A novel heterobidentate chiral phosphine and its coordination chemistry in transition metal clusters

Article abstract of DOI:10.1016/j.jorganchem.2007.03.008

The optically active ligand R,R-PHAZAN (1,3-bis[(1R)-1-Phenylethyl]-2-(2-thienyl)-1,3,2-diazaphospholane) has been prepared and the products resulting from the reactions with Rh₆(CO)₁₅NCMe, H₃RhOs₃(CO)₁₂

Full text of DOI:10.1016/j.jorganchem.2007.03.008

Journal of Organometallic Chemistry 692 (2007) 2911–2923
www.elsevier.com/locate/jorganchem
A novel heterobidentate chiral phosphine and its coordination
chemistry in transition metal clusters
a
a,
b
Marina M. Tomashevskaya , Sergey P. Tunik *, Ivan S. Podkorytov ,
c,
c
d
d
Brian T. Heaton *, Jonathan A. Iggo , Matti Haukka , Tapani A. Pakkanen ,
e
f
Pa¨ivi L. Pirila¨ , Jouni Pursiainen
a
Department of Chemistry, St. Petersburg State University, Universitetskii pr., 26, St. Petersburg 198504, Russia
b
S.V. Lebedev Central Synthetic Rubber Research Institute, Gapsalskaya 1, St. Petersburg 198035, Russia
c
Department of Chemistry, University of Liverpool, P.O. Box 147, Liverpool L69 7ZD, UK
Department of Chemistry, University of Joensuu, P.O. Box 111, FIN-80101 Joensuu, Finland
d
e
Biocenter Oulu and Department of Biochemistry, P.O. Box 3000, FIN-90014 University of Oulu, Finland
f
Department of Chemistry, P.O. Box 3000, FIN-90014 University of Oulu, Finland
Received 7 November 2006; received in revised form 23 February 2007; accepted 2 March 2007
Available online 14 March 2007
Abstract
The optically active ligand R,R-PHAZAN (1,3-bis[(1R)-1-Phenylethyl]-2-(2-thienyl)-1,3,2-diazaphospholane) has been prepared and
the products resulting from the reactions with Rh6(CO)15NCMe, H3RhOs3(CO)12, and H4Ru4(CO)12 have been investigated by X-ray
crystallography and a variety of multinuclear NMR methods. X-ray studies show that PHAZAN can behave as a bidentate ligand in
Rh6(CO)14(l2,j2-R,R-PHAZAN) (with coordination through P and S) or a monodentate ligand (through P coordination) in
H4Ru4(CO)11(j1-R,R-PHAZAN) and NMR studies show that these structures are retained in solution. In Rh6(CO)14(l2,j2-R,R-PHA-
ZAN), edge-bridging coordination of PHAZAN results in the formation of an additional two novel chiral centres and these are observed
in solution. Reaction of PHAZAN with H3RhOs3(CO)12 results in cleavage of the thienyl group and formation of the phosphido cluster,
H2RhOs3(CO)11(l2-PNN), (PNN = 1,3-bis-(1-phenylethyl)-[1,3,2]diazaphospholidine-2-yl). A variety of NMR measurements show that
the hydride site-occupancies in the solid state are retained in solution and there is evidence for interaction of an ortho-phenyl hydrogen
and a hydride through ‘‘dihydrogen’’ bonding.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Cluster compounds; Phosphines; X-ray diffraction; NMR spectroscopy; Asymmetry; Nuclear Overhauser effect
1. Introduction
ligands determining stereoinduction of the catalysts. This
stimulates growing interest in the synthesis of novel chiral
ligands, which is a booming field of academic research
and fine-chemicals business. In this area, phosphines are
extremely versatile ligands; they may include a broad range
of chiral auxiliaries incorporated into the structure of the
phosphines with a particular rigid organic fragment.
Among these chiral fragments 1-phenylethylamine is an
easily available and relatively inexpensive starting synthon,
which allows a flexible design of asymmetric auxiliaries in
the ligands of various nature. One of the simplest and
In the fast-developing area of asymmetric catalysis, tun-
ing of the reactivity of the catalysts and the chiral induction
in a particular reaction are of primary importance. One of
the main ways to reach this goal relys upon the directed
modification of steric and electronic properties of the chiral
*
Corresponding authors. Tel.: +7 812 4284028; fax: +7 812 4286939
(S.P. Tunik).
E-mail address: stunik@chem.spbu.ru (S.P. Tunik).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.03.008

2912
M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
Me
Me
Me
Me
(d)
N
N
N
N
P
P
O
Ar'
O
Ph
Ph
OAr
(b)
(c)
Ph
Ph
Me
Me
(a)
Me
NH
HN
NH
2
Ph
Ph
Me
Me
N
N
P
Ar
Ph
Ph
Scheme 1. (a) BrCH2CH2Br, Et3N, 115 ꢁC; (b) ArOP(O)Cl2, Et3N/CH2Cl2, rt; (c) ArPCl2, Et3N/THF, ꢀ50 ꢁC; (d) n-BuLi/THF, ꢀ78 ꢁC.
effective ways to introduce this chiral fragment into the
structure of a phosphorus containing ligand is the
condensation of dichlorophosphine or dichlorophosphine
oxide with the diamine derived from 1-phenylethylamine,
see Scheme 1.
This synthetic approach has been applied to obtain
the corresponding chiral phosphines [1,2] and phosphine
oxides [3,4], which were further used in asymmetric catal-
ysis [1,4–8], as chiral inductors in stoichiometric reactions
[3,9–11] and as probing reagents for establishing the
enantiomeric excess by means of 31P NMR spectroscopy
[12–15].
It is quite surprising that despite the wide use of these
ligands in catalysis there have been no reports on the
studies of their coordination chemistry neither in mono-
nor in poly-nuclear metal complexes. It is worth noting
that asymmetric induction of these ligands can be sub-
stantially improved by functionalization of the third sub-
stituent at the phosphorus atom [4]. These structural
modifications may provide an additional interaction of
the ligands with catalytic substrates or allow their multid-
entate coordination thus supporting the conformational
rigidity of the catalyst chiral pocket. Understanding of
the nature of these effects, as well as the directed tuning
of the catalytic enantioselectivity requires an investigation
of the coordination chemistry of the ligand, the structure
and properties of the corresponding complexes. In the
present paper, we report the synthesis of a related biden-
tate phosphine (2) containing an additional thienyl
coordinating function and describe the study of the coor-
dination chemistry of (2) in tetra- and hexa-nuclear car-
bonyl clusters.
All solvents were dried over appropriate drying agents
and distilled prior to use. The reaction of the cluster com-
pounds with the chiral phosphine was carried out under an
argon atmosphere using standard Schlenk techniques.
Products were separated in air by column chromatography
on silica (5-40 mesh) (Lenchrom Ltd., St. Petersburg). Ele-
mental analysis was carried out in the analytical laboratory
of the University of Joensuu. EI and ESI mass spectra were
recorded on MX-1321 and Bruker BioAPEX II 47e instru-
ments, respectively. Fast atom bombardment (FAB+)
mass spectra were obtained on a Trio 2000 instrument.
The IR spectra were measured using a Specord M80 spec-
trophotometer. CD spectra were recorded on a Jasco J-715
spectropolarimeter.
2.2. NMR measurements
1H, 13C and 31D NMR spectra were recorded on a Bru-
ker DPX 300 instrument. HMQC spectra were recorded on
a Bruker AMX2 200 or Avance2 400 spectrometer as pre-
viously described [20].
2.3. N,N0-bis(1-(R)-1-phenylethylamine)-1,2-
ethylenediamine (1)
A
solution of (R)-(+)-1-phenylethylamine (5.16 g,
43 mmol), 1,2-dibromethane (1.88 g, 10 mmol) and Et3N
(2.02 g, 20 mmol) in acetonitrile was placed into an ace
pressure tube and heated in an oil bath (110 ꢁC) for 15 h.
By this time, the reaction mixture darkened and
Et3N Æ HBr was precipitated. The solution was then filtered
and concentrated in vacuo to give a viscous yellow oil,
which was diluted with CH2Cl2 (15 cm3) and washed
(2 · 10 cm3) with KOH 5% aqueous solution saturated
with NaCl. The organic layer was dried over sodium sul-
fate, concentrated and distilled under reduced pressure.
The excess (R)-(+)-1-phenylethylamine (3.57 g) was dis-
tilled off at 78–80 ꢁC (18 mm Hg) and the product (1)
(1.93 g, 73%) was obtained as the second fraction of the
distillation, bp 205 ꢁC/4 mm Hg. The compound was iden-
tified by comparison of its spectroscopic characteristics
with the literature data [21].
2. Experimental
2.1. General comments
Reagent grade (R)-(+)-1-phenylethylamine (Acros),
1,2-dibromoethane and Et3N were used without further
purification. Dichloro(thiophene-2-yl)phosphine [16], Rh6-
(CO)15 (NCMe) [17], H4Ru4(CO)12 [18], and H3Os3Rh(CO)12
[19] were synthesized according to published procedures.

M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
2913
2.4. 1,3-bis[(1R)-1-Phenylethyl]- 2-(2-thienyl)-1,3,2-
diazaphospholane-R,R-PHAZAN) (2)
J = 6.6 Hz, 3H, CH3), **1.61 (d, J = 6.6 Hz, 3H, CH3),
*
*1.59 (d, J = 9.0 Hz, 3H, CH3), 1.42 (d, J = 9.0 Hz, 3H,
31
*
CH3). P NMR (121 MHz, CDCl3, 25 ꢁC, major diaste-
Dicloro(thiophene-2-yl)phosphine (0.28 g, 1.5 mmol)
was added dropwise at ꢀ50 ꢁC under an argon atmosphere
to a solution of N,N0-bis(1-(R)-1-phenylethylamine)-1,2-
ethylenediamine (1) (0.40 g, 1.5 mmol) and Et3N (0.31 g,
1.5 mol) in THF (8 cm3). The resulting mixture was
allowed to warm up to room temperature and stirred for
another 0.5 h. The precipitate of Et3N Æ HCl was filtered
off and the filtrate concentrated in vacuo to give a viscous
pale yellow oil. It was dissolved in THF (1 cm3) and the
desired product was extracted with hexane (4 · 5 cm3).
The solvent was removed and the residue (colourless oil)
was dried in vacuo for 5 h to give 0.43 g of (2). The product
was left for a month at ꢀ20 ꢁC under an argon atmosphere
to give a white amorphous solid. Yield 80%, mp 42 ꢁC.
1H NMR (300 MHz, CDCl3, 25 ꢁC): d = 7.60 (d,
J = 4.4 Hz, 1H, thienyl), 7.12–7.48 (m, 12H, ArH), 4.10
(pseudo-quintet, J = 6.6 Hz, 1H, CH), 3.72 (pseudo-quin-
tet, J = 6.6 Hz, 1H, CH), 2.72–3.15 (m, 4H, CH2), 1.65
reomer, **minor diastereomer): d = **89.23 (d, JRh–P
=
*
173 Hz), 88.84 (d, JRh–P = 173 Hz). MS-FAB (m/z): 1390
(M+) (calc 1390), [M+ꢀnCO], n = 1–14. Anal. Calc. for
C36H25N2O14PSRh6: C, 31.11; H, 1.81; N 2.02. Found:
C, 31.23; H, 1.86; N 2.08%. Single crystals of 3 suitable
for X-ray analysis were obtained by slow evaporation of
the hexane solution at ꢀ20 ꢁC.
2.6. H2RhOs3(CO)11(PNN) (4)
A solution of H3RhOs3(CO)12 (25 mg, 0.025 mmol) and
R,R-PHAZAN) (11 mg, 0.028 mmol) in degassed CHCl3-
(25 cm3) was stirred at room temperature for 30 min under
an argon atmosphere. By this time, the colour of the
mixture turned orange and a TLC spot test (eluent
CH2Cl2–hexane (2/5 v/v)) showed the presence of one
major product and some starting cluster. The reaction mix-
ture became bright-yellow after stirring at 40 ꢁC for 30 min.
A TLC spot test showed complete consumption of the
starting cluster and formation of a new product. The sol-
vent was then evaporated under reduced pressure, the
resulting mixture was diluted with CH2Cl2 (1.5 cm3) and
hexane (3 cm3) and transferred onto a chromatographic
column (2 · 10 cm). Careful separation gave the cluster 4
as a major product (23 mg, 72%).
4
4
(d, JHꢀ P = 6.6 Hz, 3H, CH3), 1.55 (d, JH–P = 5.5 Hz,
3H, CH3), 13C NMR (75 MHz, CDCl3, 25 ꢁC): phenyl
and thienyl signals: d = 145.81, 145.75, 145.56, 145.46,
132.98, 132.60, 130.52, 128.94, 128.77, 128.67, 128.10,
128.04, 127.67, 127.62, 127.54, 127.39, 127.35, 127.22,
2
2
60.15 (d, JC–P = 87.2 Hz, CH), 58.94 (d, JC–P = 47.6 Hz,
2
2
CH), 50.03 (d, JC–P = 31.7 Hz, CH2), 49.83 (d, JC–P
=
3
35.7 Hz, CH2), 24.86 (d, JC– P = 59.5 Hz, CH3), 23.58
IR (CHCl3, cmꢀ1), m(CO) 2090 m, 2060 s, 2027 vs, 2012
sh, 1990 m, 1980 sh, 1870 w, br. 1H NMR (300 MHz,
CDCl3, 25 ꢁC): d = 7.29–7.53 (m, 10H, Ph), 4.34–4.50
(m, 1H, CH), 4.00–4.15 (m, 1H, CH), 3.47-3.75 (m, 2H,
CH2), 3.23–3.39 (m, 2H, CH2), 1.69 (d, J = 6.6 Hz, 3H,
(d, JC–P = 71.4 Hz, CH3). 31P NMR (121 MHz, CDCl3,
3
25 ꢁC): d = 79.94 (s). EI MS (m/z): 380 (M+) (calc 380).
Anal. Calc. for C22H25N2PS: C, 69.45; H, 6.62; N 7.36.
Found: C, 69.39; H, 6.82; N 7.26%.
CH3), 1.67 (d, J = 6.6 Hz, 3H, CH3), ꢀ22.63 (d, JH–P
=
2.5. Rh6(CO)14(l2-R,R-PHAZAN) (3)
6.5 Hz, 1H, hydride), ꢀ22.74 (d, JH–P = 6.5 Hz, 1H,
hydride). 31P NMR (121 MHz, CDCl3, 25 ꢁC): d = 259.7
(s). MS-FAB (m/z): 1282 (M+) (calc. 1282), [M+ꢀnCO],
n = 1–11. Anal. Calc. for C39H24N2O11PRhOs3: C, 27.19;
H, 1.89; N 2.19. Found: C, 27.13; H, 1.88; N 2.20%.
Single crystals of 4 suitable for X-ray analysis were
obtained by slow diffusion of hexane into a CH2Cl2solution
at ꢀ3 ꢁC.
A mixture of Rh6(CO)15NCMe (80 mg, 0.074 mmol)
and R,R-PHAZAN (31 mg, 0.081 mmol) in degassed
CHCl3 (50 cm3) was stirred for 1.5 h at 40 ꢁC. By this time,
a TLC spot test (eluent CH2Cl2–hexane (1/2 v/v)) showed
the presence of the major product (red-brown band) and
a minor one (brown band). The reaction mixture was con-
centrated in vacuo to ca. 1.5 cm3, diluted with hexane
(3 cm3) and transferred onto a chromatographic column
(2.5 · 13 cm). Separation with CH2Cl2–hexane (1/2 v/v)
mixture gave the following bands in the order of elution:
trace amount of Rh6(CO)16; Rh6(CO)15(j1-(R/R)-PHA-
ZAN) (5 mg, 5%) and Rh6(CO)14(l,j2-R,R-PHAZAN)
(3, 65 mg, 64%).
2.7. H4Ru4(CO)11(j1-R,R-PHAZAN) (5)
H4Ru4(CO)12 (60 mg, 0.080 mmol) and R,R-PHAZAN)
(34 mg, 0.088 mmol) were dissolved in degassed CHCl3
(35 cm3) and a solution of Me3NO.2H2O (9 mg, 0.088
mmol) in 10 cm3 CHCl3 was added dropwise with vigorous
stirring. The reaction mixture was stirred at 50 ꢁC until a
TLC spot test (eluent CH2Cl2–hexane (1/3 v/v)) showed
complete consumption of the starting cluster into the major
product (orange band). The solvent was then removed in
vacuo, the residue dissolved in CH2Cl2 (1.3 cm3) and
diluted with hexane (3 cm3) leaving some amorphous
crystalline material, which was filtered off. The solution
obtained was purified by column chromatography (2.5 ·
IR (CHCl3, cmꢀ1), m(CO) 2090 m, 2060 vs, 2032 m, 2005
w, 1782 w, br. 1H NMR (300 MHz, CDCl3, 25 ꢁC, * major
diastereomer, **minor diastereomer): d = **7.66 (t, J =
4.4 Hz, 1H, thienyl), *7.63 (t, J = 4.4 Hz, 1H, thienyl),
*
7.29–7.58 (m, 10H, Ph), 7.05 (t, J = 4.4 Hz, 1H, thienyl),
**7.01 (t, J = 4.4 Hz, 1H, thienyl), 6.13 (dd, J = 4.4,
2.2 Hz, 1H, thienyl), **5.48–5.60 (m, 2H, CH), 5.21–5.38
*
(m, 2H, CH), 2.91–3.33 (m, 4H, CH2), **1.74 (d,

2914
M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
SHELXL-97 [28]. The thiophene ring in 5 was disordered hav-
ing two orientations. The S1 and C33 atoms were refined
over two positions with equal coordinates and occupancies
of 0.84 and 0.16. The idealized positions of the hydride
hydrogens in 4 and 5 were estimated with XHYDEX [29] pro-
gram. All other hydrogens were positioned geometrically
and allowed to ride on their parent atoms. The crystallo-
graphic details are summarized in Table 1 and the selected
bond lengths and angles in Table 2.
12 cm) using CH2Cl2–hexane (1/3 v/v) mixture as eluent.
The following products were isolated in the order of elu-
tion: trace amount of H4Ru4(CO)12 and a main orange
band of (5) (42 mg, 48%).
IR (CHCl3, cmꢀ1), m(CO) 2092 m, 2084 m, 2058 s, 2024
s. 1H NMR (300 MHz, CDCl3, 25 ꢁC): d = 7.72
(t, J = 3.3 Hz, 1H, thienyl), 7.05–7.62 (m, 10H, Ph), 6.82
(d, J = 7.7 Hz, 1H, thienyl), 4.62–4.75 (m, 1H, CH),
4.42–4.54 (m, 1H, CH), 3.16–3.33 (m, 1H, CH2), 2.75–
3.12 (m, 3H, CH2), 1.60 (d, J = 6.6 Hz, 3H, CH3), 1.58
(d, J = 6.6 Hz, 3H, CH3), ꢀ17.29 (br. s, 4H, hydrides).
Hydride signals at ꢀ50 ꢁC: ꢀ17.21 (d, JH–P = 4.9 Hz,
4. Results and discussion
1,3-bis[(1R)-1-Phenylethyl]-2-(2-thienyl)-1,3,2-diazaphos-
pholane R,R-PHAZAN) was synthesized according to
Scheme 2.
2H), ꢀ17.46 (d, JH–P = 13.3 Hz, 1H), ꢀ17.59 (d, JH–P
=
9.5 Hz, 1H). 31P NMR (121 MHz, CDCl3, 25 ꢁC): d =
108.6 (s). MS-FAB (m/z): 1098 (M+) (calc 1098),
[M+ꢀnCO], n = 1–11. Anal. Calc. for C33H29N2O11PS
Ru4: C, 36.13; H, 2.66; N 2.55. Found: C, 36.28; H, 2.83;
N, 2.32%. Single crystals of 5 suitable for X-ray analysis
were obtained by slow diffusion of hexane into a CH2Cl2
solution in the presence of a few drops of methanol at
ꢀ20 ꢁC.
To optimize the yield of N,N0-bis(1-(R)-1-Phenylethyl-
amine)-1,2-ethylenediamine, the synthesis was carried out
in an ace pressure tube under high temperature and
pressure. The reaction of the diamine with dicloro(thio-
phene-2-yl)phosphine gave the phosphine (2) as a white
amorphous solid in high yield. The structure of (2) was
1
determined using H, 13C and 31P NMR spectroscopy. As
expected, the diamine (1) and the phosphine (2) display
nearly identical Cotton responses in their CD spectra
below 280 nm (Fig. S1) which is indicative of the same
source of asymmetry in both compounds. The coordina-
tion behaviour of (2) relies upon the presence of the phos-
phorus and thienyl coordinating functions, which in
principle allow bridging or chelating coordination of this
ligand in polynuclear transition metal complexes.
3. X-ray crystal structure determinations
The crystals were immersed in cryo-oil, mounted in a
Nylon loop and measured at a temperature of 120 K.
The X-ray diffraction data was collected by means of a
Nonius Kappa CCD diffractometer using Mo Ka radiation
˚
(k = 0.71073 A). The Denzo-Scalepack [22] program pack-
age was used for cell refinements and data reductions. All
of the structures were solved by direct methods using the
SIR97, SIR2004, or SHELXS-97 [23–25] with the WINGX [26]
graphical user interface. An empirical absorption correc-
tion was applied to all of the data (XPREP in SHELXTL
v.6.14-1) [27]. Structural refinements were carried out using
4.1. Rh6(CO)14(l2-R,R-PHAZAN) (3)
Reaction of the labile cluster, Rh6(CO)15NCMe, with
the PHAZAN ligand, accompanied by warming the reac-
Table 1
Crystal data and structure refinement for 3, 4 and 5
Rh6(CO)14(l2-j2-R,R-PHAZAN) (3)
H2RhOs3(CO)11(l2-PNN) (4)
H4Ru4(CO)11(j1-R,R-PHAZAN) (5)
Empirical formula
Molecular weight
Crystal system
Space group
C
36H25N2O14PRh6S
C29H24N2O11Os3PRh
1280.98
Monoclinic
P21
18.1671(5)
8.2765(2)
23.6046(3)
90ꢁ
108.5130(10)
90
3365.52(13)
120(2)
C33H29N2O11PRu4S
1096.89
Orthorhombic
P21 21 21
9.14450(10)
17.4658(2)
24.1155(3)
90
1390.07
Monoclinic
P21
9.42510(10)
17.8492(3)
12.82930(10)
90
104.9470(10)
90
2085.25(4)
120(2)
˚
a (A)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
90
3
˚
V (A )
3851.63(8)
120(2)
T (K)
Z
2
4
4
Dcalc (g cmꢀ3
)
2.214
2.475
2.528
11.879
1.892
1.692
l (mmꢀ1
)
Number of reflections collected
31989
56755
54062
Number of unique reflections
9459
15254
8811
Rint
Ra
wR2a
0.0415
0.0243
0.0483
0.0730
0.0499
0.1187
0.0623
0.0271
0.0474
a
I > 2r.

M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
2915
Table 2
Selected bond lengths in Rh6(CO)14(l2,j2-R,R-PHAZAN) (3), H2RhOs3(CO)11(l2-PNN) (4) and H4Ru4(CO)11(j1-R,R-PHAZAN) (5)
(3)
(4)
(5)
Rh(1)–Rh(2)
Rh(1)–Rh(6)
Rh(1)–Rh(5)
Rh(1)–Rh(4)
Rh(2)–Rh(3)
Rh(2)–Rh(5)
Rh(2)–Rh(6)
Rh(3)–Rh(6)
Rh(3)–Rh(4)
Rh(3)–Rh(5)
Rh(4)–Rh(5)
Rh(4)–Rh(6)
Averagea
2.7647(4)
2.7776(4)
2.7876(4)
2.8016(4)
2.7097(4)
2.7152(4)
2.7376(4)
2.7613(4)
2.7638(4)
2.7949(4)
2.7287(4)
2.7634(4)
2.759(29)
Os(1)–Rh(1)
Os(1)–Os(2)
Os(1)–Os(3)
Os(2)–Rh(1)
Os(2)–Os(3)
Os(3)–Rh(1)
2.7325(14)
2.8762(8)
2.9739(8)
2.7680(14)
2.9871(8)
2.7328(14)
Ru(1)–Ru(4)
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Ru(2)–Ru(4)
Ru(3)–Ru(4)
Averagea
2.7972 (3)
2.9699 (3)
2.9760 (4)
2.7912 (3)
2.9729 (4)
2.9672 (4)
2.901 (88)
Os(1)–C(1)
Os(1)–C(2)
Os(2)–C(5)
Os(2)–C(4)
Os(3)–C(7)
Os(3)–C(8)
Os(3)–C(9)
Rh(1)–C(10)
Rh(1)–C(11)
Os(1)–C(3)
Rh(1)–C(3)
Os(2)–C(6)
Rh(1)–C(6)
1.882(16)
1.899(18)
1.861(17)
1.891(18)
1.888(17)
1.925(16)
1.926(19)
1.873(15)
1.892(16)
2.082(16)
2.200(17)
2.035(15)
2.283(14)
Ru(1)–C(2)
Ru(1)–C(1)
Ru(2)–C(3)
Ru(2)–C(5)
Ru(2)–C(4)
Ru(3)–C(6)
Ru(3)–C(8)
Ru(3)–C(7)
Ru(4)–C(10)
Ru(4)–C(9)
Ru(4)–C(11)
Averagea
1.880(4)
1.882(4)
1.900(4)
1.910(4)
1.933(4)
1.894(4)
1.905(4)
1.922(4)
1.892(4)
1.897(4)
1.947(3)
1.905(20)
Averagea. Rh–C(O)term
1.900(10)
Rh(1)–C(2)
Rh(2)–C(2)
Rh(5)–C(2)
Rh(1)–C(9)
Rh(4)–C(9)
Rh(6)–C(9)
Rh(2)–C(7)
Rh(3)–C(7)
Rh(6)–C(7)
Rh(3)–C(6)
Rh(4)–C(6)
Rh(5)–C(6)
Averagea
2.184(4)
2.140(4)
2.238(4)
2.153(4)
2.211(4)
2.185(4)
2.112(4)
2.244(4)
2.222(4)
2.200(4)
2.217(4)
2.159(4)
2.189(39)
2.3017(9)
2.3830(9)
1.745(4)
1.821(4)
1=2
Os(1)–P(1)
Os(2)–P(1)
2.363(4)
2.353(4)
Rh(1)–P(1)
Rh(2)–S(1)
S(1)–C(15)
P(1)–C(15)
a
2
Values of variance S ¼ ½ðxi ꢀ ꢀxÞ =ðn ꢀ 1Þꢁ for the averages are given in parentheses.
120 ºC,15 h
Br
H
N
Et3N
NH2
+
+
Br
N
H
-Et3N*HBr
THF, Et3N
-Et3N*HCl
H
N
N
S
N
P
+
PCl2
N
S
H
Scheme 2.
tion mixture, readily affords the cluster (3) with edge-bridg-
ing coordination of the phosphine through phosphorus and
thienyl sulfur. The solid state structure of (3) was estab-
lished using X-ray crystallography. An ORTEP view of
(3) is shown in Fig. 1 with selected structural parameters
in Table 2. The ligand occupies two terminal sites on adja-
cent rhodium atoms to form a five-membered dimetallacy-
cle, which is a typical structural motif for the coordination
of thienylphosphines on the Rh6-framework [30]. The sub-
stitution does not change the cluster electron count which
corresponds to a closed octahedral structure of the rho-
dium framework in (3). Bond lengths and angles in (3)
(see Table 2) are not significantly distorted when compared
to the closely analogous clusters, Rh6(CO)14(l,j2-
Ph2PThienyl) and Rh6(CO)14(l,j2-PhPThienyl2) [30]; this
is indicative of an essentially non-strained coordination
of the bulky PHAZAN ligand. The solid state conforma-
tions of the chiral auxiliaries in coordinated PHAZAN
allows minimization of the ligand nonbonding interactions
with adjacent CO’s. The presence of a few short contacts

2916
M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
is associated with the coordinated tetrahedral sulfur atom
whereas the other is a planar chiral ‘‘Rh3PS’’ fragment
[30]. Crystallographic analysis in P21 group revealed only
one isomeric form of the molecule in the crystal cell of
(3). Stereochemically, this isomer can be assigned to
RRPHAZANRSRpl configuration, where subscript ‘‘S’’ and
‘‘pl’’ denote conformations of coordinated sulfur and pla-
nar chiral fragments, respectively. However, the 31P and
1H NMR data (Fig. 2) clearly show duplicate sets of sig-
nals, with essentially similar spectroscopic characteristics,
that points to the presence of two isomeric forms in the
bulk sample. Relative intensities of the corresponding res-
onances in the major and minor sets are 3/1 irrespective
of the sample used in the measurements. Appearance of
these isomers is most probably due to the formation of
two diastereoisomers, which are shown schematically
below.
Fig. 1. ORTEP view of Rh6(CO)14(l2,j2-R,R-PHAZAN) (3).
˚
˚
(H(20)–O(2) 2.898 A, H(23)–O(2) 2.545 A, H(31)–O(9)
˚
˚
2.349 A, H(38)–O(9) 2.642 A) does not affect the general
motif and particular structural parameters of the carbonyl
environment, which is close similar to the other
Rh6(CO)14(l,j2-PX) clusters characterized earlier [30,31].
Edge-bridging coordination of PHAZAN results in the
formation of two novel chiral centers in (3). One of them
Fig. 2. 1H and 31P NMR spectra of Rh6(CO)14(l2,j2-R,R-PHAZAN) (3), CDCl3, 25 ꢁC. ‘‘maj’’ and ‘‘min’’ denote the signals of major and minor
diastereomers of (3).

M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
2917
˚
These forms of the molecule differ in stereoconfiguration of
the planar chiral ‘‘Rh3PS’’ fragment (R or S), which in turn
dictates [30] the configuration of the coordinated sulfur to
minimize nonbonding interaction of the thienyl ring with
the adjacent C(12)O group. The diastereomers are evi-
dently different in the interaction of the ligand chiral auxil-
iaries with the carbonyl environment of the triangle but this
difference is not energetically significant because both con-
figurations are present in solution in comparable amounts.
The excess of an isomer with a certain stereoconfiguration
of the planar chiral ‘‘Rh3PS’’ center was also detected by
CD measurements, Fig. S2. In addition to the ligand in-
duced Cotton effects below 300 nm, the spectrum of (3) dis-
plays the absorption bands at 320, and 370 nm that
indicates asymmetry of the molecular fragments, which in-
clude metal atoms of the cluster skeleton.
angle. The Os(1)–Os(2) bond (2.8762(8) A) bridged by the
phosphide ligand is considerably shorter compared to the
˚
other Os–Os bonds (Os(1)–Os(3) (2.9739(8) A) and
Os(2)–Os(3) (2.9871(8) A). This observation clearly points
˚
to coordination of the hydrides over the latter edges of
the cluster skeleton. These effects of the bridging hydrides
and phosphides are absolutely typical for osmium clusters
[35–45] and can be used to reliably locate the hydride
ligands over certain bonds of metal skeleton. This assign-
ment is in agreement with the analysis of the difference
Fourier map which allows the site occupancies of the
hydrides to be deduced as shown in Fig. 3. This assignment
of the site occupancy of the hydrides has been confirmed by
NMR measurements, see below. The carbonyl environ-
ment of (4) consists of 11 CO’s, nine of which are terminal
and two CO’s span Os(1)–Rh(1) and Os(2)–Rh(1) edges.
The coordination of the bridging carbonyls along the two
Os–Rh edges is strongly asymmetric; the Os–C(O) bond
Variable temperature 31P measurements (25–70 ꢁC)
showed no line broadening and no changes in the relative
intensities of the signals that is indicative of conforma-
tional rigidity of the isomers in this temperature range. It
has to be noted that the rhodium–sulfur bond in (3) is
not broken by gaseous CO to form a j1-coordinated ligand
in contrast to structurally analogous Rh6-alkenylphosphine
derivatives studied earlier [32], when the bridging ligand
easily breaks the rhodium–alkenyl bond to change the con-
formation of the alkenyl fragment or is substituted by CO.
The carbonyl environment of (3) is nonrigid at room tem-
perature and the low temperature limiting spectrum is
obtained at ꢀ55 ꢁC. The 13C–{103Rh} and 31P–{103Rh}
HMQC experiments run at this temperature (Figs. S3
and S4) allow unambiguous assignments of the signals cor-
responding to the major diastereomer, and these results are
summarised in Table 3. The data obtained show that the
structure of the carbonyl environment found in the solid
state is retained in solution. These spectroscopic data cor-
respond well with the data obtained earlier for the
Rh6(CO)14(l,j2-Ph2PThienyl) cluster [31], including the
considerable lowfield shift of the signal corresponding to
sulfur bound rhodium atom.
˚
lengths (2.035 and 2.082 A) are considerably shorter than
the Rh–C(O)’s. This is completely in line with the influence
of the adjacent phosphide, which increases the electronic
density on the osmium atoms to strengthen the basicity
of these metal centers and their p-back donation to the cor-
responding carbonyl ligands. This influence moves the
bridging CO’s from rhodium towards these osmium atoms.
The solution structure of (4) was investigated by a broad
range of NMR techniques: 1H, 13C, 31P, 31P–{103Rh}
HMQC, 13C–{103Rh} HMQC and H NOE, see Table 3,
1
Figs. 4, 5, S5, S6 and by CD measurements, Fig. S7. The
solid state structure of the isolated ‘‘(l-H)2Os3Rh-
(CO)9(l-CO)2(l-P)’’ fragment in (4), in principle, implies
the presence of a symmetry plane through P(1), Os(3)
and Rh(1). However, two chiral auxiliaries in the phos-
phide ligand make the structure of (4) asymmetric and give
rise to the spectroscopic patterns corresponding to the
absence of symmetry elements in the molecule. The coordi-
nation sphere of (4) is stereochemically rigid at room tem-
perature to give 11 multiplets due to the CO ligands in the
carbonyl region of the 13C NMR spectrum. Analysis of the
13C{1H} (Table 3) and 13C–{103Rh} HMQC (Fig. S6) spec-
tra together with the 13C–{1Hhydrides} selective decoupling
experiments (Fig. S5) shows that the structure of the car-
bonyl environment and mutual disposition of the hydride
and carbonyl ligands found in the solid state remain
unchanged in solution. The ‘‘organic’’ region of the proton
spectrum of (4) displays two sets of multiplets (CH3, CH2
and CH protons together with unresolved resonance, due
to the phenyl rings), Fig. 4, corresponding to inequivalent
chiral auxiliaries disposed over and out of the osmium tri-
angle. The two hydrides generate the doublets at ꢀ22.74
and ꢀ22.63 ppm and the coupling constants, (2J(P–H) =
6.6 Hz), correspond to a cis disposition of the hydrides
over adjacent Os–Os bonds [37,41,42,44,45]. It is
worth noting that the asymmetry of the {–C(13)HC-
(14)H3Ph}-moieties results in a specific orientation the chi-
ral unit with respect to the osmium triangle to minimize
nonbonding interaction of the phenyl ring with the nearest
4.2. H2RhOs3(CO)11(PNN*) (4)
The mixed metal H3RhOs3(CO)12 cluster readily reacts
with R,R-PHAZAN to give H2RhOs3(CO)11(l,j1-PNN*)
(4), containing the phosphide PNN* ligand coordinated
along an Os–Os bond, see Scheme 3.
The phosphide fragment is formed through oxidative
cleavage of the P-thienyl bond followed by reductive elim-
ination of thiophene to give (4). The solid state structure of
(4) was established by X-ray crystallography and an
ORTEP view of this molecule is shown in Fig. 3; selected
structural parameters are given in Table 2. The electron
count for (4) (60 electrons) fits exactly to a closed tetrahe-
dral structure [33,34] of the cluster framework. The Os–Rh
˚
bond lengths fall in a narrow range 2.7325–2.7680 A,
whereas the Os–Os distances differ substantially due to
the effects of the ligands coordinated over the osmium tri-

2918
M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
Table 3
The 13C, 31P and 103Rh NMR spectroscopic data for the clusters (3) and (4)
C(O)a
d, ppm, 13C
J(C–P), Hz
J(C–Rh), Hz
(3)(major isomer) (298 K, CDCl3)
C(1)O
C(3)O
C(4)O
C(5)O
184.2 dd
11.4
–
–
–
–
23.8
–
24.7
–
–
71.6
70.0
65.1
72.3
71.6
69.1
68.2
68.7
69.1
68.2
181.5 d
183.7 d
180.8 d
180.9 d
179.7 dd
184.3 d
183.3 dd
179.6 d
179.4 d
247.8 s
232.5 s
242.2 s
238.4 s
103Rh, d, ppm
ꢀ308
C(8)O
C(14)O
C(10)O
C(11)O
C(12)O
C(13)O
l3-C(2)O
l3-C(6O
l3-C(7)O
l3-C(9)O
Rh(1)
Rh (2)
Rh (3)
Rh (4)
Rh (5)
Rh (6)
+7
ꢀ365
ꢀ383
ꢀ380
ꢀ428
31P, d, ppm
87.7 d
J(P–Rh), Hz
172.3
172.3
Major isomer
Minor isomer
89.8 d
C(O)b
d, ppm, 13C
J(C–P), Hz
J(C–Rh), Hz
J(C–Ha), Hz
J(C–Hb), Hz
4(298 K, CDCl3)
l2-C(3)O
l2-C(6)O
C(1)O
C(4)O
C(2)O
C(5)O
C(7)O
C(8)O
C(9)O
211.5 dd
209.4 dd
182.5 d
181.3 d
168.7 m
167.2 m
172.9 d
168.4 s
67.6
65.6
5.1
4.3
5.2
–
2.2
–
–
17.7
14.5
–
–
–
–
–
3.5
3.5
–
–
8.9
–
–
74.6
63.0
3.1
10.7
5.5
–
10.8
3.0
168.2 s
186.6 dd
169.0 d
C(10)O
C(11)O
–
–
Hydrides
H(1)
H(2)
1H, d, ppm
ꢀ22.62
J(H–P)
6.6
6.6
ꢀ22.73
31P, d, ppm
259.7 s
P
a
Assignment can be reversed for the following resonances: C(4)O/C(5)O, C(12)O/C(13)O.
Assignment can be reversed for the following resonances: C(3)O/C(6)O, C(1)O/C(4)O, C(2)O/C(5)O.
b
R
N
N
N
S
P
R
R
N
P
H
H
H
H
H
H
H
H
N
N
R
R
R
P
+
S
- CO
OC
S
CO
Rh
Rh
Rh
(CO)3
(CO)2
(CO)3
- Os(CO)2
R = -CH(CH3)Ph
- Os(CO)3;
(4)
N
N
R
R
PNN* =
P
Scheme 3.

M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
2919
Fig. 3. ORTEP view of H2RhOs3(CO)11(l2-PNN) (4).
CH3
hydrides
phenyl
-22.0
-23.0
CH2
CH
8.0
7.0
6.0
5.0
4.0
3.0
2.0
(ppm)
Fig. 4. 1H NMR spectrum of H2RhOs3(CO)11(l2-PNN) (4), CDCl3, 25 ꢁC. Inset shows the hydride area of the spectrum. Residual signal of
deuterochloroform is marked with an asterisk.
environment (see Fig. 3). This conformation of the molec-
ular fragment contains a few very short nonbonding con-
tacts between the hydrides and nearest protons of the
solution and conformational rigidity of (4) was confirmed
by the H NOE measurements, Fig. 5. The negative part
1
of the NOE spectrum displays three crosspeaks between
the hydride signals and resonances of the CH and CH3
groups. These connectivities are related to through space
interaction the hydrides with the chiral moiety disposed
over the osmium triangle and allow easy assignment of
the corresponding signals in the 1D spectrum through com-
parison of the NMR and X-ray data. The low frequency
hydride resonance evidently corresponds to H(1) because
of its short contacts with the protons of CH and CH3
˚
˚
ligand, H(13)–H(2) 2.19(2) A, H(13)–H(1) 2.63(2) A,
˚
H(14a)–H(1) 2.55(2) A. These contacts are very probably
determined by attractive electrostatic interaction between
positively charged protons and negatively charged
hydrides. The interaction of this sort (so-called ‘‘dihydro-
gen bonding’’) proved to be quite strong and in some cases
may determine the particular configuration of the molecule
as a whole [46–50]. The presence of these interactions in

2920
M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
Fig. 5. Negative parts of the NOE spectrum of (4), C6D6, (a) 298 K and (b) 343 K.
groups, vide supra, which, in turn, are clearly displayed by
the corresponding crosspeaks in the NOE spectrum. Thus,
the high frequency hydride resonance is due to H(2), which
has a short contact with the same CH proton. This interac-
tion is visualized by another crosspeak related to the CH
multiplet. A weaker NOE crosspeak connecting a reso-
nance from the phenyl region and the high frequency
hydride resonance has no direct support in the crystallo-
graphic data. It is, however, evident that rotation of the
phenyl ring around the C(13)–C(15) bond may bring an
ortho phenyl proton into the close vicinity of H(2) to give
the conformation of the molecule which accounts for the
NOE signal observed in the spectrum. This conformation
proved to be a potential sink supported by ‘‘dihydrogen
bonding’’. At higher temperature (+70 ꢁC, Fig. 5b), this
crosspeak disappears because of free rotation of the phenyl
ring that results in averaging of rotational conformations
to increase the average distance between correlated nuclei.
Three other crosspeaks remain unchanged, even at this
substantially higher temperature, which is indicative of
the strength of the ‘‘dihydrogen bonding’’ in the molecule.
This observation points once more to the importance of
this type of interaction for the solution structure of hydride
complexes containing hydrocarbon fragments in the ligand
sphere.
4.3. H4Ru4(CO)11-R,R-PHAZAN (5)
H4Ru4(CO)12 reacts with R,R-PHAZAN in the pres-
ence of Me3NO to give a monosubstituted cluster
H4Ru4(CO)11-R,R-PHAZAN in a reasonable yield. The
solid state structure of this cluster was established by
X-ray crystallography and an ORTEP view of the mole-
cule is shown in Fig. 6; selected structural parameters are
given in Table 2. The phosphine in (5) is coordinated
through the phosphorus atom only and occupies a termi-
nal position in the starting H4Ru4(CO)12 cluster. Substi-
tution of a CO ligand by the phosphine does not change
the cluster electron count and the closed tetrahedral
structure of the Ru4-framework is unchanged. The con-
figuration of the remaining 11 carbonyl ligands is nearly
unchanged from the starting material. In contrast to the

M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
2921
Rh6(CO)16 derivative (3), the thienyl function of PHA-
ZAN remains uncoordinated probably because of the
mismatch of the short ligand bite angle and angular
parameters of the terminal sites available at adjacent
metal atoms. This situation is quite typical for bridging
derivatives of H4Ru4(CO)12. The only example of a
bridging five-membered dimetallacycle in this system is
H4Ru4(CO)10(dppm) [51] with the Ru–Ru–P angles equal
to ca. 92ꢁ, whereas unstrained configurations of the
coordinating functions at the hydride bridged Ru–Ru
bonds give the ‘‘Ru–Ru–X’’ angle values in the range
102–109ꢁ [52–55]. It has to be noted that a closely anal-
ogous P(thienyl)3 ligand [56] also does not form a phos-
phino-thienyl bridge in the reaction with H4Ru4(CO)12 to
afford the monosubstituted H4Ru4(CO)11(j1-P(thienyl)3)
cluster in a manner similar to (5). This observation
shows that the bite angle of the phosphino-thienyl moi-
ety (not the bulkiness of PHAZAN) is the main factor,
which determines the coordination mode of these ligands.
In the solid state, H4Ru4(CO)11L mono-substituted
derivatives containing phosphorus donor ligands display
two motifs for the disposition of the hydrides over the
‘‘Ru4’’ skeleton (A and B below).
Fig. 6. ORTEP view of H4Ru4(CO)11(j1-R,R-PHAZAN) (5).
Fig. 7. VT 1H NMR of (5) in the hydride region: (a) CDCl3, (b) CD2Cl2.

2922
M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
lence of the symmetrically disposed hydrides is clearly
A
B
due to the asymmetry of the phosphine ligand that makes
these hydrides diastereotopic, which differentiates sub-
stantially their chemical shifts and coupling constants.
The remote location of two other hydrides in the struc-
ture (A) leads to a substantially lower coupling con-
stant, 4.9 Hz. Unfortunately, the minor form of the
cluster cannot be characterized with the same level of cer-
tainty because, even at the lowest temperature (176 K) it
was impossible to obtain the necessary resolution to assign
the signals and to deduce the possible structure of the other
isomer.
P
P
H
H
H
H
H
Ru
Ru
Ru
Ru
Ru
Ru
H
H
H
Ru
Ru
The isomer (A) was found in solid state structure of
H4Ru4(CO)11(P(OMe)3) [57], H4Ru4(CO)11(P(C6F5)3) [57]
and H4Ru4(CO)11(PPh3) [58] whereas the H4Ru4(CO)11-
(PPhMe2) cluster [57] exists in form (B). Analysis of the dif-
ference Fourier map obtained for (5) indicates that the
hydrides adopt the (A) structural pattern in the crystal cell
of this complex. Completely in line with the general trend
observed in the H4Ru4(CO)12-substituted derivatives
[56–58], the Ru–Ru edges spanned by the hydride ligands
are the longest in the tetrahedron (see Table 2). This is also
consistent with the structure of the ‘‘H4Ru4P’’ fragment
corresponding to (A) isomer.
5. Conclusion
The optically active ligand R,R-PHAZAN (1,3-bis-
[(1R)-1-Phenylethyl]-2-(2-thienyl)-1,3,2-diazaphospholane)
reacts with various transition metal carbonyl clusters to
give products which contain PHAZAN as either a biden-
tate ligand (with coordination through P and S) or a
monodentate ligand (through P coordination); in addition,
cleavage of the thienyl group can occur to give phosphido
clusters. Edge-bridging coordination of PHAZAN in
Rh6(CO)14(l2,j2-R,R-PHAZAN) results in the formation
of an additional two novel chiral centres and this bodes
well for their future use in asymmetric catalysis. A variety
of multinuclear NMR methods show that the solid state
structures are retained in solution. In particular, it has been
found that ‘‘dihydrogen bonding’’ between protons of
organic ligand and hydrides plays an important role in
retaining the conformation of the cluster molecules in
solution.
Similar to the other H4Ru4(CO)11(PR3) derivatives stud-
ied by solution NMR spectroscopy [57,59], the hydride
environment of (5) is fluxional at room temperature giving
rise to a singlet at ꢀ17.29 ppm, which corresponds to fast
1
exchange of all the hydrides at this temperature. The H
VT spectra of (5) are shown in Fig. 7. Lowering the temper-
ature to 223 K results in the appearance three doublets
(ꢀ17.21 ppm 2H, 17.46 ppm 1H, 17.59 ppm 1H) with dif-
ferent P–H coupling constants: 4.9, 13.3 and 9.5 Hz,
respectively. The phosphorus–hydride spin–spin interac-
tions have been established by selective 1H{31P} decoupling
experiments. The 31P{1H} NMR spectrum at 223 K dis-
plays one slightly broadened signal at 108.6 ppm, which
at 176 K splits into two well resolved singlets at 105.7
and 111.6 ppm with relative intensities of ca. 3:1
(Fig. S8). In the same temperature range, the proton spec-
trum is complicated because of the dynamics of the
hydrides, which are not static, even at 176 K. These obser-
vations can be explained by the exchange between the two
isomeric forms of the hydride environment, for example
between the (A) and (B) isomers shown above. This would
be analogous to the dynamics found in the H4Ru4-
(CO)11(PR3) clusters, suggested earlier [57,59]. Under the
framework of this hypothesis, the proton spectrum of the
system at 223 K is a weighted average of the spectra of
the exchange components. If the equilibrium mixture is
enriched with one of them, the experimental spectrum is
weighted with the dominating form. These characteristics
fit well with the structure of the (A) isomer. For example,
two high field doublets may be assigned to the hydrides
adjacent to the phosphorus ligand, the values of the
2J(P–H) coupling constants (9.5 and 13.3 Hz) being in a
very good agreement with the other examples of cis-(P–H)
interaction in the clusters of this sort [50]. The inequiva-
Acknowledgments
Financial support from the Royal Society for an Inter-
national Joint Awards grant and Journals Grants for
International Authors (S.T) is gratefully acknowledged.
M.T. appreciates greatly financial support from the Uni-
versity of Joensuu in a bilateral exchange program with
St. Petersburg State University. The financial support of
the Russian Foundation for Basic Research (Grant 05-
03-33266) and of EPSRC (Grant EP/C0005643) is also
gratefully acknowledged.
Appendix A. Supplementary material
CCDC 620564, 620565 and 620566 contain the supple-
mentary crystallographic data for 3, 4 and 5. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk. Supplementary data associated with this
article (Figs. S1–S8) can be found, in the online version,
at doi:10.1016/j.jorganchem.2007.03.008.

M.M. Tomashevskaya et al. / Journal of Organometallic Chemistry 692 (2007) 2911–2923
2923
[30] S.P. Tunik, I.O. Koshevoy, A.J. Poe¨, D.H. Farrar, E. Nordlander,
M. Haukka, T.A. Pakkanen, Dalton Trans. (2003) 2457.
[31] E.V. Grachova, M. Haukka, B.T. Heaton, E. Nordlander, T.A.
Pakkanen, I.S. Podkorytov, S.P. Tunik, Dalton Trans. (2003) 2468.
[32] D.V. Krupenya, S.I. Selivanov, S.P. Tunik, M. Haukka, T.A.
Pakkanen, Dalton Trans. (2004) 2541.
[33] M. McPartlin, D.M.P. Mingos, Polyhedron 3 (1984) 1321.
[34] M.S. Owen, Polyhedron 7 (1988) 253.
[35] V.D. Patel, A.A. Cherkas, D. Nucciarone, N.J. Taylor, A.J. Carty,
Organometallics 4 (1985) 1792.
References
[1] G. Pracejus, H. Pracejus, Tetrahedron Lett. 18 (1977) 3497.
[2] A. Alexakis, S. Mutti, P. Mangeney, J. Org. Chem. 57 (1992) 1224.
[3] F. Slowinski, C. Aubert, M. Malacria, Tetrahedron Lett. 40 (1999)
5849.
[4] Z. Yang, Z. Zhou, K. He, L. Wang, G. Zhao, Q. Zhou, C. Tang,
Tetrahedron: Asymmetry 14 (2003) 3937.
[5] B. Burns, N.P. King, H. Tye, J.R. Studley, M. Gamble, M. Wills, J.
Chem. Soc., Perkin Trans. 1 (1998) 1027.
[36] S.B. Colbran, P.T. Irele, B.F.G. Johnson, F.J. Lahoz, J. Lewis, P.R.
Raithby, J. Chem. Soc., Dalton Trans. (1989) 2023.
[37] A.J. Deeming, S. Doherty, M.W. Day, K.I. Hardcastle, H. Minas-
sian, J. Chem. Soc., Dalton Trans. (1991) 1273.
[38] H.G. Ang, C.H. Koh, L.L. Koh, W.L. Kwik, W.K. Leong, W.Y.
Leong, J. Chem. Soc., Dalton Trans. (1993) 847.
[6] B. Breit, J. Mol. Catal. A 143 (1999) 143.
[7] Z.-H. Yang, Z.-H. Zhou, L.-X. Wang, K.-Y. Li, Q.-L. Zhou, C.-C.
Tang, Synth. Commun. 32 (2002) 2751.
[8] K. Li, Z. Zhou, G. Zhao, C. Tang, Heteroatom Chem. 14 (2003) 546.
[9] Y. Miyake, H. Takada, K. Ohe, S. Uemura, J. Chem. Soc., Perkin 1
(2000) 1595.
[39] A.J. Deeming, M.B. Smith, J. Chem. Soc., Dalton Trans. (1993) 3383.
[40] W.R. Cullen, S.J. Rettig, T.C. Zheng, Organometallics 12 (1993) 688.
[41] A.J. Arce, A.J. Deeming, Y. De Sanctis, A.M. Garcia, J. Manzur,
Organometallics 13 (1994) 3381.
[42] W.R. Cullen, S.J. Rettig, H. Zhang, Inorg. Chim. Acta 251 (1996) 53.
[43] B.F.G. Johnson, J. Lewis, E. Nordlander, P.R. Raithby, Inorg.
Chim. Acta 259 (1997) 345.
[44] A.J. Arce, R. Machado, Y. De Sanctis, T. Gonzalez, R. Atencio,
A.J. Deeming, Inorg. Chim. Acta 344 (2003) 123.
[45] V.I. Ponomarenko, T.S. Pilyugina, V.D. Khripun, E.V. Grachova,
S.P. Tunik, M. Haukka, T.A. Pakkanen, J. Organomet. Chem. 691
(2006) 111.
[46] T.B. Richardson, T.F. Koetzle, R.H. Crabtree, Inorg. Chim. Acta
250 (1996) 69.
[47] W. Xu, A.J. Lough, R.H. Morris, Can. J. Chem. 75 (1997) 475.
[48] Y.A. Abramov, L. Brummer, W.T. Klooster, R.M. Bullock, Inorg.
Chem. 37 (1998) 6317.
[10] G.E. Moreno, L. Quintero, S. Bernes, C. Anaya de Parrodi,
Tetrahedron Lett. 45 (2004) 4245.
[11] F. Slowinski, C. Aubert, M. Malacria, J. Org. Chem. 68 (2003) 378.
[12] R. Hulst, N. Koen de Vries, B.L. Feringa, Tetrahedron: Asymmetry
5 (1994) 699.
[13] P.G. Devitt, T.P. Kee, Tetrahedron 51 (1995) 10987.
[14] P.G. Devitt, M.C. Mitchell, J.M. Weetman, R.J. Taylor, T.P. Kee,
Tetrahedron: Asymmetry 6 (1995) 2039.
[15] S.R. Davies, M.C. Mitchell, C.P. Cain, P.G. Devitt, R.J. Taylor,
T.P. Kee, J. Organomet. Chem. 550 (1998) 29.
[16] M. Bentov, L. David, E.D. Bergmann, J. Chem. Soc. (1964) 4750.
[17] S.P. Tunik, A.V. Vlasov, V.V. Krivykh, Inorg. Synth. 31 (1997)
239.
[18] S.A.R. Knox, J.W. Koepke, M.A. Andrews, H.D. Kaesz, J. Am.
Chem. Soc. 97 (1975) 3942.
[19] P. Sundberg, B. Noren, B.F.G. Johnson, J. Lewis, P.R. Raithby, J.
Organomet. Chem. 353 (1988) 383.
[49] R. Custelcean, J.E. Jackson, Chem. Rev. 101 (2001) 1963.
[50] S.P. Tunik, T.S. Pilyugina, I.O. Koshevoy, S.I. Selivanov, M.
Haukka, T.A. Pakkanen, Organometallics 23 (2004) 568.
[51] F. Mansilla, G. Lavigne, J.J. Bonnet, Acta Crystallogr., Sect. C 42
(1986) 1011.
[52] R.D. Wilson, S.M. Wu, R.A. Love, R. Bau, Inorg. Chem. 17 (1978)
1271.
[53] M.A. Churchill, R.A. Lashewicz, J.R. Shapley, S.I. Richter, Inorg.
Chem. 19 (1980) 1277.
[54] J. Puga, A. Arce, D. Braga, N. Centritto, F. Grepioni, R. Castillo, J.
Ascanio, Inorg. Chem. 26 (1987) 867.
[55] P. Homanen, R. Persson, M. Haukka, T.A. Pakkanen, E. Nord-
lander, Organometallics 19 (2000) 5568.
[56] T.M. Rasanen, S. Jaaskelainen, T.A. Pakkanen, J. Organomet.
Chem. 553 (1998) 453.
[57] M.G. Ballinas-Lopez, E.V. Garcia-Baez, M.J. Rosales-Hoz, Polyhe-
dron 22 (2003) 3403.
[20] B.T. Heaton, J.A. Iggo, I.S. Podkorytov, D.J. Smawfield, S.P. Tunik,
R. Whyman, J. Chem. Soc., Dalton Trans. (1999) 1917.
[21] Z. Yang, Z. Zhou, K. He, L. Wang, G. Zhao, Q. Zhou, C. Tang,
Tetrahedron: Asymmetry 14 (2003) 3937.
[22] Z. Otwinowski, W. Minor, in: C.W. CarterJr., R.M. Sweet (Eds.),
Methods in Enzymology, Macromolecular Crystallography, part A,
Academic Press, New York, USA, 1997, pp. 307–326.
[23] A. Altomare, M.C. Burla, M.C. Camalli, C. Giacovazzo, A.
Guagliardi, A.G.G. Moliterni, G. Polidori, R. Spagna, J. Appl.
Crystallogr. 32 (1999) 115.
[24] M.C. Burla, M.C. Camalli, B. Carrozzini, G.L. Cascarano, C.
Giacovazzo, G. Polidori, R. Spagna, J. Appl. Crystallogr. 38 (2005)
381.
[25] G.M. Sheldrick, in: SHELXS97, Program for Crystal Structure Deter-
mination’, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[26] L.J. Farrugia, J. Appl. Cryst 32 (1999) 837.
[27] G.M. Sheldrick, SHELXTL v. 6.14-1, Bruker Analytical X-ray Systems,
Bruker AXS Inc., Madison, WI, USA, 2005.
[28] G.M. Sheldrick, SHELXL97, Program for Crystal Structure Refine-
ment, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[29] M. Nardelli, J. Appl. Crystallogr. 32 (1999) 563.
[58] A.U. Haerkoenen, M. Ahlgren, T.A. Pakkanen, J. Pursiainen, J.
Organomet. Chem. 530 (1997) 191.
[59] S. Aime, M. Botta, R. Gobetto, L. Milone, D. Osella, R. Gellert, E.
Rosenberg, Organometallics 14 (1995) 3693.