Diastereomerically enriched analogues of the water-soluble phosphine PTA. Synthesis of phenyl(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]dec-6- yl)methanol (PZA) and the sulfide PZA(S) and X-ray crystal structures of the oxide PZA(O) and [Cp*IrCl2(PZA)]

Article abstract of DOI:10.1021/ic701795y

A diastereomerically enriched analogue of 1,3,5-triaza-7-phosphaadamantane (PTA) was obtained by the reaction of PTA lithium salt with benzaldehyde to give the water-soluble derivative phenyl-(1,3,5-triaza-7-phosphatricyclo[3.3.1. 1^3,7]dec-6-yl)methanol (PZA, 1) as a mixture of two diastereoisomers. PZA derivatives phenyl-(1,3,5-triaza-7-phospha-tricyclo[3.3.1.1 ^3,7]dec-6-yl)methanol sulfide [PZA(S), 2] and oxide [PZA(O), 3] were also synthesized. The latter was isolated in the solid state, and the X-ray crystal structure of a single diastereoisomer was obtained. Compound 1 was used as a k¹-P monodentate ligand toward iridium(III) moieties, and the piano-stool complex [Cp*IrCl₂(PZA)] (4) was obtained as a mixture of diastereoisomers both in solution and in the solid state.

Full text of DOI:10.1021/ic701795y

Inorg. Chem. 2008, 47, 8−10
Diastereomerically Enriched Analogues of the Water-Soluble Phosphine PTA.
Synthesis of Phenyl(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]dec-6-yl)methanol
(PZA) and the Sulfide PZA(S) and X-ray Crystal Structures of the Oxide
PZA(O) and [Cp*IrCl2(PZA)]
Mikael Erlandsson, Luca Gonsalvi,* Andrea Ienco, and Maurizio Peruzzini*
Istituto di Chimica del Composti Organometallici, Consiglio Nazionale delle Ricerche
(ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy
Received September 12, 2007
A diastereomerically enriched analogue of 1,3,5-triaza-7-phos-
phaadamantane (PTA) was obtained by the reaction of PTA lithium
salt with benzaldehyde to give the water-soluble derivative phenyl-
(1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]dec-6-yl)methanol (PZA, 1)
as a mixture of two diastereoisomers. PZA derivatives phenyl-
(1,3,5-triaza-7-phospha-tricyclo[3.3.1.13,7]dec-6-yl)methanol sulfide
[PZA(S), 2] and oxide [PZA(O), 3] were also synthesized. The
latter was isolated in the solid state, and the X-ray crystal structure
of a single diastereoisomer was obtained. Compound 1 was used
as a k1-P monodentate ligand toward iridium(III) moieties, and the
piano-stool complex [Cp*IrCl2(PZA)] (4) was obtained as a mixture
of diastereoisomers both in solution and in the solid state.
derivatives of PTA. Most of these structural changes are
relatively far from the coordinating P atom and thus unlikely
to impart significant stereoelectronic effects often required
for chemo- or enantioselective catalytic applications and for
fine-tuning of biological effects in the design of hydrosoluble
(3) (a) Bolan˜o, S.; Gonsalvi, L.; Zanobini, F.; Vizza, F.; Bertolasi, V.;
Romerosa, A.; Peruzzini, M. J. Mol. Catal. A: Chem. 2004, 224, 61-
70. (b) Horva´th, H.; Laurenzy, G.; Katho, A. J. Organomet. Chem.
2004, 689, 1036-1045. (c) Mebi, C. A.; Frost, B. J. Organometallics
2005, 24, 2339-2346. (d) Krogstad, D. A.; Cho, J.; DeBoer, A. J.;
Klitzke, J. A.; Sanow, W. R.; Williams, H. A.; Halfen, J. A. Inorg.
Chim. Acta 2006, 359, 136-148. (e) Krogstad, D. A.; Owens, S. B.;
Halfen, J. A.; Young, V. G., Jr. Inorg. Chem. Commun. 2005, 8, 65-
69. (f) Krogstad, D. A.; DeBoer, A. J.; Ortmeier, W. J.; Rudolf, J.
W.; Halfen, J. A. Inorg. Chem. Commun. 2005, 8, 1141-1144. (g)
Ruiz, J.; Cutillas, N.; Lo´pez, F.; Lo´pez, G.; Bautista, D. Organome-
tallics 2006, 25, 5768-5773. (h) Korthals, B.; Go¨ttker-Schnetmann,
I.; Mecking, S. Organometallics 2007, 26, 1311-1316. (i) Mebi, C.
A.; Nair, R. P.; Frost, B. J. Organometallics 2007, 26, 429-438.
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Jennerat, L.; Dyson, P. J. Inorg. Chem. 2006, 45, 9006-9013. (b)
Scolaro, C.; Bergamo, A.; Brescacin, L.; Delfino, R.; Cocchietto, M.;
Laurenczy, G.; Geldbach, T. J.; Sava, G.; Dyson, P. J. J. Med. Chem.
2005, 48, 4161-4171. (c) Dorcier, A.; Dyson, P. J.; Gossens, C.;
Rothlisberger, U.; Scopelliti, R.; Tavernelli, I. Organometallics 2005,
24, 2114-2123. (d) Dorcier, A.; Ang, W. H.; Bolan˜o, S.; Gonsalvi,
L.; Juillerat-Jennerat, L.; Laurenczy, G.; Peruzzini, M.; Phillips, A.
D.; Zanobini, F.; Dyson, P. J. Organometallics 2006, 25, 4090-4096.
(e) Ang, W. H.; Dyson, P. J. Eur. J. Inorg. Chem. 2006, 4003-4018.
(f) Romerosa, A.; Campos-Malpartida, T.; Lidrissi, C.; Saoud, M.;
Serrano-Ruiz, M.; Peruzzini, M.; Garrido-Cardenas, J. A.; Garc´ıa-
Maroto, F. Inorg. Chem. 2006, 45, 1289-1298. (g) Romerosa, A.;
Saoud, M.; Campos-Malpartida, T.; Lidrissi, C.; Serrano-Ruiz, M.;
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2007, 2803-2812.
(5) Gutkin, V.; Gun, J.; Prikhodchenko, P. V.; Lev, O.; Romerosa, A.;
Campos Malpartida, T.; Lidrissi, C.; Gonsalvi, L.; Peruzzini, M. J.
Electrochem. Soc. 2007, 154, F7-F15.
(6) Rossin, A.; Gonsalvi, L.; Phillips, A. D.; Maresca, O.; Lledos, A.;
Peruzzini, M. Organometallics 2007, 26, 3289-3296.
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12, 579-580. (b) Fluck, E.; Weissgraeber, H. J. Chem.-Ztg. 1977,
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337-339. (c) Navech, J.; Kraimer, R.; Majoral, J. P. Tetrahedron Lett.
1980, 21, 1449-1452. (d) Darensbourg, D. J.; Yarbrough, J. C.; Lewis,
S. J. Organometallics 2003, 22, 2050-2056.
During the past few years, there has been a renewed
interest in the use of the neutral water-soluble cage mono-
dentate phosphine 1,3,5-triaza-7-phosphaadamantane (PTA)1
and its structural modifications, as witnessed by the work
of many groups in various fields of applications.2 PTA has
a small cone angle (103°) comparable to that of PH2Me, with
the advantage being that it is solid, less toxic, and air-stable,
hence easier to handle. Its high water solubility (ca. 253 g/L)
makes it an ideal ligand to bring metal and organometallic
fragments into the water phase. The renaissance of PTA as
a water-soluble ligand has resulted in a large number of
coordination compounds being synthesized very recently and
their catalytic,3 medical,4 and electrochemical properties5
being investigated, together with mechanistic aspects of Ru-
PTA-mediated hydrogen activation in water.6
Modifications of the PTA frame have so far been focused
on either alkylation at P or N atoms7,8 or opening of the cage
to yield potentially bidentate P,N9 or tridentate P,N,N10
* To whom correspondence should be addressed. E-mail: l.gonsalvi@
iccom.cnr.it (L.G.), mperuzzini@iccom.cnr.it (M.P.).
(1) Daigle, D. J.; Pepperman, A. B., Jr.; Vail, S. L. J. Heterocycl. Chem.
1974, 11, 407-408.
(2) For a review on coordination chemistry and the use of PTA covering
the literature up to the beginning of 2004, see: Phillips, A. D.;
Gonsalvi, L.; Romerosa, A.; Vizza, F.; Peruzzini, M. Coord. Chem.
ReV. 2004, 248, 955-993 and references cited therein.
8
Inorganic Chemistry, Vol. 47, No. 1, 2008
10.1021/ic701795y CCC: $40.75
© 2008 American Chemical Society
Published on Web 12/11/2007

COMMUNICATION
Scheme 1 Syntheses of 1-4
Figure 1. Asymmetric units of (R,S-S,R)-3. Ellipsoids are shown at 30%
probability.
metal-based drugs. Therefore, there is an interest in develop-
ing chiral PTA derivatives that are substituted at the
methylene groups bridging P and N atoms.
the case of 3, the oxidation of PZA was monitored by 31P-
{1H} NMR in D2O. Two singlets at 1.99 and 1.41 ppm in
an approximate 1:1 integration ratio were observed soon after
the reaction was started, and no remaining PZA could be
detected. After 5 min, the formation of a white precipitate
was observed, accompanied by a decrease of the intensity
of the high-field singlet, to reach a final ratio of 1:0.76 in
solution at room temperature. The precipitate was filtered,
dried, and redissolved in DMSO-d6. The 31P{1H} NMR
spectrum (-3.38 ppm, s) indicates that the precipitate
contains only the most insoluble diastereoisomer.
An interesting PTA derivative introducing a binding arm
and a chiral center on the CR to P was obtained by Wong et
al. by the reaction of PTA with n-BuLi and ClPPh2, resulting
in the bidentate phosphine PTA-PPh2.11 Although this ligand
is not soluble in water and the racemic mixture was not
resolved, the method opens for the synthesis of a new class
of chiral PTA-based ligands. Herein we present the synthesis
of a novel water-soluble multifunctional P,O ligand with two
chiral centers, i.e., phenyl(1,3,5-triaza-7-phospha-tricyclo-
[3.3.1.13,7]dec-6-yl)methanol (PZA, 1), together with the
corresponding sulfide [PZA(S), 2] and oxide [PZA(O), 3].
In order to test the coordination ability of this ligand, the
iridium(III) complex (k1-P)-[Cp*IrCl2(PZA)] (4) was syn-
thesized and its X-ray crystal structure was determined,
together with that of 3.
Gas chromatography-mass spectrometry (MS) data of
1-3 reveal peaks corresponding to the parent cations at m/z
) 263 for 1, 295 for 2, and 279 for 3, respectively. The
electrospray ionization (ESI)-MS analysis of 4 indicates the
presence of the cationic species [Cp*IrCl(PZA)]+ (m/z )
628). The IR spectra of 2 and 3 (KBr pellets) show the
presence of the PdO and PdS groups with bands at 1153
and 610 cm-1, respectively, which compare well to those of
PTA(O) (1167 cm-1)15 and PTA(S) (629 cm-1).15b
Ligands 1 and 2 were straightforwardly prepared by
reacting benzaldehyde with the lithium salts of PTA11 and
PTA(S),12 respectively, while 3 was obtained by oxidizing
1 using aqueous H2O2 (35%), as for PTA(O).13 Finally,
complex 4 was prepared by reacting 1 with the dimer
Compound 1 shows remarkably high water solubility
(S20 °C ) 1.05 g mL-1), about 4 times more soluble than
PTA.2 PZA dissolves also in MeOH, EtOH, and chlorinated
solvents and is poorly soluble in tetrahydrofuran. Compound
2, on the other hand, is much less soluble in water, alcohols,
and chlorinated solvents but soluble in DMSO, while one
diastereoisomer of 3 is only sparingly soluble in DMSO and
precipitates from water solutions (vide supra). The iridium
complex 4 is only sparingly soluble in water (S20 °C ) 1.8 ×
10-3 g mL-1), as is the corresponding PTA complex
[Cp*IrCl2(PTA)] (S20 °C ) 2.2 × 10-3 g mL-1).16 Slow
concentration of a methanol solution of 1 in air resulted in
crystals suitable for X-ray diffraction analysis. The compound
isolated in the solid state turned out to be the oxide 3, as
shown in Figure 1. This suggests that 1 is more sensitive to
oxidation than PTA, in agreement with findings by Wong
14
[Cp*IrCl(µ-Cl)]2 in CH2Cl2, as shown in Scheme 1 (see
the Supporting Information for details). The synthesis of 1
results in a racemic mixture (1:1) of two diastereoisomers,
as expected from the presence of two chiral centers, and is
confirmed by the 31P{1H} NMR spectrum in D2O, which
consists of two singlets at -103.4 and -106.6 ppm in a 1:1
ratio slightly upfield shifted with respect to PTA (-96.2 ppm).
The formation of a pair of diastereoisomers is also evident
in the case of 2 showing 31P{1H} NMR singlets (deuterated
dimethyl sulfoxide, DMSO-d6) at -10.5 ppm (21.9%) and
-14.1 ppm (78.1%), similar to PTA(S) (-20.01 ppm).12 In
(9) (a) Assmann, B.; Angermaier, K.; Schmidbaur, H. J. Chem. Soc.,
Chem. Commun. 1994, 941-942. (b) Assmann, B.; Angermaier, K.;
Paul, M.; Schmidbaur, H. Chem. Ber. 1995, 128, 891-900. (c) Phillips,
A. D.; Bolan˜o, S.; Bosquain, S. S.; Daran, J.-C.; Malacea, R.; Peruzzini,
M.; Poli, R.; Gonsalvi, L. Organometallics 2006, 25, 2189-2200.
(10) Mena-Cruz, A.; Lorenzo-Luis, P.; Romerosa, A.; Saoud, M.; Serrano-
Ruiz, M. Inorg. Chem. 2007, 46, 6120-6128.
(15) (a) Darensbourg, D. J.; Stafford, N. W.; Joo´, F.; Reibenspies, J. H. J.
Organomet. Chem. 1995, 488, 99-108. (b) Jogun, K. H.; Stezowski,
J. J.; Fluck, E.; Weidlein, J. Phosphorus Sulfur Relat. Elem. 1978, 4,
199-204. (c) Marsh, R. E.; Kapon, M.; Hu, S.; Herbstein, F. H. Acta
Crystallogr., Sect. B: Struct. Sci. 2002, 58, 62-77.
(16) Erlandsson, M.; Landaeta, V. R.; Gonsalvi, L.; Peruzzini, M.; Phillips,
A. D.; Dyson, P. J.; Laurenczy, G. Eur. J. Inorg. Chem. 2007, DOI:
10.1002/ejic.200700792.
(11) Wong, G. W.; Harkreader, J. L.; Mebi, C. A.; Frost, B. J. Inorg. Chem.
2006, 45, 6748-6755.
(12) For the synthesis of PTA(S), see: Fischer, K. J.; Alyea, E. C.;
Shahnazarian, N. Phosphorus, Sulfur Silicon Relat. Elem. 1990, 48,
37-40.
(13) Daigle, D. J. Inorg. Synth. 1998, 32, 40-48.
(14) White, C.; Yates, A.; Maitlis, P. Inorg. Synth. 1992, 29, 228-234.
Inorganic Chemistry, Vol. 47, No. 1, 2008
9

COMMUNICATION
et al.,11 who observed that the bidentate phosphine ligand
PTA-PPh2 was slowly oxidized over time in a CH2Cl2
solution. The X-ray crystal structure of 3 shows that only
the R,S-S,R diastereoisomer is present in the asymmetric unit.
By dissolution of a few crystals in DMSO-d6, it was possible
to confirm that it corresponds to the species with a 31P{1H}
NMR singlet at -3.38 ppm.
In the molecular structure of (R,S-S,R)-3, the P atom is
tetrahedrally bound to three C atoms and one O atom with
O-P-C angles [ave 116.8(3)°] larger than the C-P-C ones
[ave 101.2(3)°; Figure 1].17
Figure 2. ORTEP diagram of 4. Ellipsoids are shown at 30% probability.
The hydroxyl group is disordered over two sites with an occupancy of 51.6%
for O(1a). Only the H atoms involved in the hydrogen bonds or bonded to
the stereocenter C(1) are shown.
The PdO oxygen forms a strong intermolecular hydrogen
bond with the hydroxyl group of a neighboring PZA(O)
molecule [O(1)‚‚‚O(2)#1 distance ) 2.717(6) Å].18 As a
consequence of this intramolecular hydrogen bonding, a 1D
infinite chain parallel to the b axis is formed (Figure S1 in
the Supporting Information), which could account for the
poor solubility of this diastereoisomer. This weak solid-state
interaction lengthens the P(1)-O(2) distance [1.490(1) Å]
in 3 of ca. 0.02 Å more than the P-O distances of oxides of
PTAandderivativespreviouslydescribedintheliterature.7b,15b,19
For the latter compounds, the O atom is not involved in
hydrogen bonding. The P(1)-C(1) and C(1)-N(1) [1.833-
(6) Å and 1.502(6) Å, respectively] bonds belonging to the
upper rim of PZA(O) are slightly longer than the corre-
sponding P(1)-C(2), P(1)-C(3) and C(2)-N(2), C(3)-N(3)
bonds [ave 1.813(6) and 1.489(7) Å, respectively] of PTA.15b
Crystals of 4, suitable for X-ray diffraction analysis, were
obtained by slow concentration of a dichloromethane/ethanol
solution of 4 (Figure 2).20 The X-ray analysis reveals the P
coordination of the PZA ligand, with the Ir atom coordinated
octahedrally by the two chloride ligands and the Cp* ring
occupying three contiguous sites of the coordination poly-
hedron. In a CD2Cl2 solution, the 31P{1H} NMR spectrum
shows two singlets of comparable intensity at -59.3 and
-72.3 ppm, indicating that both diastereoisomers are present
as observed in the solid state. The hydroxyl group is
disordered over two sites, with an occupancy of 51.6%. There
are evident intramolecular hydrogen bonds between Cl(2)
and the disordered hydroxyl group [O(1a)-Cl(2) ) 3.319-
(6); O(1b)-Cl(2) ) 3.112(6) Å].
The presence of such hydrogen bonds influences the Cl-
(2)-Ir(1) distance as well as the length of the Ir(1)-P(1)
bond. We have recently described16 the X-ray crystal
structure of [Cp*IrCl2(PTA)] (5), whose structural parameters
can be compared to those belonging to 4. In 5, the Ir-Cl
distances are both 2.418(4) Å, while in 4, Ir(1)-Cl(1) is
2.4127(10) Å and Ir(1)-Cl(2) is slightly longer at 2.4273-
(10) Å. The Ir-P bond is 2.2971(9) Å in 4, and it has to be
compared with 2.274(3) Å of 5. On the contrary, the Cp*-
(centroid)-Ir distance is 1.8187(16) Å in 4, while in 5, it is
1.812(5) Å. Also, the adamantane cage in 4 is more
asymmetric than that in 5, and in particular the P(1)-C(1)
bond is 0.01 Å longer than the other two P-C bonds.
The synthesis of 1 represents an important step toward
the full exploitation of the synthetic protocol for the
functionalization of the “upper rim” of PTA. Work aiming
at the resolution of PZA and the synthesis of other enantio-
merically pure water-soluble PTA derivatives and at their
applications in both enantioselective catalysis and biological
applications is in progress.
Acknowledgment. Thanks are expressed to EC for
promoting this scientific activity through the FP6 Research
Training Network AQUACHEM (Contract MCRTN-2003-
503864). We also thank “Firenze Hydrolab”, a project
sponsored by Ente Cassa di Risparmio di Firenze, for access
to high-field NMR facilities. M.E. thanks the foundation
Bengt Lundqvist minne (Sweden) for extra financial support.
Supporting Information Available: General methods, synthe-
ses, and NMR data for 1-4, Figure S1, and X-ray crystallographic
files in CIF format for 3 and 4. This material is available free of
charge via the Internet at http://pubs.acs.org.
(17) Summary of the crystallographic data for 3: C13H18N3O2P, Mw
)
279.27, monoclinic, P21/c, a ) 10.485(3) Å, b ) 11.337(4) Å, c )
11.004(5) Å, â ) 97.97(3)°, V ) 1295.4(8) Å3, Z ) 4, Fcalc ) 1.432
Mg/m3; µ ) 0.214 mm-1, F(000) ) 592, crystal size ) 0.50 × 0.50
× 0.05 mm3, collected/unique ) 2408/2277 [R(int) ) 0.0587], R1 )
0.0787, wR2 ) 0.1391 [I > 2σ(I)]; R1 ) 0.1930, wR2 ) 0.1708 (all
data). The data collection was performed at room temperature on an
Enraf Nonius CAD4 diffractometer equipped with a graphite mono-
chromator and Mo KR radiation. Selected bond distances (Å) and
angles (deg): P(1)-O(2), 1.490(4); P(1)-C(1), 1.833(6); P(1)-C(2)
1.808(6); P(1)-C(3), 1.818(5); N(1)-C(1), 1.502(6); N(1)-C(4),
1.469(8); N(1)-C(6), 1.468(7); N(2)-C(2), 1.493(7); N(2)-C(4),
1.457(8); N(2)-C(5), 1.461(8); N(3)-C(3), 1.485(7); N(3)-C(5),
1.461(8); N(3)-C(6), 1.455(7); C(1)-C(7), 1.527(7); O(2)-P(1)-
C(1), 117.7(2); O(2)-P(1)-C(2), 117.7(3); O(2)-P(1)-C(3), 115.0-
(2); C(1)-P(1)-C(2), 103.7(3); C(1)-P(1)-C(3), 100.0(3); C(2)-
P(1)-C(3), 100.0(3); C(1)-N(1)-C(4), 112.3(4); C(1)-N(1)-C(6),
111.4(4); C(2)-N(2)-C(4), 110.0(4); C(2)-N(2)-C(5), 110.7(5);
C(3)-N(3)-C(5), 110.0(5); C(3)-N(3)-C(6), 109.8(4); C(4)-N(1)-
C(6), 108.4(5); C(4)-N(2)-C(5), 109.3(5); C(5)-N(3)-C(6), 108.3(5).
(18) The symmetry transformation used to generate the equivalent atom is
IC701795Y
(20) Summary of the crystallographic data for 4: C23H33Cl2IrN3OP, Mw
) 661.59, monoclinic, P21/c, a ) 8.87890(17) Å, b ) 13.626(2) Å,
c ) 20.3750(4) Å, â ) 90.4071(18)°, V ) 2465.0(4) Å3, Z ) 4, Fcalc
) 1.783 Mg/m3, µ ) 5.719 mm-1, F(000) ) 1304, crystal size )
0.40 × 0.20 × 0.20 mm3, collected/unique ) 16383/7502 [R(int) )
0.0294], absorption correction ) Ψ scan, R1 ) 0.0292, wR2 ) 0.0557
[I > 2σ(I)]; R1 ) 0.0600, wR2 ) 0.0671 [all data]. The data collection
was performed at room temperature on an Oxford Diffraction Excalibur
3 diffractometer equipped with Mo KR radiation. Selected bond
distances (Å) and angles (deg): Ir(1)-P(1), 2.2971(9); Ir(1)-Cl(1),
2.4127(10); Ir(1)-Cl(2), 2.4273(10); Ir(1)-Cp*(centroid), 1.8187(16);
P(1)-C(1), 1.864(4); P(1)-C(2), 1.853(4); P(1)-C(3), 1.837(4);
O(1a)-Cl(2), 3.319(6); O(1b)-Cl(2), 3.112(6); P(1)-Ir(1)-Cl(1),
85.55(4); P(1)-Ir(1)-Cl(2), 88.70(4); Cl(1)-Ir(1)-Cl(2), 89.38(4);
P(1)-Ir(1)-Cp*(centroid), 133.20(4); Cl(1)-Ir(1)-Cp*(centroid),
123.49(4); Cl(2)-Ir(1)-Cp*(centroid), 123.38(4).
1
1
as follows: #1, -x + 1, y + /2, -z + /2.
(19) Frost,B.J.;Mebi,C.A.;Gingrich,P.W.Eur.J.Inorg.Chem.2006,1182.
10 Inorganic Chemistry, Vol. 47, No. 1, 2008