Synthesis and complexing properties of phosphorus-substituted pyridine-2-carboxylic acid anilides

Article abstract of DOI:10.1080/10426507.2014.905571

Novel phosphorus-containing ligands have been synthesized by the condensation of 2-(thio)phosphorylated anilines with 2,6-dichloro-and 4-chloropyridine-2-carbonyl chlorides in the presence of Et₃N and unsubstituted pyridine-2-carboxylic acid using P(OPh)₃ as a coupling agent. The compounds derived readily form complexes with a range of transition metals (M=Re(I), Pd(II), and Cu(II)), serving as bi-or tridentate monoanionic ligands. The composition and structure of the resulting metallocycles depend both on the presence/amount of the Cl atoms in the pyridine ring and on the nature of the donor atom X in the P=X moiety. The novel compounds were characterized by multinuclear NMR and IR spectroscopy as well as X-ray crystallography.

Full text of DOI:10.1080/10426507.2014.905571

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis and complexing properties of phosphorus-
substituted pyridine-2-carboxylic acid anilides
Diana V. Aleksanyana, Yulia V. Nelyubinaa, Zinaida S. Klemenkovaa & Vladimir A. Kozlova
a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Accepted author version posted online: 14 May 2014.
To cite this article: Diana V. Aleksanyan, Yulia V. Nelyubina, Zinaida S. Klemenkova & Vladimir A. Kozlov (2014): Synthesis and
complexing properties of phosphorus-substituted pyridine-2-carboxylic acid anilides, Phosphorus, Sulfur, and Silicon and the
Related Elements, DOI: 10.1080/10426507.2014.905571
To link to this article: http://dx.doi.org/10.1080/10426507.2014.905571
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Synthesis and complexing properties of phosphorus-substituted
pyridine-2-carboxylic acid anilides
Diana V. Aleksanyan*, Yulia V. Nelyubina, Zinaida S. Klemenkova and Vladimir A. Kozlov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul.
Vavilova 28, Moscow, 119991 Russia
Corresponding author: aleksanyan.diana@ineos.ac.ru
Shortened title: P(V)-substituted picolinamides as novel ligands
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Abstract
Novel phosphorus-containing ligands have been synthesized by the condensation of 2-
(thio)phosphorylated anilines with 2,6-dichloro- and 4-chloropyridine-2-carbonyl chlorides in
the presence of Et3N and unsubstituted pyridine-2-carboxylic acid using P(OPh)3 as a coupling
agent. The compounds derived readily form complexes with a range of transition metals (M =
Re(I), Pd(II), and Cu(II)), serving as bi- or tridentate monoanionic ligands. The composition and
structure of the resulting metallocycles depend both on the presence/amount of the Cl atoms in
the pyridine ring and on the nature of the donor atom X in the P=X moiety. The novel
compounds were characterized by multinuclear NMR and IR spectroscopy as well as X-ray
crystallography.
X
Ph
Ph
X = S, O
M = Re, Pd, Cu
P
N
M
N
Ln
X
N
S
N
NH
Pd
N
S
O
N
O
N
O
X = O, S
n = 0, 1, 2
Cu
N
Cln
N
Key words: phosphorus ligands, pyridinecarboxamides, transition metals, metallocycles
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Introduction
Over the past few decades functionalized carboxamides have attracted considerable interest
in organometallic and coordination chemistry. Much attention has been given to pyridine-2-
carboxylic (picolinic) acid derivatives, which are capable of forming complexes with a variety of
metals both in neutral and anionic form.1 An attractive feature of this type of ligands is a
possibility of easy modification of a ligand backbone to change the properties of resulting metal
complexes. Thus, the introduction of ancillary donating groups into the amine part of a ligand
opens up the way to novel types of metal chelates with variable geometry and different
physicochemical properties,2–9 finding application as efficient catalysts (e.g., complex I10, Figure
1) and convenient models for investigation of metal binding modes in natural systems (e.g.,
compounds II11 and III12, Figure 1). As a rule, the additional coordination-active fragments are
nitrogen and sulfur donor groups. To the best of our knowledge, the literature data on the related
phosphorus-containing derivatives is restricted to a single report.13
Within the project devoted to the synthesis of novel oligodentate ligands via modular
assembling of 2-(thio)phosphorylanilines with various carbonyl derivatives,14–17 recently we
have shown that P(X)-modified (X = O, S) (thio)phosphorylacetamides can serve as versatile
ligands for transition metals, readily undergoing cyclometallation at the amide nitrogen atom.18,19
Taking this into account, it seems interesting to utilize pyridine-2-carboxylic acid as a carbonyl
component. Therewith, introduction of the chlorine atoms into the pyridine ring will allow one to
estimate the effect of additional steric and electronic factors on the structure of resulting metal
complexes.
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Herein, we report on the synthesis of novel phosphorus-containing ligands by the
condensation of 2-(thio)phosphorylanilines with unsubstituted, 4-chloro- and 3,6-
dichloropicolinic acids and their complexing features towards transition metal ions.
Results and Discussion
The target (thio)phosphoryl-functionalized picolinamides bearing chlorine substituents in
the pyridine ring (compounds 1a,b and 2) were obtained by the condensation of 2-
(thio)phosphorylanilines with the corresponding acid chlorides, generated in situ under action of
sulfuryl or thionyl chloride according to the literature procedures (Scheme 1).20,21 It is well
known that the treatment of pyridinecarboxylic acids with common chlorinating agents even
under mild conditions is often complicated by the chlorination of the heterocycle. Therefore, the
synthesis of P(S)-modified pyridine-2-carboxamide 3 was accomplished directly from the
corresponding acid using triphenylphosphite as a coupling agent (Scheme 1). The key anilines
were obtained by the previously published methods.18
The structures of P(S)-functionalized picolinamides 1–3 were unambiguously confirmed
based on the multinuclear NMR (31P, 1H, and 13C) and IR spectral data. Thus, the singlet signals
of the phosphorus atoms in the 31P NMR spectra of 1–3 are observed in the regions expected for
phosphine oxide (1a) and phosphine sulfide (1b, 2 and 3) derivatives (at ca. 33 and 39 ppm,
respectively). The characteristic signals of the amide protons in the 1H NMR spectra of 1–3 were
detected at 10.75–12.02 ppm, respectively. The 13С NMR spectral data of the compounds
obtained were also well consistent with the proposed structures (e.g., δC=O = 160.15–162.52
ppm). Note that unlike the proton NMR spectra, the signals of the carbon atoms of the aniline
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and pyridine rings do not overlap with those of the СPh-atoms of peripheral phenyl moieties (see
Experimental) and can be readily identified. The IR spectra of 1–3 show the adsorption bands
associated with the presence of the secondary amide group at 1682–1698 (C=O bond stretching
vibrations), 3192–3297 (N–H stretching), and 1506–1531 cm–1 (amide II bands with a major
contribution of N–H bending vibrations). The characteristic adsorption bands of the
(thio)phosphoryl functional groups are observed at 1181 cm–1 (P=O group in 1a) and 634–639
cm–1 (P=S groups in 1b, 2, and 3).
The complexing features of (thio)phosphoryl-substituted picolinamides 1–3 were studied
towards several transition metal ions. Independently from the presence and amount of chlorine
substituents in the pyridine ring and the nature of the donor atom X in the (thio)phosphoryl
moiety, the interaction of 1a, 2, and 3 with Re(CO)5Br in refluxing toluene in the presence of a
base proceeded as the cyclometallation at the amide nitrogen atom accompanied by coordination
with the (thio)phosphoryl and pyridine fragments, resulting in κ3-X,N,O-complexes 4–6 (X = O,
S) with five- and six-membered fused metallocycles (Scheme 2).
The tridentate monoanionic coordination mode of thiophosphoryl-substituted picolinamides
2 and 3 was observed also in Pd(II) complexes 8 and 9 (Scheme 3), readily prepared in the
reaction with PdCl2(PhCN)2 in dichloromethane solution at room temperature. Therewith, the
reaction of 1b with the same palladium precursor resulted in κ2-S,N-complex 7 with two ligand
anions per a metal ion even in the case of equimolar amounts of the reagents. This phenomenon
is likely to be explained by the steric hindrances of the ortho-chlorine substituent in the pyridine
ring, hampering its participation in coordination. Note that no complexation was observed in the
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reaction of PdCl2(PhCN)2 with phosphoryl-substituted picolinamide 1a, probably due to the
presence of the hard oxygen donor atom instead of the soft sulfur one.
The result of reactions of (thio)phosphoryl-functionalized picolinamides with Cu(II) salts
was dictated mainly by the nature of the substituent X in the P=X moiety. Thus, the interaction
of copper(II) acetate with P(O)-substituted ligand 1a afforded κ3-O,N,N-complex 10a of (L–
H)2M composition, while its thiophosphorylated counterparts 1b, 2, and 3 afforded metallocycles
10b, 11, and 12 with one tridentately bound ligand anion per a metal atom in reactions with
Cu(OAc)2 (10a) or CuCl2 (11,12) (Scheme 4).
The complexes obtained are pale yellow (Re(I) compounds 4–6), orange (7), red (8, 9) or
green (Cu(II) complexes 10–12) crystalline solids, thermally stable up to 180ºC as well as air and
moisture resistant. The suggested structures were supported by the elemental analysis, IR and
NMR spectral data and, in some cases, X-ray crystallography. Thus, a shift of the phosphorus
31
resonances in the P NMR spectra of complexes 4–6, 8, and 9 compared to the signals of free
ligands (reaching up to 12.8 ppm) gave evidence of complexation by the P=X groups.
Unfortunately, Pd(II) complex 7 appeared to be insoluble in common organic solvents, and no
NMR spectra were observed for the Cu(II) complexes, suggesting that compounds 10–12 are
paramagnetic in solution. However, the coordination of the (thio)phosphoryl groups in all the
complexes obtained is confirmed by a strong low-frequency displacement of the P=X bond
stretching vibrations in the IR spectra (Δν = 30–57 cm–1). The absence of the NH proton signals
in the 1H NMR spectra of compounds 4–6, 8, and 9 and lack of characteristic N–H stretching and
bending (amide II band) vibrations along with a strong shift of the C=O stretching frequency (Δν
= 43–86 cm–1) in the IR spectra of all complexes unequivocally confirm coordination of the
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amide group in a deprotonated form. A downfield shift of the C1 (Δδ = 14.32 ppm) and C8 (Δδ =
5.33 ppm) carbon resonances (carbon atoms connected with the amide moiety) with a
concomitant displacement of the C=O group carbon signal (Δδ = 5.82 ppm) in the 13C NMR
spectrum of complex 6 compared to the signals of free ligand 3 are also indicative of complex
formation. Furthermore, a downfield displacement by ~4.3 ppm observed for the carbon atom of
the pyridine ring adjacent to the nitrogen center (C12) can be associated with participation of the
pyridine moiety in coordination.
The solid-state structures of complexes 4, 5, 8, 10a, and 12 were also studied by X-ray
diffraction analysis (Figures 2–6). According to its results, in all cases (thio)phosphorylated
picolinamides are coordinated in a tridentate monoanionic fashion. Re(I) complexes 4 (Figure 2)
and 5 (Figure 3) feature nearly ideal octahedral environment of the metal center. Note that the
introduction of bulky chlorine substituents in the case of complex 4 violates the coplanarity of
the amide fragment and pyridine ring: the C7 and O2 atoms deviate from the mean heterocycle
plane by 0.41 Ǻ and 0.76 Ǻ, respectively. The Pd(II) ion in metallocycle 8 (Figure 4) is
characterized by a square-planar configuration with the N1–N2–Cl1–S1 dihedral angle being
4.3º. The coordination environment of the copper atom varies from distorted square-planar in 12
(Figure 5) (the corresponding dihedral angle is 32.7º) to elongated octahedral in 10a (Figure 6),
reflecting the changes in the metal binding mode from 4 (12) to [4 + 2] (10a). Therewith, the
lengths of the Cu–N bonds for the amide and pyridine moieties in complex 10a compose
1.999(2)–2.025(2) Å and 2.539(2)–2.544(2) Å, respectively. Interestingly, two picolinamide
ligands in 10a feature cisoid arrangement which is likely to be supported by stacking interactions
between aniline (C1–C6) and pyridine rings. As for the conformations of resulting metallocycles,
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the five-membered metal-containing ring adopt flat (in complex 12) or envelope (in the other
compounds) conformation with the maximum deviation of the N2 atom in 10a by 0.737 Å. The
six-membered chelate ring is half-chair (in complex 8) or boat (in the other complexes) with the
N(1) and P(1) atoms deviating by 0.384–0.835 and 0.485–0.882 Å, respectively. The main bond
lengths and angles are given in Table S1 in electronic supplementary information.
Conclusions
To summarize the results presented, condensation of 2-(thio)phosphorylated anilines with
2,6-dichloro- and 4-chloropyridine-2-carbonyl chlorides and unsubstituted picolinic acid
afforded novel oligodentate ligands, namely, P(X)-functionalized pyridinecarboxamides (X = O,
S). The compounds obtained serve as tridentate monoanionic ligands upon complexation with
Re(I), Pd(II), and Cu(II) ions; therewith, the structure and composition of the resulting
metallocycles are dictated by the nature of the donor atom X in the P=X group and presence of
additional chlorine substituents in the pyridine ring.
Experimental
General remarks
If not noted otherwise, all manipulations were carried out without taking precautions to
exclude air and moisture. Dichloromethane and acetonitrile were distilled from P2O5. Benzene
was distilled over sodium benzophenone ketyl. 2-(Diphenylphosphoryl)aniline and its thio-
analog were obtained according to the literature procedures.18 Crude 3,6-dichloro-20 and 4-
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chloropyridine-2-carbonyl21 chlorides were prepared by the published methods. All other
chemicals and solvents were used as purchased.
NMR spectra were recorded on Bruker Avance-300 and Bruker Avance-400 spectrometers,
and the chemical shifts (δ) were internally referenced by the residual solvent signals relative to
tetramethylsilane (1H and 13C) or externally to H3PO4 (31P). The 13C NMR spectra were
registered using the JMODECHO mode; the signals for the C atoms bearing odd and even
numbers of protons have opposite polarities. The numeration of carbon atoms in description of
the NMR spectral data of all the compounds obtained is in accordance with the labeling schemes
presented in Figures 2–6.
Column chromatography was carried out using Merck silica gel 60 (230–400 mesh
ASTM). IR spectra were recorded on a Magna-IR750 Fourier spectrometer (Nicolet), resolution
2 cm–1, 128 scans. The assignment of absorption bands in the IR spectra was made according to
ref.22 Melting points were determined with MPA 120 EZ-Melt Automated Melting Point
Apparatus and were uncorrected.
Synthesis of ligands
3,6-Dichloro-N-[2-(diphenylphosphoryl)phenyl]pyridine-2-carboxamide (1a)
A solution of 3,6-dichloropyrdine-2-carbonyl chloride (1.0 g, 4.8 mmol) in 7 mL of
acetonitrile was slowly dropwise added to a solution of 2-(diphenylphosphoryl)aniline (1.4 g, 4.8
mmol) and triethylamine (0.7 mL, 5.0 mmol) in 10 mL of MeCN. The reaction mixture was left
under ambient conditions for 12 h, then filtered and evaporated to dryness. The residue obtained
was dissolved in dichloromethane, and the resulting solution was washed with dilute
hydrochloric acid and water, dried over anhydrous Na2SO4, and evaporated to dryness. The
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resulting residue was recrystallized from EtOH to give 1.75 g of ligand 1a as a white crystalline
31
1
solid. Yield: 79%. Mp: 173–174°С. Р{1H} NMR (161.98 MHz, (CD3)2SO): δ 33.16 ppm. Н
3
NMR (400.13 MHz, (CD3)2SO): δ 7.17 (dd, 3JPH = 13.8 Hz, JHH = 7.6 Hz, 1Н, Н(С3)), 7.26 (t,
3JHH = 7.6 Hz, 1Н, Н(C4)), 7.57–7.60 and 7.65–7.70 (both m, 4H + 7Н, HAr), 7.80 (d, 3JHH = 8.5
3
3
4
Hz, 1Н, Н(C11)), 8.17 (d, JHH = 8.5 Hz, 1Н, Н(C10)), 8.53 (dd, JHH = 8.1 Hz, JPH = 4.2 Hz,
1Н, Н(C6)), 12.02 (s, 1Н, NH). IR (КBr, ν/cm–1): 495(w), 519(m), 537(m), 545(s), 550(m),
662(w), 681(w), 692(w), 699(m), 710(s), 723(m), 738(m), 753(m), 764(m), 789(w), 837(w),
916(w), 1039(m), 1072(w), 1100(w), 1121(m), 1139(m), 1154(m), 1165(m), 1172(m), 1181(s)
(Р=О), 1206(w), 1242(w), 1287(m), 1298(m), 1414(m), 1438(s), 1457(w), 1483(w), 1527(s)
(C(O)NH), 1563(w), 1575(s), 1594(w), 1698(s) (С=О), 3056(w), 3297(w) (NH). Anal. Calcd for
С24Н17Сl2N2O2P: С, 61.69; Н, 3.67; N, 5.99. Found: С, 61.59; Н, 3.55; N, 5.79%.
3,6-Dichloro-N-[2-(diphenylthiophosphoryl)phenyl]pyridine-2-carboxamide (1b)
A solution of 3,6-dichloropyrdine-2-carbonyl chloride (0.8 g, 3.8 mmol) in 3 mL of
benzene was slowly dropwise added to a solution of 2-(diphenylthiophosphoryl)aniline (1.2 g,
3.9 mmol) in 10 mL of pyridine. The reaction mixture was left under ambient conditions for 2
days and then evaporated to dryness. The residue obtained was dissolved in chloroform, and the
resulting solution was washed with water, dried over anhydrous Na2SO4, and evaporated to
dryness. The resulting residue was recrystallized from EtOAc–CHCl3 (1:1) to give 1.15 g of
ligand 1b as a white crystalline solid. Yield: 63%. Mp: 228–229°С. 31Р{1H} NMR (161.98 MHz,
(CD3)2SO): δ 38.36 ppm. 1Н NMR (400.13 MHz, (CD3)2SO): δ 6.91 (dd, 3JPH = 14.3 Hz, 3JHH
=
3
7.6 Hz, 1Н, Н(С3)), 7.30 (t, JHH = 7.6 Hz, 1Н, Н(С4)), 7.48–7.53 (m, 4H, HAr), 7.56–7.60 (m,
2Н, HAr), 7.69–7.77 (m, 6Н, HAr), 8.04–8.07 (m, 2H, H(C10) + H(C6)), 10.75 (s, 1Н, NH).
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1
3
13C{1H} NMR (100.61 MHz, CDCl3): δ 124.31 (d, JРС = 85.2 Hz, С2), 124.37 (d, JРС = 12.3
3
3
Hz, С4), 125.15 (d, JРС = 7.1 Hz, С6), 127.30 (s, С11), 128.36 (d, JРС = 12.9 Hz, m-С in
P(S)Ph2), 130.34 (s, С9), 130.48 (d, 1JРС = 85.5 Hz, ipso-С in P(S)Ph2), 131.73 (d, 4JРС = 3.1 Hz,
2
2
p-С in P(S)Ph2), 132.06 (d, JРС = 8.6 Hz, С3), 132.15 (d, JРС = 11.1 Hz, o-С in P(S)Ph2),
4
2
132.51 (d, JРС = 2.2 Hz, С5), 139.88 (d, JРС = 4.3 Hz, С1), 142.22 (s, С10), 145.30 (s, С8),
147.58 (s, С12), 160.15 (s, С=О). IR (КBr, ν/cm–1): 471(w), 505(m), 516(m), 532(m), 614(w),
625(w), 634(m) (P=S), 660(w), 680(w), 692(m), 699(m), 712(s), 731(m), 752(m), 763(m),
792(w), 831(w), 924(w), 999(w), 1039(m), 1101(m), 1104(m), 1132(w), 1140(w), 1155(m),
1208(w), 1299(m), 1416(m), 1433(s), 1439(s), 1457(w), 1480(w), 1506(m), 1513(s) (C(O)NH),
1559(w), 1576(m), 1593(w), 1691(s) (С=О), 3054(w), 3230(m) (NH). Anal. Calcd for
С24Н17Сl2N2OPS: С, 59.64; Н, 3.55; N, 5.80. Found: С, 59.67; Н, 3.49; N, 5.74%.
4-Chloro-N-[2-(diphenylthiophosphoryl)phenyl]pyridine-2-carboxamide (2)
A solution of 4-chloropyridine-2-carbonyl chloride (0.9 g, 5.1 mmol) in 10 mL of
dichloromethane was slowly dropwise added to a solution of 2-(diphenylthiophosphoryl)aniline
(1.6 g, 5.2 mmol) and triethylamine (0.75 mL, 5.4 mmol) in 15 mL of CH2Cl2. The resulting
mixture was left under ambient conditions for 12 h, then washed with water, dried over
anhydrous Na2SO4, and evaporated to dryness. The resulting residue was purified by silica gel
column chromatography (eluent: EtOAc–hexane (1:1)) to give 1.2 g of ligand 2 as a white
crystalline solid. Yield: 52%. Mp: 175–176°С. 31Р{1H} NMR (121.49 MHz, (CD3)2SO): δ 38.39
ppm. 1Н NMR (300.13 MHz, (CD3)2SO): δ 6.91 (dd, 3JPH = 14.6 Hz, 3JHH = 7.7 Hz, 1Н, Н(C3)),
3
7.29 (t, JHH = 7.7 Hz, 1Н, Н(С4)), 7.45–7.54 and 7.67–7.78 (both m, 6H + 6Н, HAr), 7.84 (d,
3
4
3
4JHH = 2.0 Hz, 1Н, H(C9)), 8.08 (dd, JHH = 8.0 Hz, JPH = 5.7 Hz, 1Н, Н(С6)), 8.55 (d, JHH
=
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5.3 Hz, 1H, H(C12)), 10.84 (s, 1Н, NH). 13C{1H} NMR (100.61 MHz, CDCl3): δ 122.53 (s, С9),
3
1
3
124.45 (d, JРС = 12.0 Hz, С4), 124.97 (d, JРС = 85.2 Hz, С2), 125.56 (d, JРС = 7.1 Hz, С6),
126.12 (s, C11), 128.30 (d, 3JРС = 12.9 Hz, m-С in P(S)Ph2), 130.50 (d, 1JРС = 85.5 Hz, ipso-С in
P(S)Ph2), 131.66 (d, 4JРС = 2.8 Hz, p-С in P(S)Ph2), 132.11 (d, 2JРС = 11.1 Hz, о-С in P(S)Ph2),
2
4
2
132.13 (d, JРС = 8.9 Hz, С3), 132.58 (d, JРС = 2.2 Hz, С5), 139.81 (d, JРС = 4.3 Hz, С1),
145.12 (s, С8), 148.87 (s, C12), 150.56 (s, С10), 161.44 (s, С=О). IR (КBr, ν/cm–1): 470(w),
505(m), 520(m), 614(w), 639(m) (P=S), 695(m), 714(s), 729(m), 754(s), 778(w), 841(w),
996(w), 1070(w), 1100(m), 1127(w), 1233(w), 1253(w), 1296(m), 1392(w), 1439(s), 1455(w),
1481(m), 1506(s) (C(O)NH), 1556(m), 1570(m), 1590(w), 1682(m) (С=О), 3056(w), 3192(w)
(NH). Anal. Calcd for С24Н18ClN2OPS·0.2СН2Cl2: С, 63.06; Н, 4.00; N, 6.10. Found: С, 62.97;
Н, 3.81; N, 5.97%.
N-[2-(Diphenylthiophosphoryl)phenyl]pyridine-2-carboxamide (3)
Triphenylphosphite (2.0 g, 6.5 mmol) was slowly dropwise added to a solution of pyridine-
2-carboxylic acid (0.8 g, 6.5 mmol) and 2-(diphenylthiophosphoryl)aniline (2.0 g, 6.5 mmol) in
10 mL of pyridine at 100°С. The stirred reaction mixture was heated for 10 h. After cooling to
room temperature, the solvent was removed in vacuo, and the residue obtained was dissolved in
chloroform. The resulting solution was sequentially washed with water, saturated aqueous
solution of NaHCO3, and again with water, dried over anhydrous Na2SO4, and evaporated to
dryness. The residue was recrystallized from EtOAc to give 1.7 g of ligand 4 as a white
crystalline solid. Yield: 63%. Mp: 183–184°С. 31Р{1H} NMR (161.98 MHz, CDCl3): δ 39.26
1
3
3
ppm. Н NMR (400.13 MHz, CDCl3): δ 6.95 (dd, JPH = 14.6 Hz, JHH = 7.6 Hz, 1H, H(C3)),
3
7.13 (t, JHH = 7.6 Hz, 1Н, Н(С4)), 7.36–7.45 (m, 7Н, HAr), 7.58–7.62 (m, 1H, HAr), 7.73–7.77
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3
3
3
(m, 1H, HAr), 7.82 (dd, JPH = 13.6 Hz, JHH = 7.6 Hz, 4H, o-H in P(S)Ph2), 7.97 (d, JHH = 7.9
Hz, 1H, H(C9)), 8.26 (dd, 3JHH = 8.0 Hz, 4JPH = 5.0 Hz, 1H, H(C6)), 8.58 (d, 3JHH = 4.4 Hz, 1Н,
Н(С12)), 11.21 (s, 1Н, NH). 13C{1H} NMR (100.61 MHz, CDCl3): δ 121.85 (s, С9), 124.12 (d,
1
3
3JРС = 12.3 Hz, С4), 124.74 (d, JРС = 85.5 Hz, С2), 125.38 (d, JРС = 6.8 Hz, С6), 125.94 (s,
С11), 128.21 (d, 3JРС = 12.6 Hz, m-С in P(S)Ph2), 130.54 (d, 1JРС = 85.5 Hz, ipso-С in P(S)Ph2),
131.54 (d, 4JРС = 2.8 Hz, p-С in P(S)Ph2), 132.06 (d, 2JРС = 11.1 Hz, о-С in P(S)Ph2), 132.08 (d,
2JРС = 8.0 Hz, С3), 132.48 (d, 4JРС = 2.5 Hz, С5), 136.65 (s, С10), 140.06 (d, 2JРС = 4.3 Hz, C1),
147.85 (s, С12), 148.93 (s, С8), 162.52 (s, С=О). IR (КBr, ν/cm–1): 447(w), 513(m), 524(m),
613(w), 636(m) (P=S), 662(w), 687(m), 694(m), 713(s), 720(m), 734(m), 749(m), 754(m),
760(m), 998(m), 1070(w), 1093(m), 1098(m), 1114(w), 1233(w), 1293(m), 1299(m), 1429(m),
1435(s), 1438(s), 1448(w), 1463(w), 1478(w), 1517(s), 1531(s) (C(O)NH), 1587(w), 1575(s),
1691(s) (С=О), 3057(w), 3280(m) (NH). Anal. Calcd for С24Н19N2OPS: С, 69.55; Н, 4.62; N,
6.76. Found: С, 69.57; Н, 4.57; N, 6.64%.
Synthesis of complexes
General procedure for the synthesis of Re(I) complexes 4–6
A stirred mixture of the corresponding ligand (0.150 mmol), Re(CO)5Br (61 mg, 0.150
mmol), and Et3N (21 μL, 0.150 mmol) in 10 mL of toluene was refluxed for 1 h. After cooling to
room temperature, the solvent was removed in vacuo, and the resulting residue was purified by
silica gel column chromatography (eluent: EtOAc–hexane (1:1) (4, 5) or CHCl3 (6)) to give
complexes 4–6 as pale yellow crystalline solids.
[κ3-О,N,N-(L–H)Re(I)(CO)3] (4)
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Yield: 77 mg (70%). Mp: >245С (decomp.). 31Р{1H} NMR (121.49 MHz, CDCl3): δ
1
3
3
45.95 ppm. Н NMR (300.13 MHz, CDCl3): δ 6.97 (dd, JPH = 13.0 Hz, JHH = 7.7 Hz, 1Н,
3
Н(С3)), 7.16–7.28 (m, 5Н, HAr), 7.54 (d, JHH = 8.7 Hz, 1H, HC(10) or H(C11)), 7.35–7.40 (m,
1Н, HAr), 7.59–7.66 and 7.70–7.83 (both m, 4Н + 4H, HAr). IR (КBr, ν/cm–1): 504(w), 521(w),
530(w), 544(m), 555(m), 574(m), 592(w), 630(w), 659(w), 685(w), 694(m), 718(m), 727(m),
739(w), 749(w), 758(w), 764(w), 854(w), 970(w), 997(w), 1026(w), 1057(m), 1087(m), 1124(m)
(Р=О), 1147(w), 1167(m), 1202(w), 1272(w), 1325(m), 1364(m), 1436(sh, m), 1440(m),
1451(m), 1464(m), 1559(m), 1585(m), 1638(s) (С=О), 1878(vs) (СО), 1902(vs) (СО), 1922(vs)
(СО), 2020(vs) (СО), 3055(m). Anal. Calcd for С27Н16Сl2N2O5PRe: С, 44.03; Н, 2.19; N, 3.80.
Found: С, 43.91; Н, 2.24; N, 3.74%.
[κ3-S,N,N-(L–H)Re(I)(CO)3] (5)
Yield: 85 mg (79%). Mp: >285С (decomp.). 31Р{1H} NMR (161.98 MHz, CDCl3): δ
1
3
3
41.76 ppm. Н NMR (400.13 MHz, CDCl3): δ 6.90 (dd, JРH = 13.9 Hz, JHH = 7.8 Hz, 1Н,
3
Н(С3)), 7.18–7.26 (m, 4Н, HAr), 7.40–7.65 (m, 10Н, HAr), 7.76 (t, JHH = 7.6 Hz, 1Н, Н(C5)),
8.68 (d, 3JHH = 7.3 Hz, 1H, H(C12)). IR (КBr, ν/cm–1): 483(w), 502(m), 517(m), 530(m), 593(m)
and 606(m) (both P=S), 621(w), 644(w), 690(m), 703(m), 711(m), 729(w), 751(m), 786(w),
966(w), 998(w), 1072(w), 1103(m), 1125(w), 1159(w), 1234(w), 1355(m), 1417(w), 1438(m),
1462(m), 1482(w), 1507(w), 1548(w), 1582(m), 1593(s), 1637(s) (С=О), 1888(vs) (СО),
1910(vs) (СО), 1936(sh, vs) (CO), 2017(vs) (СО), 3059(w). Anal. Calcd for
С27Н17ClN2O4PReS: С, 45.16; Н, 2.39; N, 3.90. Found: С, 44.92; Н, 2.27; N, 3.70%.
[κ3-S,N,N-(L–H)Re(I)(CO)3] (6)
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Yield: 77 mg (75%). Mp: >296С (decomp.). 31Р{1H} NMR (161.98 MHz, CDCl3): δ
1
3
3
41.72 ppm. Н NMR (400.13 MHz, CDCl3): δ 6.91 (dd, JРH = 13.6 Hz, JHH = 7.6 Hz, 1Н,
Н(С3)), 7.13–7.26 (m, 5Н, HAr), 7.33–7.52 (m 5H, HAr), 7.55–7.61 (m, 4Н, HAr), 7.70–7.77 (m,
3
13
2Н, HAr), 8.79 (d, JHH = 5.0 Hz, 1H, H(C12)). C{1H} NMR (100.61 MHz, CDCl3): δ 123.85
3
(d, 1JPC = 87.2 Hz, C2), 124.41 (d, JPC = 13.2 Hz, C4), 125.35 (s, C9), 126.41 (s, C11), 126.96
1
1
(d, JPC = 86.7 Hz, ipso-C in P(S)Ph), 127.41 (d, JPC = 86.1 Hz, ipso-C in P(S)Ph), 127.72 (d,
3JPC = 7.6 Hz, C6), 128.03 (d, 3JPC = 13.6 Hz, m-C in P(S)Ph), 128.89 (d, 3JPC = 12.5 Hz, m-C in
2
4
P(S)Ph), 131.91 (d, JPC = 11.0 Hz, o-C in P(S)Ph), 132.03 (d, JPC = 3.4 Hz, p-C in P(S)Ph),
2
4
2
132.70 (d, JPC = 8.3 Hz, C3), 132.72 (d, JPC = 3.4 Hz, p-C in P(S)Ph), 133.15 (d, JPC = 10.2
4
Hz, o-C in P(S)Ph), 134.75 (d, JPC = 2.3 Hz, C5), 137.75 (s, C10), 152.10 (s, C12), 154.26 (s,
C8), 154.38 (d, 2JPC = 3.8 Hz, C1), 168.34 (s, C=O), 189.57 (s, CO), 195.04 (s, CO), 196.44 (d,
3JPC = 4.9 Hz, CO). IR (KBr, ν/cm–1): 485(w), 507(w), 524(w), 534(w), 549(w), 594(m) and
604(m) (both P=S), 621(w), 644(w), 689(m), 705(w), 716(w), 750(m), 767(w), 814(w), 998(w),
1070(w), 1101(m), 1124(w), 1150(w), 1292(w), 1356(m), 1437(m), 1442(m), 1461(m), 1482(w),
1564(w), 1581(m), 1600(s), 1638(s) (С=О), 1879(vs) (СО), 1890(vs) (СО), 1916(vs) (СО),
2016(vs) (СО), 3075(w). Anal. Calcd for С27Н18N2O4PReS: С, 47.43; Н, 2.65; N, 4.10. Found:
С, 47.47; Н, 2.61; N, 4.04%.
[κ2-S,N-(L–H)2Pd(II)] (7)
A solution of PdCl2(PhCN)2 (29 mg, 0.076 mmol) in 3 mL of dichloromethane was slowly
dropwise added to a solution of ligand 1b (73 mg, 0.152 mmol) and Et3N (21 μL, 0.152 mmol) in
5 mL of CH2Cl2. The reaction mixture was left under ambient conditions for 3 days. The
resulting precipitate was filtered off, washed with CH2Cl2 and Et2O, and dried in air to give 77
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mg of complex 7 as an orange crystalline solid. Yield: 93%. Mp: >285°С (decomp.). IR (КBr,
ν/cm–1): 503(w), 527(m), 532(w), 578(m) and 595(s) (both P=S), 621(w), 695(m), 712(m),
729(w), 749(w), 755(m), 763(m), 826(w), 871(w), 975(w), 998(w), 1038(w), 1074(w), 1101(m),
1144(m), 1160(w), 1186(w), 1266(w), 1312(w), 1333(m), 1384(m), 1431(m), 1438(m), 1460(m),
1482(w), 1547(m), 1564(m), 1577(m), 1605(s) (С=О), 2924(w), 3052(w). Anal. Calcd for
С48Н32Сl4N4O2P2PdS2·0.33CH2Cl2: С, 52.80; Н, 2.99; N, 5.10. Found: С, 52.71; Н, 2.87; N,
5.94%.
[κ3-S,N,N-(L–H)Pd(II)Cl] (8)
A solution of PdCl2(PhCN)2 (76 mg, 0.198 mmol) in 5 mL of dichloromethane was slowly
dropwise added to a solution of ligand 2 (92 mg, 0.198 mmol) and Et3N (28 μL, 0.198 mmol) in
7 mL of CH2Cl2. The reaction mixture was left under ambient conditions for 3 days and then
evaporated to dryness. The resulting residue was purified by silica gel column chromatography
(eluent: CHCl3) to give 65 mg of complex 8 as a red crystalline solid. Yield: 56%. Mp: >300°С
(decomp.) 31Р{1H} NMR (121.49 MHz, CDCl3): δ 38.62 ppm. 1Н NMR (300.13 MHz, CDCl3): δ
6.74 (dd, 3JРH = 15.6 Hz, 3JHH = 7.8 Hz, 1Н, Н(С3)), 7.03 (dt, 3JHH = 7.8 Hz, 4JPH = 2.7 Hz, 1Н,
Н(С4)), 7.41 (dd, 3JHH = 6.0 Hz, 4JHH = 2.2 Hz, 1Н, Н(С11)), 7.53–7.58 (m, 5Н, HAr), 7.62–7.66
(m, 2Н, HAr), 7.71–7.81 (m, 5Н, HAr), 7.94 (d, 4JHH = 2.2 Hz, 1Н, Н(С9)), 9.01 (d, 3JHH = 6.0 Hz,
1Н, Н(С12)). IR (КBr, ν/cm–1): 506(m), 513(m), 524(m), 602(m) (P=S), 620(w), 691(m),
704(m), 717(w), 751(m), 755(m), 775(m), 846(w), 998(w), 1071(w), 1108(m), 1131(w),
1158(w), 1184(w), 1270(w), 1329(s), 1419(w), 1436(s), 1465(m), 1481(w), 1557(w), 1581(m),
1594(s), 1634(s) (С=О), 3053(w), 3076(w). Anal. Calcd for С24Н17Cl2N2OPPdS: С, 48.88; Н,
2.91; N, 4.75. Found: С, 48.85; Н, 2.94; N, 4.69%.
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[κ3-S,N,N-(L–H)Pd(II)Cl] (9)
A solution of PdCl2(PhCN)2 (47 mg, 0.123 mmol) in 4 mL of dichloromethane was slowly
dropwise added to a solution of ligand 3 (51 mg, 0.123 mmol) and Et3N (17 μL, 0.123 mmol) in
5 mL of CH2Cl2. The reaction mixture was left under ambient conditions for 3 days. The
resulting precipitate was filtered off, washed with CHCl3 and Et2O, and dried in air to give 61
31
mg of complex 9 as a red crystalline solid. Yield: 85%. Mp: >301 °С (decomp.). Р{1H} NMR
1
3
(121.49 MHz, (CD3)2SO): δ 37.84 ppm. Н NMR (300.13 MHz, (CD3)2SO): δ 6.71 (dd, JРH
=
15.2 Hz, 3JHH = 7.8 Hz, 1Н, Н(С3)), 7.13 (m, 1Н, НAr), 7.59 (t, 3JHH = 7.3 Hz, 1H, H(C5)), 7.62–
3
3
4
7.79 (m, 12Н, HAr), 7.87 (d, JHH = 7.7 Hz, 1Н, Н(С9)), 8.19 (dt, JHH = 7.7 Hz, JHH = 1.4 Hz,
3
1Н, Н(С10)), 8.89 (d, JHH = 4.8 Hz, 1Н, Н(С12)). IR (КBr, ν/cm–1): 504(m), 509(m), 534(w),
603(m) (P=S), 620(w), 682(m), 690(m), 706(m), 717(w), 725(w), 736(w), 752(m), 804(w),
846(w), 997(w), 1052(w), 1070(w), 1104(m), 1151(w), 1186(w), 1261(w), 1268(w), 1291(m),
1333(s), 1437(m), 1464(m), 1481(w), 1559(w), 1581(m), 1601(m), 1633(s) (С=О), 3053(w).
Anal. Calcd for С24Н18ClN2OPPdS·0.2CHCl3: С, 50.18; Н, 3.17; N, 4.84%. Found: С, 50.66; Н,
3.17; N, 4.77%.
[κ3-O,N,N-(L–H)2Cu(II)] (10a)
A stirred mixture of ligand 1a (200 mg, 0.428 mmol) and Cu(OAc)2·H2O (43 mg, 0.214
mmol) in 10 mL of methanol was refluxed till complete dissolution. The reaction mixture was
left under ambient conditions for 12 h. The resulting precipitate was filtered off, washed with hot
MeOH and Et2O, and dried in vacuo to give 167 mg as a green crystalline solid. Yield: 77%. Mp:
>180°С (decomp.). IR (КBr, ν/cm–1): 524(m), 539(m), 552(s), 570(m), 582(w), 693(m), 719(m),
738(w), 756(w), 796(w), 866(w), 938(w), 955(w), 999(w), 1026(m), 1041(m), 1058(m),
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1086(m), 1129(s) and 1141(sh, m) (both Р=О), 1271(w), 1328(s), 1365(m), 1420(m), 1439(s),
1460(m), 1483(w), 1548(m), 1563(m), 1579(m), 1614(s), 1631(s) (С=О), 3057(w), 3413(br, w).
Anal. Calcd for С48Н32Сl4СuN4O4P2·H2O: С, 56.85; Н, 3.38; N, 5.52. Found: С, 56.48; Н, 3.07;
N, 5.41%.
[κ3-S,N,N-(L–H)Cu(II)OAc] (10b)
A mixture of ligand 1b (46 mg, 0.095 mmol) and Cu(OAc)2·H2O (19 mg, 0.095 mmol) in
10 mL of methanol was refluxed for 1.5 h. The resulting precipitate was filtered off, washed with
hot methanol, and recrystallized from CH2Cl2–Et2O (1:2) to give 41 mg of complex 10b as a
green crystalline solid. Yield: 70%. Mp: >182°С (decomp.). IR (КBr, ν/cm–1): 508(w), 525(m),
589(w), 604(m) (P=S), 624(w), 680(w), 690(m), 711(m), 751(w), 758(w), 831(w), 878(w),
935(w), 971(w), 998(w), 1040(w), 1056(m), 1071(w), 1102(m), 1130(w), 1154(m), 1164(m),
1210(w), 1259(w), 1280(w), 1324(m), 1367(m), 1436(s), 1450(sh, m), 1460(m), 1480(w),
1493(w), 1538(m), 1561(m), 1578(w), 1648(s) (С=О), 1701(w), 2924(w), 3053(w). Anal. Calcd
for С26Н19Сl2СuN2O3PS·0.5H2O: С, 50.86; Н, 3.28; N, 4.56. Found: С, 50.97; Н, 3.19; N,
4.45%.
[κ3-S,N,N-(L–H)Cu(II)Cl] (11)
A mixture of ligand 2 (82 mg, 0.176 mmol), CuCl22H2O (30 mg, 0.176 mmol), and
triethylamine (24 μL, 0.176 mmol) in methanol was refluxed till complete dissolution. The
precipitate formed upon cooling was filtered off, washed with hot methanol, and dried in air to
give 88 mg of complex 11 as a green crystalline solid. Yield: 90%. Mp: >185°С (decomp.). IR
(КBr, ν/cm–1): 507(m), 524(s), 543(w), 608(m) and 624(m) (both P=S), 693(m), 706(m), 715(m),
730(w), 752(m), 774(m), 783(w), 870(w), 998(w), 1021(w), 1071(w), 1103(m), 1131(w),
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1161(w), 1184(w), 1270(w), 1356(s), 1418(m), 1437(s), 1465(m), 1480(w), 1557(m), 1580(s),
1590(s), 1622(s) (С=О), 3057(w), 3443(br, w). Anal. Calcd for С24Н17Сl2СuN2OPS·0.5H2O: С,
51.85; Н, 3.26; N, 5.04. Found: С, 51.90; Н, 3.45; N, 4.89%.
[κ3-S,N,N-(L–H)Cu(II)Cl] (12)
A mixture of ligand 3 (66 mg, 0.159 mmol), CuCl2·2H2O (27 mg, 0.159 mmol), and
triethylamine (22 μL, 0.159 mmol) in 10 mL of methanol was refluxed for 1.5 h. The resulting
precipitate was filtered off, washed with hot methanol, and dried in air to give 70 mg of complex
12 as a green crystalline solid. Yield: 81%. Mp: >230°С (decomp.). IR (КBr, ν/cm–1): 499(m),
511(m), 541(w), 598(w), 606(m) (P=S), 621(w), 686(s), 707(m), 718(w), 740(w), 754(m),
764(m), 849(w), 938(w), 997(w), 1026(m), 1050(w), 1071(w), 1103(m), 1129(w), 1152(w),
1271(w), 1299(m), 1342(s), 1356(s), 1436(s), 1465(m), 1560(w), 1570(m), 1578(m), 1598(s),
1615(s), 1636(m) (С=О), 2925 (m), 3055(w). Anal. Calcd for С24Н18ClСuN2OPS·CH3OH: С,
55.15; Н, 4.07; N, 5.14. Found: С, 55.14; Н, 4.07; N, 5.33%.
Crystal structure determination and data collection
Single crystals suitable for X-ray experiments were obtained by recrystallization from
CHCl3–hexane (4, 5, 8, 10a) or CHCl3–EtOH (12). X-ray diffraction experiments were carried
out with a SMART APEX2 CCD diffractometer using graphite monochromated Mo-Kα
radiation (λ = 0.71073 Å, ω-scans) at 100 (4, 8, 12) and 120 K (5, 10a). The structures were
solved by direct method and refined by full-matrix least-squares method against F2 in anisotropic
approximation for non-hydrogen atoms. The H(C) atom positions were calculated. All hydrogen
atoms were refined in isotropic approximation in riding model. Crystal data and structure
refinement parameters for 4, 5, 8, 10a, and 12 are given in Table 1. All calculations were
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performed using the SHELXTL software.23 CCDC 982067–982071 contain the supplementary
crystallographic data for compounds 4, 5, 8, 10a, and 12. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge, B2 1EZ, UK; fax: +44 1223 336033;
or e-mail: deposit@ccdc.cam.ac.uk).
Acknowledgments
This work was supported by the Russian Foundation for Basic Research, project no. 12-03-
00793-a.
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Table 1 Crystal data and structure refinement parameters for complexes 4, 5, 8, 10a, and 12.
4
5
8
10a
12
C51H41Cl5Cu
C27H16Cl2N2 C27H17ClN2O4 C49H35Cl7N4 C48H32Cl4Cu
Empirical formula
2
O5PRe
PReS
O2P2Pd2S2
N4O4P2
N4O4P2S2
Formula weight
736.49
100
718.11
120
1298.82
100
996.09
1204.27
100
T, K
120
Crystal system
Orthorhombic Monoclinic
Triclinic
P-1
Monoclinic
Triclinic
P-1
Space group
P212121
4
P21/c
4
P21
Z
1
2
1
a, Å
b, Å
c, Å
, °
11.2092(5)
14.9173(6)
15.5681(6)
90
10.5124(5)
15.2277(7)
8.4893(4) 12.5648(5)
9.3167(4) 14.0611(6)
9.5729(4)
10.5364(5)
13.8653(9)
101.5240(10)
21.1892(10) 16.1744(7) 14.3861(6)
90
95.6840(10)
90
92.1720(10)
90
104.0670(10 106.4350(10
, °
90
96.3440(10)
)
)
, °
90
2603.16(19)
1.879
95.1880(10)
90
109.6970(10)
V, Å3
3375.3(3) 1233.45(10) 2437.81(17) 1265.94(11)
Dcalc (g cm−1)
Linear absorption,
1.413
3.817
1.749
1.304
1.357
0.779
1.580
1.300
4.977
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 (mm−1)
F(000)
1424
58
1392
58
646
60
1014
58
612
56
2max, °
Reflections
measured
Independ.
reflections
Observed
reflections [I >
2(I)]
31284
6931
8986
8986
15783
7144
12623
12623
13431
6058
6682
7245
6365
10728
5228
Parameters
R1
344
334
325
568
347
0.0292
0.0629
1.045
0.0288
0.0642
0.998
0.0278
0.0817
1.001
0.0386
0.0769
0.959
0.0363
0.0973
1.030
wR2
GOF
Δmax/ Δmin (e
Å−3)
1.127/-1.832 1.374/-1.299 0.777/-0.857 0.450/-0.311 0.668/-0.776
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X
PPh2
NH2
X = O, S
Cl
N
C(O)Cl
Cl
N
C(O)Cl
N
COOH
Cl
Et3N, MeCN, r.t., 12 h (a)
C6H6, Py, r.t., 2 days (b)
P(OPh)3, Py, 100oC, 10 h
Et3N, CH2Cl2, r.t., 12
Ph
X
Ph
Ph
Ph
O
Ph
O
Ph
O
P
P
S
P
S
NH
NH
N
NH
N
N
Cl
Cl
Cl
X = O 79% (1a)
X = S 63% (1b)
52% (2)
63% (3)
Scheme 1 Synthesis of P(X)-substituted picolinamides 1–3.
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1a, 2 or 3
Re(CO)5Br, Et3N
PhMe, reflux, 1 h
Ph
O
Ph
Ph
S
Ph
O
Ph
O
Ph
O
P
N
P
N
P
N
S
Re(CO)3
Re(CO)3
Re(CO)3
N
Cl
N
N
Cl
Cl
70% (4)
79% (5)
75% (6)
Scheme 2 Re(I) complexes of (thio)phosphoryl-functionalized picolinamides.
Cl
Ph
S
Ph
O
P
N
Ph
S
Ph
O
P
N
N
Cl
Cl
Pd
PdCl2(PhCN)2, Et3N
CH2Cl2, r.t., 3 days
PdCl2(PhCN)2, Et3N
CH2Cl2, r.t., 3 days
N
1b, 2 or 3
Pd
N
S
Cl
N
P
O
Ph
Ph
Cl
R
R = Cl 56% (8)
R = H 85% (9)
93% (7)
Scheme 3 Pd(II) complexes of (thio)phosphoryl-functionalized picolinamides.
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1-3
Cu(OAc)2 H2O
MeOH, reflux, 0.5 h
CuCl2 2H2O, Et3N
MeOH, reflux, 0.5-1.5 h
Cu(OAc)2 H2O
MeOH, reflux, 1.5 h
Ph
Ph
Ph
O
Ph
O
Ph
P
Ph
Cl
Cl
P
P
S
S
N
O
N
O
OAc
Cl
Cu
Cu
N
N
Cu
O
N
N
Cl
N
O
N
P
Ph
Cl
Cl
Cl
Ph
R
R = Cl 90% (11)
R = H 81% (12)
77% (10a)
70% (10b)
Scheme 4 Cu(II) complexes of (thio)phosphoryl-functionalized picolinamides.
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N
O
O
N
N
Ac
O
N
N
Co
N
O
S
N
N
N
S
N
Pd
N
Cu
Cu
Na
Cl
O
O
N
N
N
Ac
O
O
N
I
II
III
Figure 1
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Figure 2 General view of complex 4 showing atom labeling scheme. Hereinafter, the
nonhydrogen atoms are represented as thermal ellipsoids at 50% probability level, and all
hydrogen atoms are omitted for clarity.
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