Synthesis of new heterotridentate ligands comprising mixed hard-soft donor sets, and their complexation with Group 10 metals

Article abstract of DOI:10.1039/a805847d

The new phosphorus-containing heterotridentate ligands 2-(2-Ph₂P)C₆H₄CH=NCH(Me)CH(OH)Ph-1S,2R (HL¹) and 2-(2-Ph₂P)C₆H₄N=CHC₆H₄OH (HL²) were prepared by the condensation of 2-(diphenylphosphino)-benzaldehyde with 1S,2R-norephedrine (HL¹) and 2-(diphenylphosphino)aniline with salicylaldehyde (HL²). The co-ordination chemistry of HL¹ and HL² with Group 10 metals was explored, together with that of the previously reported ligand 2-(2-Ph₂P)C₆H₄CH=NC₆H₄OH (HL³) which is isomeric with (HL²). Compound HL¹ affords cationic complexes of general formula [M(HL¹)Cl]Cl, where M = Ni (1), Pd (2) or Pt (3). Spectroscopic, microanalytical and crystallography data for 1-3 confirm that deprotonation of the hydroxyl group does not occur on complexation. In contrast, both HL² and HL³ deprotonate on complexation to form neutral species of general formula [MLCl] where L = L², M = Ni (4), Pd (5) or Pt (6); L = L³, M = Ni (7), Pd (8) or Pt (9). The crystal structures of 4, 5, 7 and 9 confirm tridentate PNO co-ordination of the deprotonated ligands to the metal centres, forming 5- and 6-membered rings.

Full text of DOI:10.1039/a805847d

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Synthesis of new heterotridentate ligands comprising mixed
hard–soft donor sets, and their complexation with Group 10 metals
Pravat Bhattacharyya, Jonathan Parr* and Alexandra M. Z. Slawin
Department of Chemistry, Loughborough University, Loughborough, Leics., UK LE11 3TU
Received 27th July 1998, Accepted 28th August 1998
The new phosphorus-containing heterotridentate ligands 2-(2-Ph P)C H CH᎐NCH(Me)CH(OH)Ph-1S,2R
᎐
2
6
4
(HL1) and 2-(2-Ph P)C H N᎐CHC H OH (HL2) were prepared by the condensation of 2-(diphenylphosphino)-
᎐
2
6
4
6
4
benzaldehyde with 1S,2R-norephedrine (HL1) and 2-(diphenylphosphino)aniline with salicylaldehyde (HL2). The
co-ordination chemistry of HL1 and HL2 with Group 10 metals was explored, together with that of the previously
reported ligand 2-(2-Ph P)C H CH᎐NC H OH (HL3) which is isomeric with (HL2). Compound HL1 affords cationic
᎐
2
6
4
6
4
complexes of general formula [M(HL1)Cl]Cl, where M = Ni (1), Pd (2) or Pt (3). Spectroscopic, microanalytical and
crystallographic data for 1–3 confirm that deprotonation of the hydroxyl group does not occur on complexation.
In contrast, both HL2 and HL3 deprotonate on complexation to form neutral species of general formula [MLCl]
where L = L2, M = Ni (4), Pd (5) or Pt (6); L = L3, M = Ni (7), Pd (8) or Pt (9). The crystal structures of 4, 5, 7
and 9 confirm tridentate PNO co-ordination of the deprotonated ligands to the metal centres, forming 5- and
6-membered rings.
Over the past fifteen years or so there has been a growing inter-
est in bidentate ligands which combine both hard and soft
donor atoms. Typically these are heterofunctionalised phos-
phines, where the phosphorus is the soft donor, and the hard
donor is either an oxygen or nitrogen atom.1 These ligands can
exhibit partial lability, where the co-ordination mode alternates
between bidentate and monodentate, leading to co-ordinative
unsaturation at the metal centre. This is a particularily desirable
characteristic for complexes which might have applications in
homogeneous catalysis, and since the majority of metals used
in such systems are late or middle transition metals it is
usually the soft donor which is continually bound to the metal.
The incorporation of a chiral centre into such ligands allows
enantioselectivity in catalytic transformations mediated by
complexes of these ligands.1c,i Furthermore, the unco-ordinated
donor atom may be used to bind to a second metal centre,
affording bimetallic species.1e,f There are, however, few tri-
dentate PNE (E = NЈ, O or S) donor ligands which have been
prepared or studied in this regard. For E = O, the known
examples can be subdivided into monobasic ligands containing
ionisable (OH or NH) groups2–6 and those comprising ether
donor groups.7–10 Ruthenium() complexes containing ligands
in this second category have been shown to be active catalysts
for the transfer hydrogenation of ketones in the presence of
PriOH.9,10 There are in the literature even fewer examples
reported of such ligands where E = NЈ or S.11–13
available from the condensation of 2-(diphenylphosphino)benz-
aldehyde and 2-aminophenol, the relative positions of the
phosphine and aryloxy substituents of the C᎐N bonds being
᎐
reversed.6 Compounds HL1 and HL2 are, in common with
HL3, soluble in a range of organic solvents and stable to both
aerial oxidation and hydrolysis under ambient conditions.
While HL1 is amenable to further reaction without purification,
it is necessary to recrystallise HL2 from chloroform–diethyl
ether to free the compound from the traces of salicylaldehyde
1
which inevitably persist. In the H NMR spectrum of HL1 the
imine proton is coupled to the 31P nucleus, J(31P–1H) 4 Hz,
which is comparable with the value of 5.5 Hz seen for HL3. In
the case of HL2 there is no observed (31P–1H) coupling for the
corresponding imine proton. The molecular structure of HL2
has been determined using a crystal grown from chloroform–
diethyl ether.
HO
PPh2
HL1
N
CH3
HO
We report here new tridentate ligands providing PNO donor
sets which are readily accessible from simple condensation
reactions and outline their complexation behaviour with the
Group 10 metals.
PPh2
HL2
N
Results and discussion
Ligand synthesis
HO
PPh2
HL3
N
Condensation reactions of 2-(diphenylphosphino)benzalde-
hyde and 1S,2R-norephedrine [PhCH(OH)CH(Me)NH2] or
of 2-(diphenylphosphino)aniline with salicylaldehyde, both
performed in refluxing thf, lead to new functionalised hetero-
tridentate ligands HL1 and HL2 in good yield. These have been
characterised by mass spectrometry, NMR and IR spectro-
scopies; HL2 is isomeric with the known compound HL3,
Complexation reactions of HL1–3
The stoichiometric reaction of HL1 with either NiCl2ؒ6H2O in
ethanol or [M(cod)Cl2], where M = Pd or Pt, in dichloro-
J. Chem. Soc., Dalton Trans., 1998, 3609–3614
3609

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Table 1 Selected spectroscopic (31P-{1H} and 1H NMR, IR and MS) and microanalytical data (calc. values in parentheses) for 1–9. Data for HL1–3
included for comparison
Analysis (%)
Compound
C
H
N
δ(31P) [J(PtP)/Hz]a ν(CN)/cmϪ1
m/zb
δ(CH᎐N)a
[α]589 e /deg cm3 gϪ1 dmϪ1
᎐
(HL1
Ϫ10.5
—
1638
1631s
8.62
—
ϩ1.1)
ϩ20.0
1 [Ni(HL1)Cl]Cl
60.4
(60.6)
55.9
(55.8)
48.6
5.1
(4.9)
4.8
(5.7)
4.0
2.2
516
564
654
(2.5)c
2.1
2 [Pd(HL1)Cl]Cl
3 [Pt(HL1)Cl]Cl
45.6
1640m
1631m
8.36
8.66
ϩ67.0
ϩ52.7
(2.2)d
1.8
9.7 [4042]
(48.8)
(4.1)
(2.0)d
(HL2
Ϫ14.6
—
1614
1608s
8.40)
—
4 [NiL2Cl]
63.2
(63.3)
57.3
(57.4)
48.8
4.0
(4.0)
3.5
(3.7)
2.9
3.0
(2.9)
2.8
(2.7)
2.3
489
536
626
5 [PdL2Cl]
6 [PtL2Cl]
47.1
1606s
1607s
8.65
9.03
12.9 [3814]
(49.1)
(3.1)
(2.3)
(HL3
Ϫ9.0
—
1624
1582m
8.92)
—
7 [NiL3Cl]
63.1
(63.3)
57.8
(57.4)
48.7
4.4
(4.0)
3.8
(3.7)
3.3
3.3
(2.9)
2.6
(2.7)
2.2
474
522
611
8 [PdL3Cl]
9 [PtL3Cl]
32.6
1579m
1580m
8.44
8.75
3.2 [3559]
(49.1)
(3.1)
(2.3)
a No NMR observed for nickel complexes 1, 4 and 7. b
M
ϩ Ϫ HCl for complexes 1–3, Mϩ for 4–9. c As 0.25 EtOH solvate. d As 0.5 EtOH solvate.
e In 0.01 M solution in MeOH at 28 ЊC.
methane gives the cationic complexes [ML1Cl]Cl 1–3 respec-
tively in high yield. These complexes are all soluble in ethanol
but largely insoluble in other common organic solvents. The
equivalent reactions of HL2 and HL3 give the neutral com-
plexes [MLCl] 4–9 which are all highly soluble in chlorinated
solvents, thf and acetone. This is supported by elemental
analysis and FABϩ mass spectrometry (Table 1), where the
parent molecular ions give rise to the most prominent peak in
the observed mass spectra.
IR spectroscopy
Selected IR data for the complexes 1–9 and the ligands HL1–3
are presented in Table 1. For 1–3 the most salient features are
the broad bands of medium intensity seen at 2400–2500 cmϪ1
,
assigned to ν(OH), which are absent from the spectra of 4–9.
The bands due to ν(C᎐N) are also readily identified, and are
᎐
found to vary little from the free HL values for 1–6. For 7–9,
however, there is a consistent and significant bathochromic shift
of ca. 40 cmϪ1 compared to the value for free HL3.
Fig. 1 Crystal structure of HL2.
NMR spectroscopy
Single crystal X-ray diffraction studies
Selected NMR data for complexes 1–9 are collected in Table 1.
For the complexes of NiII, 1, 4 and 7, there were no NMR
spectra observed, indicating that in solution these samples
are paramagnetic. Since complexes of NiII which have a
square planar geometry are expected to be diamagnetic,
this observation indicates that these complexes are distorted
somewhat from their expected geometry.
The crystal structure of HL2 (Fig. 1) reveals that in the solid
state the molecule exhibits the same trans planar configuration
of the central C(2)–C(1)–N(1)–C(8) backbone and orientation
of P(1) towards O(1) [P(1) ؒ ؒ ؒ O(1) 4.06 Å], which is consistent
with that observed in the structure of HL3.6 Additionally for
HL2 there is an intramolecular hydrogen-bonding interaction
between the imine nitrogen atom N(1) and the phenolic
hydrogen H(1o) of O(1) [N(1) ؒ ؒ ؒ H(1o) 1.59 Å, O(1)–H(1o)–
N(1) 155Њ] to form a pseudo six membered ring, a feature not
observed in HL3 but common in other related imine–phenol
compounds.14 There are small distortions in the pyramidal
geometry at P(1), with C–P–C angles between 100.6(1) and
103.1(2)Њ. The C(1)–N(1) length of 1.282(3) Å in HL2 is
marginally longer than the corresponding distance in HL3
The 31P-{1H} NMR spectra show singlets for the palla-
dium() and platinum() complexes, with resolved coupling to
195Pt for 3, 6 and 9. The J(195Pt–31P) couplings are consistent
1
1
with a phosphine ligand disposed trans to oxygen, with the J
values decreasing in the order 3 > 6 > 9. Interestingly there is
a ca. 7% increase in J for [PtL2Cl] 6 over its isomeric form
1
[PtL3Cl] 9. In the H NMR spectra of the palladium() and
1
platinum() complexes no coupling of the imine proton with
the 31P or 195Pt (in the case of 3, 6 and 9) nuclei was observed.
The hydroxyl protons of 2 and 3 are not observed in spectra
recorded in C2D5OD, which is perhaps unsurprising since there
is likely to be rapid exchange of this hydroxyl proton with the
(OD) deuteron.
[1.269(3) Å],6 in which the substituents on the C᎐N bond are
reversed.
The crystal structures of the Group 10 metal complexes 1–5, 7
and 9 (Figs. 2–4; selected bond lengths and angles are presented
in Table 2) reveal in general a square planar geometry at the
᎐
3610
J. Chem. Soc., Dalton Trans., 1998, 3609–3614

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Fig. 4 Crystal structure of [NiL3Cl] 7 (hydrogen atoms omitted for
clarity); [PtL3Cl] 9 has the same geometry.
All of the crystal structures exhibit distortions from idealised
square-planar geometry at the metal, due to the bulk of the
phosphine group and to the bite angle of the N,O chelate;
the trans O–M–P [168.3(2)–176.14(8)Њ] and trans N–M–Cl
[171.15(11)–176.63(6)Њ] axes are less than 180Њ in all of the
complexes. The cis P–M–N and cis N–M–O angles vary
between the complexes and are seemingly dependent upon the
sizes of the P,N and N,O chelate rings. Thus cis N–M–O for the
HL1 and (L3)Ϫ complexes 1–3, 7 and 9, which all have five-
membered N,O chelate rings, are in the range 81.6(3)–86.6(3)Њ,
considerably smaller than those seen for 4 and 5, 96.09(7)
and 94.02(8)Њ, which both contain a six-membered N,O ring.
Conversely, the cis N–M–P angles exceed 90Њ for 1–3, 7 and 9,
with six membered P,N chelate rings, as compared to 87.92(6)
and 86.03(6)Њ for 4 and 5.
Fig. 2 Crystal structure of [Ni(HL1)Cl]Cl 1 (hydrogen atoms omitted
for clarity); [Pd(HL1)Cl]Cl 2 and [Pt(HL1)Cl]Cl 3 have the same
geometry.
The structures of the nickel complexes 1, 4 and 7 allow com-
parisons between the bonding parameters for the tridentate
ligands HL1, (L2)Ϫ and (L3)Ϫ. In 1, 4 and 7 there is little vari-
ation among the Ni–N and Ni–P distances (Table 2), suggesting
similar basicities for the nitrogen and phosphorus atoms in all
of these PNO ligands, although the Ni–Cl distance in 4 is ca.
0.04 Å longer than in either 1 or 7. In [Ni(HL1)Cl]Cl 1 there is
an elongation of the Ni–O distance by ca. 0.1 Å compared with
4 and 7 which reflects the combined effects of O-protonation
and the non-phenolic nature of the hydroxyl group in HL1.
Similar lengthening by ca. 0.12 Å of the M–O distances in the
HL1 complexes compared with those of (L2)Ϫ and (L3)Ϫ is
observed with palladium and platinum [Pd–O 2.155(6) in 2,
2.030(2) Å in 5; Pt–O 2.147(6) Å in 3, 2.038(3) Å in 9]. The
M–N and M–P bond lengths in the palladium and platinum
complexes, as seen for nickel, vary little with the phosphine
employed, the Pd–N distance in [Pd(HL1)Cl]Cl 2 exceptionally
being ca. 0.03 Å shorter than in [PdL2Cl] 5. The complex
[NiL2Cl] 4 has the smallest cis O–M–Cl, cis N–M–P and cis
P–M–Cl angles of all the nickel complexes [88.54(5), 87.92(6)
and 87.65(2)Њ respectively], whereas the corresponding values
for 1 and 7 are all greater than 90Њ.
Fig. 3 Crystal structure of [NiL2Cl] 4 (hydrogen atoms omitted for
clarity); [PdL2Cl] 5 has the same geometry.
metal atom with tridentate PNO co-ordination of the ligand,
where the remaining bound chloride ligand is obligatorily
disposed trans to N(1). The complexes 1–3 are cations and
the proximity of the unbound chloride Cl(2) to the innocent
alcohol oxygen O(21) [Cl(2) ؒ ؒ ؒ O(21) 2.88–2.93 Å, O(21)–
H(21) ؒ ؒ ؒ Cl(2) 147–164Њ] in the crystal lattices suggests a
strong hydrogen-bonding interaction with the undissociated
hydroxyl proton H(21), corroborating the IR spectral assign-
ments.
The complexes 4–9 are neutral owing to deprotonation of the
oxygen atom of the tridentate ligand upon complexation,
presumably due to the greater acidity of the phenolate protons
compared to that of the alcohol. The ligand in complexes 4–6
is isomeric with that in 7–9 in that the relative positions of the
six- and five-membered P,N and N,O chelate rings formed on
complexation are reversed.
Conclusion
New tridentate PNO donor ligands are readily synthesized
from condensation reactions of 2-(diphenylphosphino)-aniline
or -benzaldehyde, leading to stable complexes with the
Group 10 metals. Differences in the acidity of the hydroxyl
group and the sizes of the P,N and N,O chelate rings formed
upon co-ordination dramatically affect the co-ordination
behaviour and spectroscopic parameters for complexes of
HL1–HL3.
J. Chem. Soc., Dalton Trans., 1998, 3609–3614
3611

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Table 2 Selected bond lengths (Å) and angles (Њ) for complexes 1–5, 7 and 9 (estimated standard deviations in parentheses)
1
2
3
4
5
7
9
M–P
M–N
M–O
M–Cl(1)
2.138(1)
1.877(3)
1.975(2)
2.144(1)
1.297(4)
1.441(4)
2.93
2.190(2)
1.985(7)
2.155(6)
2.267(3)
1.323(9)
1.441(10)
2.89
2.185(2)
2.005(2)
2.147((6)
2.278(3)
1.270(12)
1.469(10)
2.88
2.132(1)
1.892(2)
1.863(2)
2.187(1)
1.311(3)
1.301(3)
—
2.194(1)
2.016(2)
2.030(2)
2.306(1)
1.442(3)
1.293(3)
—
2.142(2)
1.900(7)
1.875(5)
2.148(3)
1.260(11)
1.324(10)
—
2.198(1)
2.003(3)
2.038(3)
2.282(1)
1.289(5)
1.322(5)
—
C᎐N
᎐
C–O
O ؒ ؒ ؒ Cl(2)
N–M–O
N–M–P
O–M–Cl(1)
P–M–Cl(1)
O–M–P
N–M–Cl(1)
C–N–M
84.67(11)
91.48(9)
91.98(8)
91.80(4)
176.14(8)
171.70(10)
134.1(3)
111.0(2)
164
81.6(3)
90.8(2)
94.3(2)
93.11(9)
172.3(2)
172.5(2)
109.1(5)
108.7(5)
147
82.0(3)
91.3(2)
92.2(2)
94.50(9)
173.2(2)
172.9(2)
106.7(6)
109.6(5)
160
96.09(7)
87.92(6)
88.54(5)
87.65(2)
174.16(5)
174.75(6)
121.1(2)
111.2(6)
—
94.02(8)
86.03(6)
88.70(5)
91.40(3)
176.00(6)
176.63(6)
119.1(2)
125.4(2)
—
86.3(3)
91.7(2)
90.4(2)
92.25(10)
168.3(2)
175.1(2)
131.0(5)
111.2(6)
—
83.02(13)
96.66(11)
89.07(9)
91.65(4)
173.37(8)
171.15(11)
128.1(3)
110.7(3)
—
C–O–M
O–H ؒ ؒ ؒ Cl(2)
s, CH᎐N) and 7.5–6.8 (m, aryl H). IR (cmϪ1): ν(CN) 1614s. EI:
Experimental
᎐
m/z 381 (Mϩ).
Ligand syntheses and complexation reactions were performed
under an atmosphere of oxygen-free nitrogen; thf and di-
chloromethane were distilled under nitrogen from sodium–
benzophenone and calcium hydride respectively, all other
solvents were analytical grade and used without further
purification. The compounds [M(cod)Cl2] (M = Pt or Pd,
cod = cycloocta-1,5-diene),15 2-(diphenylphosphino)aniline16
Metal complexes 1–9
Complexes 1, 4 and 7 were all prepared according to a general
method. An ethanolic (15 cm3) solution of HL (0.1 mmol) and
NiCl2ؒ6H2O (0.1 mmol) was stirred for 2 h to give a dark red
solution. The solvent was removed in vacuo, the crude product
extracted into dichloromethane (ca. 2–3 cm3) and precipitated
with hexanes (25 cm3). Complex 1 was recrystallised from
ethanol–diethyl ether, 4 and 7 from dichloromethane–diethyl
ether.
Complexes 2, 3, 5, 6, 8 and 9 were all prepared according to a
general method. A dichloromethane (15 cm3) solution of HL
(0.1 mmol) and [M(cod)Cl2] (M = Pd or Pt; 0.1 mmol) was
stirred for 2 h to give an intensely coloured (yellow to red)
solution. The solvent was removed in vacuo, the crude product
extracted into dichloromethane (ca. 2–3 cm3) and precipitated
with hexanes (25 cm3). Complexes 2 and 3 were recrystallised
from ethanol–diethyl ether, 5, 6, 8 and 9 from dichloro-
methane–hexanes.
and 2-(2-Ph P)C H CH᎐NC H OH (HL3)6 were prepared
᎐
2
6
4
6
4
by literature methods; 2-(diphenylphosphino)benzaldehyde
(Aldrich) was used as received. The H (250.13) and 31P-{1H}
1
(36.21 MHz) NMR spectra, recorded as C2D5OD (1–3) or
CDCl3 (4–9) solutions on Bruker AM250 and JEOL FX-90Q
spectrometers, and were referenced to external tetramethyl-
silane (δ 0) and 85% phosphoric acid (δ 0) respectively using the
high-frequency positive convention. Infrared spectra (pressed
KBr discs) were recorded on a Perkin-Elmer System 2000 NIR
FT-Raman spectrometer. Elemental analyses (Perkin-Elmer
2400 CHN elemental analyser) were performed by the Uni-
versity of Loughborough Analytical Service. Electron impact
and fast atom bombardment (positive ionisation mode,
3-nitrobenzyl alcohol matrix) mass spectra were performed
by the EPSRC National Mass Spectrometry Service Centre,
Swansea, UK.
Isolated yields of microcrystalline complexes 1–9 were
typically in the range 25–60%; characterisation data are given
in Table 1.
Ligand syntheses
X-Ray crystallography
2-(2-Ph P)C H CH᎐NCH(Me)CH(OH)Ph-R,S HL1. A thf
᎐
2
6
4
(20 cm3) solution of 2-(diphenylphosphino)benzaldehyde
(0.51 g, 1.75 mmol) and 1S,2R-norephedrine (0.27 g, 1.75
mmol) was heated at reflux for 3 h, giving an orange solution.
The solvent was removed under reduced pressure and the
resulting oil pumped in vacuo for 30 min to give 0.53 g of HL1
as a pale pink solid. Yield 68% [Found (Calc. for C28H26NOP):
C, 79.4 (79.4); H, 6.2 (6.2); N, 3.4 (3.3)%]. δ(31P) Ϫ10.5 (s).
The crystal structures of complexes 1–5, 7 and 9 were deter-
mined at 298 K using a Siemens SMART diffractometer with
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å).
The structure of HL2 was recorded on a Rigaku AFC7S
instrument with Cu-Kα radiation (λ = 1.54178 Å) and ω scans.
The crystal data, a summary of the data collections and the
structure refinements are given in Table 3. All structures were
solved by direct methods and all of the non-hydrogen atoms
refined with anisotropic displacement parameters; the hydrogen
atoms bound to carbon were included in calculated positions
(C–H 0.95 Å) with a fixed isotropic displacement parameter.
The hydrogen atom H(21) associated with O(21) in 1–3 and
H(1o) associated with O(1) in HL2 were located using the
difference maps and allowed to refine isotropically with no
distance restraint. Structural refinements were by full-matrix
least-squares methods on F2, calculations being performed
using the program SHELXTL PC;17 for HL2, calculations
were performed using TEXSAN18 and empirical absorption
corrections (DIFABS)19 applied.
δ(1H) 8.62 [1 H, d, J(PH) 4, CH᎐N], 7.7–6.7 (m, aryl H),
4.53 [1 H, d, J(HH) 4, CHOH], 3.40 (1 H, m, CHMe), 0.7 [3 H,
d, J(HH) 6 Hz, CH3]. IR (cmϪ1): ν(CN) 1638s. EI: m/z 424
(Mϩ).
᎐
2-(2-Ph PC H N᎐CH)C H OH HL2. A thf solution (30 cm3)
᎐
2
6
4
6
4
of 2-(diphenylphosphino)aniline (0.7 g, 2.5 mmol) and salicyl-
aldehyde (0.33 g, 2.7 mmol) was heated at reflux for 12 h, during
which time it became orange. The solvent was removed in vacuo
and the solid product obtained recrystallised from chloroform–
diethyl ether as 0.69 g of yellow crystals. Yield 67% [Found
(Calc. for C25H20NOP): C, 78.4 (78.8); H, 5.2 (5.3); N, 3.3
(3.7)%]. δ(31P) Ϫ14.6 (s). δ(1H) 12.50 (1 H, br, OH), 8.40 (1 H,
CCDC reference number 186/1141.
3612
J. Chem. Soc., Dalton Trans., 1998, 3609–3614

Table 3 Details of the X-ray data collections and refinements for compounds HL2, 1–5, 7 and 9
HL2
1ؒ0.25EtOH
2ؒ0.5EtOH
3ؒ0.5EtOH
4
5
7
9
Empirical formula
M
C25H20NOP
381.41
C28.5H27.5Cl2NNiO1.25
564.60
P
C29H29Cl2NO1.5PPd
623.80
C29H29Cl2NO1.5PPt
712.49
C25H19ClNNiOP
474.54
C25H19ClNOPPd
522.23
C25H19ClNNiOP
474.54
C25H19ClNOPPt
610.92
Crystal system
Space group
Monoclinic
P21/n
Orthorhombic
P212121
Orthorhombic
P212121
Orthorhombic
P212121
Monoclinic
P21/c
Monoclinic
P21/c
Triclinic
P1
Monoclinic
P21/n
¯
a/Å
b/Å
c/Å
α/Њ
11.038(5)
10.589(4)
16.919(5)
10.513(1)
15.023(1)
19.019(1)
10.534(1)
15.194(1)
18.805(1)
10.573(1)
15.220(1)
18.695(1)
9.702(1)
13.006(1)
17.296(1)
9.784(1)
13.054(1)
17.284(1)
10.326(1)
10.518(1)
12.144((1)
83.06(1)
73.58(1)
71.52(1)
1199.31(3)
2
9.085(1)
16.349(1)
14.091(1)
β/Њ
92.97(3)
96.14(1)
96.81(1)
92.36(1)
γ/Њ
U/Å3
Z
1975(1)
4
1.327
3390
3003.75(10)
4
0.898
3010.0(3)
4
0.870
3008.34(12)
4
4.918
2169.9(2)
4
1.108
2191.91(8)
4
1.058
2091.18(3)
4
6.932
µ/mmϪ1
Total data
1.002
5161
18041
17938
18619
13043
12916
9057
Unique data (Rint
)
3136 (0.326)
254
6916 (0.1031)
324
0.635
7080 (0.1756)
324
0.818
7083 (0.0710)
323
0.879
5157 (0.0286)
272
0.655
5131 (0.0331)
272
0.914
3353 (0.0745)
272
0.837
3009 (0.0843)
272
0.602
No. of parameters
Goodness of fit on F2 2.87
R1, wR2 [I > 2σ(I)]a
0.041, 0.026b
0.0427, 0.0996
0.0664, 0.1085
0.0503, 0.0895
0.0298, 0.0793
0.0302, 0.0581
0.0849, 0.2390
0.0238, 0.0423
¹
2
a R1 = Σ( Fo| Ϫ |Fc )/Σ|Fo|, wR2 = [Σw(Fo2 Ϫ Fc2)2/Σw(Fo )2]²; I > 3σ(I) for HL2. b wR2 for HL2 as defined by TEXSAN.

View Online
7 K. Tani, M. Yakuta, S. Nakamura and T. Yamagata, J. Chem. Soc.,
Dalton Trans., 1993, 2781.
Acknowledgements
We are grateful to Johnson Matthey plc for a loan of precious
metals, Dr Steve Aucott for a kind gift of 2-(diphenyl-
phosphino)aniline and to the EPSRC (P. B.) for financial
support.
8 Y. Kataoka, Y. Tsuji, O. Matsumoto, M. Ohashi, T. Yamagata and
K. Tani, J. Chem. Soc., Chem. Commun., 1995, 2099.
9 H. Yang, M. Alvarez, N. Lugan and R. Mathieu, J. Chem. Soc.,
Chem. Commun., 1995, 1721.
10 H. Yang, M. Alvarez Gressier, N. Lugan and R. Mathieu, Organo-
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11 H. A. Ankersmit, N. Veldman, A. L. Spek, K. Vrieze and G. Van
Koten, Inorg. Chim. Acta, 1996, 252, 339.
12 P. Wehman, R. E. Rulke, V. E. Kaasjager, P. C. J. Kamer, H.
Kooijman, A. L. Spek, C. J. Elsevier, K. Vrieze and P. W. N. M. Van
Leeuwen, J. Chem. Soc., Chem. Commun., 1995, 331.
13 S. D. Perera, M. Shamsuddin and B. L. Shaw, Can. J. Chem., 1995,
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14 N. Gündüz, T. Gündüz, M. B. Hursthouse, H. G. Parkes, L. S. Shaw
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Paper 8/05847D
3614
J. Chem. Soc., Dalton Trans., 1998, 3609–3614