz); 73.04 (d, b-
2JCP = 19.0 Hz); 134.43 (d, ipso-C(Ph), 1JCP
=
C(C5H4); JCP = 9.9 Hz); ꢂ127.9 (d, overlapped,
3
1
106.5 Hz); 138.75 (d, ipso-C(Ph), JCP = 9.2 Hz);
31P{1H} NMR (CDCl3): d ꢀ13.80 (s, PPh2); 28.63 (s,
P{O}Ph2).
ipso-C(Ph), 1JCP ꢂ 60 Hz); 128.02 (d, m-C(Ph),
3
3JCP = 12.1 Hz); 128.22 (d, m-C(Ph), JCP = 11.9 Hz);
2
131.35 (d, o-C(Ph), JCP = 9.8 Hz); 131.60 (s, p-C(Ph));
131.76
(s,
p-C(Ph));
133.25
(d,
ipso-C(Ph),
2
3.4. Synthesis of [{Fe(g5-C5Me4PPh2)(g5-C5Me4P{O}-
Ph2}PdCl2)] (3)
1JCP = 106.7 Hz); 133.58 (d, o-C(Ph), JCP = 10.8 Hz).
31P{1H} NMR (CDCl3): d 28.27 (s, P{O}Ph2); 30.25
(s, PPh2).
To a solution of [Pd(PhCN)2Cl2] (0.69 g, 1.80 mmol)
in benzene (100 mL) a solution of 1 (1.23 g, 1.80 mmol)
in benzene (250 mL) was added dropwise at room tem-
perature. The reaction mixture was stirred for 18 h.
The precipitate was filtered off, washed with benzene
and recrystallized from hexane–CH2Cl2. Yield of 3:
1.51 g (97%). Anal. Calcd. for C42H44Cl2FeOP2Pd-
CH2Cl2: C, 51.32; H, 4.70. Found: C, 51.74; H, 4.52%.
1H NMR (CDCl3): d 1.46 (s, 3H, C5Me4); 1.50 (s, 3H,
C5Me4); 1.64 (s, 3H, C5Me4); 7.28 (m, 4H, Ph); 7.44
3.6. Interaction of [Fe(g5-C5Me4PPh2)(g5-C5Me4P{O}-
Ph2)] with [Pd(MeCN)4](BF4)2
A solution of 1 (14 mg, 0.02 mmol) in CD2Cl2
(1 mL) was added dropwise at 0 °C to a solution of
[Pd(MeCN)4](BF4)2 (9 mg, 0.02 mmol) in CD3CN
(0.3 mL) with stirring. The reaction mixture was al-
lowed to warm to room temperature and stirred for
30 min. 31P{1H} NMR: d 32.70 (s); 53.77 (s). 1H
NMR: d 1.55 (s, 3H, C5Me4); 1.76 (s, 3H, C5Me4);
1.79 (s, 3H, C5Me4); 1.86 (s, 3H, C5Me4); 2.00 (s,
6H, 2CH3CN); 7.41 (m, 8H, Ph); 7.55 (m, 8H, Ph);
7.72 (m, 4H, Ph).
3
(m, 8H, Ph); 7.84 (dd, 4H, o-H(Ph), JHH = 7.8,
3JHP = 11.3 Hz); 8.06 (m, 4H, Ph). 13C{1H} NMR
(CDCl3): d 8.78 (s, C5Me4); 8.92 (s, C5Me4); 12.39 (s,
C5Me4); 12.97 (s, C5Me4); 68.17 (d, ipso-C(C5Me4),
1
1JCP = 23.5 Hz); 68.97 (d, ipso-C(C5Me4), JCP
=
3
37.9 Hz); 85.14 (d, b-C(C5Me4), JCP = 8.0 Hz); 85.34
3.7. Synthesis of [{Os(g5-C5H4PPh2)(g5-C5H4P{O}-
Ph2)}Pd(H2O)](OTs)2 (6a)
(d, a-C(C5Me4), 2JCP = 13.2 Hz); 86.53 (d, b-
3
C(C5Me4), JCP = 6.0 Hz); 87.05 (d, a-C(C5Me4),
2JCP = 11.2 Hz); 127.68 (d, m-C(Ph), JCP = 7.0 Hz);
To a solution of 4 (0.23 g, 0.13 mmol) in CH2Cl2
(30 mL) cooled to 0 °C silver tosylate (0.15 g,
0.52 mmol) was added with stirring. The mixture was
allowed to warm to room temperature and stirred for
4 h. Precipitate of silver chloride was filtered off, the fil-
trate was concentrated to 3 mL and quenched with
Et2O (30 mL) to give yellow–brown precipitate, which
was filtered off, washed with Et2O and dried in vacuum.
3
3
128.48 (d, m-C(Ph), JCP = 12.8 Hz); 129.85 (d, ipso-
1
C(Ph), JCP = 56.7 Hz); 130.80 (d, p-C(Ph), JCP
4
=
2.0 Hz); 130.91 (d, ipso-C(Ph), JCP = 7.0 Hz); 132.11
1
4
(d, p-C(Ph), JCP = 2.8 Hz); 132.54 (d, o-C(Ph),
2JCP = 10.8 Hz); 135.71 (d, o-C(Ph), JCP = 10.4 Hz).
2
31P{1H} NMR (CDCl3): d 17.75 (s, PPh2); 44.94 (s,
P{O}Ph2).
Yield of 6a: 0.29
g
(97%). Anal. Calcd. for
3.5. Synthesis of [{Os(g5-C5H4PPh2)(g5-C5H4P{O}-
Ph2)}PdCl(l-Cl)]2 (4)
C48H44O8Os-P2PdS2: C, 49.21; H, 3.78; Os, 16.24.
Found: C, 49.76; H, 3.99; Os, 16.17%. 1H NMR
(CDCl3): d 2.30 (s, 6H, p-CH3C6H4SO3); 4.88 (s, 2H,
C5H4); 5.79 (s, 2H, C5H4); 6.08 (s, 2H, C5H4); 6.88 (s,
A solution of 2 (0.72 g, 1.02 mmol) in benzene
solution of
(150 mL) was added dropwise to
a
2H,
C5H4);
7.06
(d,
4H,
p-CH3C6H4SO3,
[Pd(PhCN)2Cl2] (0.39 g, 1.02 mmol) in benzene
(50 mL) at room temperature. The solution was stirred
for 18 h. The benzene solution was concentrated to
10 mL and then treated with hexane (50 mL). The pre-
cipitate was filtered off, washed with hexane and dried
in vacuum. Yield of 4: 0.88 g (98%). Anal. Calcd. for
C68H56Cl4O2Os2P4Pd2 ꢁ C6H6: C, 48.24; H, 3.39; Os,
3JHH = 7.2 Hz); 7.49 (m, 8H, Ph); 7.61 (m, 4H, Ph);
3
7.76 (m, 8H, Ph); 7.91 (dd, 4H, o-H(Ph), JHH = 7.6,
3JHP = 13.4 Hz). 13C{1H} NMR (CDCl3): d 21.14 (s,
p-CH3C6H4SO3);
1JCP = 56.3 Hz); 74.49 (d, a-C(C5H4); JCP = 10.8 Hz);
60.74
(d,
ipso-C(C5H4);
2
1
75.40 (d, ipso-C(C5H4); JCP = 107.4 Hz); 78.24 (d, b-
C(C5H4); 3JCP = 8.8 Hz); 78.34 (d, a-C(C5H4);
1
3
20.65. Found: C, 47.94; H, 3.69; Os, 20.34%. H NMR
2JCP = 11.1 Hz); 79.89 (d, b-C(C5H4); JCP = 8.4 Hz);
122.24 (d, ipso-C(Ph), JCP = 62.7 Hz); 126.25 (s, o-C
or m-C, p-CH3C6H4SO3); 127.66 (d, ipso-C(Ph),
1
(CDCl3): d 4.94 (s, 2H, C5H4); 4.99 (s, 2H, C5H4); 5.16
(s, 2H, C5H4); 5.66 (s, 2H, C5H4); 7.30 (m, 4H, Ph);

1716
O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
1JCP = 111.4 Hz); 128.72 (s, o-C or m-C, p-
3.10. Cross-coupling of 4-bromotolune with
4-methoxyphenylboronic acid
3
CH3C6H4SO3); 129.36 (d, m-C(Ph), JCP = 13.1 Hz);
3
129.52 (d, m-C(Ph), JCP = 12.8 Hz); 131.61 (d, o-
2
C(Ph), JCP = 11.2 Hz); 133.09 (d, p-C(Ph), JCP
4
=
2.4 Hz); 133.65 (d, p-C(Ph), JCP = 2.8 Hz); 134.84 (d,
4-Bromotoluene (50 mg 0.292 mmol), 4-meth-
oxyphenylboronic acid (59 mg, 0.385 mmol), potassium
carbonate (121 mg, 0.877 mmol) and 1 mol% palladium
catalyst in the mixture of dioxane (1.5 ml) and water
(0.5 ml) were stirred under reflux during 10 min. The
reaction mixture was quenched with water and twice ex-
tracted with CH2Cl2. The organic layer was then dried
over Na2SO4 and concentrated in vacuo. The yield of
4-methoxy-40-methylbiphenyl was determined by
4
2
o-C(Ph), JCP = 12.4 Hz); 140.32 (s, ipso-C, p-CH3-
C6H4SO3); 142.41 (s, ipso-C, p-CH3C6H4SO3).
31P{1H} NMR (CDCl3): d 13.69 (s, PPh2); 48.98 (s,
P{O}Ph2).
3.8. Synthesis of [{Os(g5-C5H4PPh2)(g5-C5H4P{O}-
Ph2)}Pd(MeCN)](BF4)2 (6b)
1
NMR, using acetylferrocene as a standard. H NMR
(CDCl3): d 2.36 (s, 3H, CH3); 3.81 (s, 3H, OCH3);
6.94 (m, 2H, C6H4); 7.20 (m, 2H, C6H4); 7.42 (m, 2H,
C6H4); 7.48 (m, 2H, C6H4).
To a solution of 4 (0.20 g, 0.11 mmol) in CH2Cl2
(30 mL) at 0 °C acetonitrile (0.1 mL) and silver tetra-
fluoroborate (0.09 g, 0.46 mmol) were added. The reac-
tion mixture was allowed to warm to room
temperature and stirred for 4 h. Silver chloride was fil-
tered off, the filtrate was concentrated to 3 mL and then
quenched with Et2O (30 mL). The precipitate was fil-
tered off, washed with Et2O and dried. Yield of 6b:
0.23 g (98%). Anal. Calcd. for C36H31B2F8NOOsP2-
Pd2ÆCH2Cl2: C, 38.17; H, 2.95. Found: C, 38.46; H,
2.86%. 1H NMR (CD2Cl2): d 2.23 (s, 3H, MeCN);
5.16 (s, 2H, C5H4); 5.61 (s, 2H, C5H4); 5.79 (s, 2H,
C5H4); 6.73 (s, 2H, C5H4); 7.5–7.9 (m, 20H, Ph).
13C{1H} NMR (CD2Cl2): d 2.98 (s, CH3CN); 59.80 (d,
3.11. X-ray structure determination
Crystals of 3 suitable for X-ray analysis were obtained
by slow diffusion of hexane into a solution of the com-
plex in dichloromethane. Crystals of 4 were obtained
by slow evaporation of a solution of the complex in chlo-
roform. X-ray diffraction experiments for 3 and 4 were
carried out with a Bruker SMART 1000 CCD area detec-
tor, using graphite monochromated Mo Ka radiation
˚
(k = 0.71073 A, x-scans with a 0.3° step in and 10 s per
1
ipso-C(C5H4); JCP = 56.7 Hz); 74.94 (d, a-C(C5H4);
frame exposure) at 110 K. Reflection intensities were
integrated using SAINT software [10] and semi-empirical
method SADABS [11]. The structures were solved by direct
method and refined by the full-matrix least-squares
against F2 in anisotropic approximation for no-hydrogen
atoms. The analysis of systematic absences as well as the
Rint value have revealed that despite b is close to 90° the
crystal of 3 is monoclinic. The inclusion of twining law
(TWIN 010 100 00ꢀ1) lead to significant decrease of
the R-factor (BASF parameter was equal to 0.407), thus
we can conclude that 3 is a twin. All hydrogen atoms
were placed in geometrically calculated positions and in-
cluded in final the refinement using the ‘‘riding’’ model
with the Uiso(H) parameters equal to 1.2 Ueq(Ci) or 1.5
Ueq(Cii), where U(Ci) and U(Cii) are respectively the
equivalent thermal parameters of the methyne and meth-
ylene carbon atoms to which corresponding H atoms are
bonded. Crystal data and structure refinement parame-
ters for 3 and 4 are given in Table 4. All calculations were
performed on an IBM PC/AT using the SHELXTL software
[12].
2JCP = 11.2 Hz); 75.83 (d, ipso-C(C5H4); 1JCP
=
2
56.7 Hz); 78.42 (d, a-C(C5H4); JCP = 10.8 Hz); 78.94
3
(d, b-C(C5H4); JCP = 8.8 Hz); 80.76 (d, b-C(C5H4);
3JCP = 8.8 Hz); 120.77 (s, CH3C N); 122.35 (d, ipso-
C(Ph); 1JCP = 65.4 Hz); 126.91 (d, ipso-C(Ph);
3
1JCP = 111.0 Hz); 129.74 (d, m-C(Ph), JCP = 13.2 Hz);
3
130.30 (d, m-C(Ph), JCP = 12.8 Hz); 131.71 (d, o-
2
C(Ph), JCP = 11.2 Hz); 134.26 (d, o-C(Ph), JCP
2
=
12.8 Hz); 134.59 (d, p-C(Ph), JCP = 3.2 Hz); 137.72 (d,
4
4
p-C(Ph), JCP = 2.4 Hz). 31P{1H} NMR (CD2Cl2): d
16.59 (s, PPh2); 53.48 (s, P{O}Ph2).
3.9. Catalytic amination of 4-bromotoluene with
morpholine
4-Bromotoluene (117 mg 0.684 mmol), morpholine
(75 mg, 0.850 mmol), sodium tert-butoxide (81 mg,
0.850 mmol) and 1 mol% palladium catalyst were stir-
red in dioxane (2.5 ml) under reflux during appropri-
ate time. The reaction mixture was quenched with
water and twice extracted with CH2Cl2. The organic
layer was then dried over Na2SO4 and concentrated
in vacuo. The yield of N-(4-tolyl)-morpholine was
determined by NMR, using acetylferrocene as a stan-
4. Supplementary material
1
dard. H NMR (CDCl3): d 2.26 (s, 3H, CH3); 3.08 (m,
4H, CH2); 3.84 (m, 4H, CH2); 6.81 (m, 2H, C6H4);
7.07 (m, 2H, C6H4).
The crystallographic data have been deposited with
the Cambridge Crystallographic Data Center, CCDC
258452 for 3 and CCDC 258452 for 4. Copies of this

O.V. Gusev et al. / Journal of Organometallic Chemistry 690 (2005) 1710–1717
1717
Table 4
Crystallographic data for complexes 3 and 4
3
4
Formula
T (K)
C42H44Cl2FeOP2PdÆ2CH2Cl2
120
C68H56Cl4O2Os2P4Pd2 Æ8CHCl3
120
Crystal system, space group
˚
Monoclinic, P21/n
11.036(4)
20.389(5)
20.005(5)
90.485(5)
4501(2), 4
1029.71
11.82
Monoclinic, P21/n
18.040(4)
10.417(3)
26.220(5)
104.955(4)
4760.2(19), 2
2718.95
39.29
a (A)
˚
b (A)
˚
c (A)
b (°)
V (A) , Z
3
˚
M
l (cmꢀ1
F(000)
)
2008
1.520
50
2632
1.897
52
dcalc (g cmꢀ3
)
2hmax (°)
No. of reflections measured (Rint
No. of independent reflections
)
25,297 (0.0761)
7850
3599
30,297 (0.0686)
9313
6051
No. of reflections with I > 2r(I)
No. of parameters
R1
517
0.0834
514
0.0602
wR2
GOF
Max./Min. peak (e A
0.1834
1.017
0.1645
0.981
ꢀ3
˚
)
1.27/ꢀ0.946
1.71/ꢀ1.71
[3] J.S.L. Yeo, J.J. Vittal, T.S.A. Hor, J. Chem Soc., Chem.
Commun. (1999) 1477.
information may be obtained free of charge from: The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: +44-1223-336033; deposit@ccdc.cam.
ac.uk or www.ccdc.cam.ac.uk).
[4] V.V. Grushin, J. Am. Chem. Soc. 121 (1999) 5831.
[5] S. Ninoreille, R. Broussier, R. Amardeil, M.M. Kubicki, B.
Gautheron, Bull. Soc. Chim. Fr. 132 (1995) 128.
[6] (a) N.M. Vinogradova, I.L. Odinets, K.A. Lyssenko, M.P.
Paschnik, P.V. Petrovskii, T.A. Mastryukova, Mendeleev Com-
mun. (2001) 219;
Acknowledgments
(b) S.J. Coles, P. Faulds, M.B. Hursthouse, D.G. Kelly, G.C.
Ranger, A.J. Toner, N.M. Walker, J. Organomet. Chem. 586
(1999) 234.
Thanks are due to the Russian Foundation for Basic
Research (Grant 03-03-32471) and to the Science Sup-
port Foundation of Russian Federation for financial
support.
[7] S.C.N. Shu, W.-Y. Yeh, M.Y. Chiang, J. Organomet. Chem. 492
(1995) 121.
[8] O.V. Gusev, A.M. Kalsin, P.V. Petrovskii, K.A. Lyssenko, Yu.F.
Oprunenko, C. Bianchini, A. Meli, W. Oberhauser, Organomet-
allics 22 (2003) 913.
[9] J.R. Doyle, P.E. Slade, H.B. Jonassen, Inorg. Synth. 6 (1960)
218.
References
[10] SMART V5.051 and SAINT V5.00, Area detector control and
integration software, 1998, Bruker AXS Inc., Madison, WI, USA.
[11] G.M. Sheldrick, SADABS, 1997, Bruker AXS Inc., Madison, WI,
USA.
[1] V.V. Grushin, Organometallics 20 (2001) 3950, and references
therein.
[2] (a) R.J. Coyle, Yu.L. Slovokhotov, M.Yu. Antipin, V.V. Grushin,
Polyhedron 17 (1998) 3059;
(b) W.J. Marshall, V.V. Grushin, Organometallics 22 (2003) 55.
[12] G.M. Sheldrick, SHELXTL-97, Version 5.10, Bruker AXS Inc.,
Madison, WI, USA.