Synthesis and structural study of divalent Cu, Zn, Cd and Pd complexes supported by 1,2,3-triazole-based chalcogen ligands

Article abstract of DOI:10.1016/j.ica.2013.11.039

Transition metal complexes of the type [M{4,5-(P(E)Ph₂) ₂tz}₂(thf)_n] [tz = 1,2,3-triazole; M = Cu, n = 2, E = S(3); M = Cu, n = 0, E = Se(4); M = Zn, n = 2, E = S(5); M = Cd, n = 2, E = S(7), Se(8); M = Pd, n = 0, E = S(9), Se(10)] and [Zn₂{4,5-(P(Se) Ph₂)₂(tz)}₄](6) were obtained by reacting [K{4,5-(P(E)Ph₂)₂tz}] with MX₂ (M = Cu, Zn, Cd, X = Cl or M = Pd, X = AcO) in a 2:1 M ratio. The structures of these compounds were investigated by IR, ¹H and ³¹P NMR spectroscopy, as well as by elemental analysis. The molecular structures of 3, 4, 5-10 were determined by single-crystal X-ray diffraction. In addition, during the crystallization process of 4, single crystals of 4a were obtained showing a structure where the replacement of a selenium atom from the non-coordinated PSe moiety by an oxygen atom gives a mixed oxygen-selenium complex. All the compounds exhibit MEPCN heterocycles as a common structural feature but in the case of 6 a bimetallic arrangement with a scorpionate-like coordination mode is also observed.

Full text of DOI:10.1016/j.ica.2013.11.039

Accepted Manuscript
Synthesis and Structural Study of divalent Cu, Zn, Cd and Pd complexes sup-
ported by 1,2,3-triazole-based Chalcogen Ligands
Jesús Pastor-Medrano, Vojtech Jancik, Erandi Bernabé-Pablo, Diego Martínez-
Otero, Marisol Reyes-Lezama, T. Jesús Morales-Juárez
PII:
S0020-1693(13)00658-0
http://dx.doi.org/10.1016/j.ica.2013.11.039
ICA 15765
DOI:
Reference:
Inorganica Chimica Acta
To appear in:
Received Date:
Revised Date:
Accepted Date:
11 June 2013
28 November 2013
30 November 2013
Please cite this article as: J. Pastor-Medrano, V. Jancik, E. Bernabé-Pablo, D. Martínez-Otero, M. Reyes-Lezama,
T. Jesús Morales-Juárez, Synthesis and Structural Study of divalent Cu, Zn, Cd and Pd complexes supported by
1,2,3-triazole-based Chalcogen Ligands, Inorganica Chimica Acta (2013), doi: http://dx.doi.org/10.1016/j.ica.
2013.11.039
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Synthesis and Structural Study of divalent Cu, Zn, Cd and Pd complexes supported
by 1,2,3-triazole-based Chalcogen Ligands.
Jesús Pastor-Medrano,a Vojtech Jancik,b Erandi Bernabé-Pablo,b Diego Martínez-Otero,b
Marisol Reyes-Lezama,b T. Jesús Morales-Juárez,a,*
aFacultad de Química, Universidad Autónoma del Estado de México, Paseo Colón SN,
Residencial Colón, 50120 Toluca, Estado de México, México.
bCentro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carr. Toluca-
Atlacomulco km 14.5, 50200 Toluca, Estado de México, México.
*Corresponding author. E-mail: jmoralesj@uaemex.mx. Fax. +52 (722) 17 38 90
Keywords: 1,2,3-triazole, X-ray structure, chalcogens, coordination compounds
Abstract:
Transition metal complexes of the type [M{4,5-(P(E)Ph2)2tz}2(thf)n] [tz = 1,2,3-
triazole; M = Cu, n = 2, E = S (3); M = Cu, n = 0, E = Se (4); M = Zn, n = 2, E = S (5); M =
Cd, n = 2, E = S (7), Se (8); M = Pd, n = 0, E = S (9), Se (10)] and [Zn2{4,5-
(P(Se)Ph2)2(tz)}4] (6) were obtained by reacting [K{4,5-(P(E)Ph2)2tz}] with MX2 (M = Cu,
Zn, Cd, X = Cl or M = Pd, X = AcO) in a 2:1 molar ratio. The structures of these
compounds were investigated by IR, 1H and 31P NMR spectroscopy, as well as by elemental
analysis. The molecular structures of 3, 4, 5–10 were determined by single-crystal X-ray
diffraction. In addition, during the crystallization process of 4, single crystals of 4a were
obtained showing a structure where the replacement of a selenium atom from the non-
coordinated P=Se moiety by an oxygen atom gives a mixed oxygen-selenium complex. All
the compounds exhibit MEPCN heterocycles as a common structural feature but in the case
of 6 a bimetallic arrangement with a scorpionate-like coordination mode is also observed.
1

1. Introduction
P-X-P-unit-containing species (X = N, C, alkyl, aryl, heterocycle) have been extensively
studied as ligands in the coordination chemistry of both p- and d-block elements[1]. The
large variety of available X linkage groups and the facile oxidation of P(III) to P(V) with
elemental chalcogens leads to further coordination diversity for these types of ligands. In
this regard, in the past decade a handful of main-group metal complexes derived from 4,5-
bis(diphenylphosphoranyl)-1,2,3-triazole ligands [4,5-{P(E)Ph2}2tz]– (tz = 1,2,3-triazole; E
= O, S, Se) have been reported[2,3]. These compounds exhibited unusual structural features
and enhanced stability for alkaline and alkaline-earth metals [3], as well as interesting
chemical properties for Group 13 metal complexes[2].
The multifunctionality of [4,5-{P(E)Ph2}2tz]– with the differing properties of the donor
atoms (N, O, S, Se) make them an interesting type of ligands for the preparation of
transition metal complexes. These properties are attractive for probing the steric and
electronic properties of various transition metal centers. However, there are only three
known examples of fully characterized transition-metal complexes supported by the [4,5-
{P(E)Ph2}2tz]– (E = O, S) ligands reported to date[4]. Further understanding of the bonding
patterns of these ligands could come from a study with transition metals, namely divalent
metal species such as Cu(II) and Zn(II) which have borderline properties and Cd(II) and
Pd(II) which are soft Lewis acids. Consequently, our interest is focused on the coordination
patterns that might arise from the use of these metals with 4,5-bis(diphenylphosphoranyl)-
1,2,3-triazoles which have the presence of both soft and hard donor atoms (i.e. sulfur and
selenium atoms attached to the phosphorus atoms and the nitrogen atoms from the triazole
ring).
Herein, we describe the synthesis and structural characterization of divalent Cu, Zn, Cd
2

and Pd complexes derived from the 1,2,3-triazole-based chalcogen ligands [4,5-
{P(E)Ph2}2tz]– (E = S, Se).
2. Experimental Section
2.1. Materials and Methods
The starting materials were purchased from commercial sources and the solvents were dried
according to conventional procedures and freshly distilled prior to use. The ligands [H{4,5-
(P(E)Ph2)2tz}] [E = S(1), Se(2); tz = 1,2,3-triazole] were prepared according to the
literature procedure [4]. FT-IR spectra were measured on a Bruker Tensor 27 spectrometer
using ATR. NMR spectra were recorded on a Bruker Avance 300 MHz spectrometer with
1H and 31P chemical shifts referenced to SiMe4, and H3PO4 (85% in H2O), respectively.
Elemental analyses (C, H, N) were measured on a MicroVARIO Cube analyzer and all the
samples were dried under vacuum for 2 h prior to the measurement. Melting points were
measured on a Büchi B-540 melting point apparatus and were not corrected. Electron
impact mass spectrometry (EI-MS) was carried out on a Shimadzu GCMS-QP2010Plus
using direct injection with the detection range 20 to 1090 m/z. The molecular mass of
compounds 3–10 are outside of the range of the equipment, and further attempts to obtain
their mass spectra on a Bruker micrOTOF II were proven to be futile. Therefore, the mass
spectra of these compounds are not reported.
2.2. Preparation of the complexes
2.2.1. Preparation of [Cu{4,5-(P(S)Ph2)2tz}2(thf)2] (3)
To a solution of 1 (0.60 g, 1.20 mmol) in 15 mL of THF was added a solution of KOH
(0.07 g, 1.20 mmol) in 6 mL of anhydrous methanol. After stirring for 15 minutes, a
solution of CuCl2·H2O (0.10 g, 0.60 mmol) was added to the reaction mixture and the
3

resulting solution was allowed to stir for 1 h at ambient temperature. The reaction mixture
was then filtered and the solid was extracted with CH2Cl2 and filtered through Celite. After
removal of the solvent, the residue was recrystallized from CH2Cl2/THF to give green
–1
~
crystals. Yield 80 % (0.58 g, 0.48 mmol). Mp 315–316 ºC. IR (ATR, cm ): v 708 (P=S),
1
658[P–S(Cu)]. H NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 1.87 [br m, 4H, O(CH2CH2)2],
3.77 [br m, 4H, O(CH2CH2)2], 7.12 [br m, 4H, (p-C6H5)], 7.35 [br m, 8H, (m-C6H5)], 7.66
31
[br m, 8H, (o-C6H5)]. P NMR (121.6 MHz, CDCl3 25 °C, ppm): δ 31.0 [br s P=S], 31.3
[br s, P–S(Cu)]. Due to the variant content of the solvent in the different samples we did not
obtain elemental analysis data of satisfactory quality.
2.2.2. Preparation of [Cu[4,5-{P(Se)Ph2}2tz]2] (4).
To a solution of 2 (0.36 g, 0.60 mmol) in 15 mL of THF was added a solution of KOH
(0.034 g, 0.60 mmol) in 6 mL of anhydrous methanol. After stirring for 15 minutes, a
solution of CuCl2·H2O (0.05 g, 0.30 mmol) was added to the reaction mixture and the
resulting solution was allowed to stir for 1 h at ambient temperature. The reaction mixture
was then filtered and the solvent removed leaving a solid residue, which was extracted with
CH2Cl2 and filtered through Celite. After the removal of the solvent, the solid was
recrystallized from CH2Cl2/THF to give red crystals. Yield 80 % (0.35 g, 0.24 mmol). Mp
–1
1
~
280–281 ºC. IR (ATR, cm ): v 585 [P=Se], 498 [P–Se(Cu)]. H NMR (300 MHz, CDCl3,
25 ºC, ppm): δ 7.45 [br m, 12H, (m, p-C6H5)], 7.52 [br m, 8H, (o-C6H5)]. 31P NMR (121.6
MHz, CDCl3 25 °C, ppm): δ 17.3 [br s, P=Se], 21.6 [br s, P–Se(Cu)]. Due to the variant
content of the solvent in the different samples we did not obtain elemental analysis data of
satisfactory quality.
2.2.3. Preparation of [Zn{4,5-(P(S)Ph2)2tz}2(thf)2](5).
4

A similar method as for 3 was used starting from 1 (0.60 g, 1.20 mmol), KOH (0.07 g, 1.20
mmol) and ZnCl2·H2O (0.10 g, 0.60 mmol). Colorless crystals were obtained with 82 %
–1
~
yield (0.60 g, 0.49 mmol). Mp 299–300 ºC. IR (ATR, cm ): v 708 [P=S], 602 [P–S(Zn)].
1H NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 1.85 [m, 4H, O(CH2CH2)2], 3.75 [m, 4H,
O(CH2CH2)2], 7.31 [m, 4H, (p-C6H5)], 7.44 [m, 8H, (m-C6H5)], 7.63 [m, 8H, (o-C6H5)]. 31P
NMR (121.6 MHz, CDCl3 25 °C, ppm): δ 29.1 [P=S], 34.5 [P–S(Zn)]. Elemental analysis
for C60H56N6P4O2S4Zn (1210.66 g·mol–1) calcd: C 59.52, H 4.66, N 6.94 %; found: C
58.72, H 4.66, N 6.9 %.
2.2.4. Preparation of [Zn2{4,5-(P(Se)Ph2)2tz}4](6).
A similar method as for 4 was used starting from 2 (0.60 g, 1.00 mmol), KOH (0.06 g, 1.00
mmol) and ZnCl2·H2O (0.03 g, 0.50 mmol). Colorless crystals were obtained with 83 %
–1
~
yield (0.52 g, 0.21 mmol). Mp 293–294 ºC. IR (ATR, cm ): v 586 [P=Se], 496 [P–
Se(Zn)]. 1H NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 7.31 [m, 4H, (p-C6H5)], 7.45 [m, 8H,
(m-C6H5)], 7.63 [m, 8H, (o-C6H5)]. 31P NMR (121.6 MHz, CDCl3 25 °C, ppm): δ 19.1
[P=Se], 21.2 [P–Se(Zn)]. Elemental analysis for C104H80N12P8Se8Zn2 (2508.06 g·mol–1)
calcd: C 49.80, H 3.22, N 6.70 %; found: C 48.89, H 3.12, N 6.14 %.
2.2.5. Preparation of [Cd{4,5-(P(S)Ph2)2tz}2(thf)2](7).
A similar method as for 3 was used starting from 1 (0.60 g, 1.20 mmol), KOH (0.07 g, 1.20
mmol) and CdCl2 (0.67 g, 0.60 mmol). Colorless crystals were obtained with 80 % yield
–1
1
~
(0.58 g, 0.48 mmol). Mp 347–348 ºC. IR (ATR, cm ): v 709 [P=S], 602 [P–S(Cd)]. H
NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 1.87 [m, 4H, O(CH2CH2)2], 3.77 [m, 4H,
O(CH2CH2)2], 7.34 [m, 4H, (p-C6H5)], 7.48 [m, 8H, (m-C6H5)], 7.71 [m, 8H, (o-C6H5)].
31P NMR (121.6 MHz, CDCl3 25 °C, ppm): δ 30.8 [P=S], 31.4 [P–S(Cd)]. Elemental
5

analysis for C60H56N6P4O2S4Cd (1210.66 g·mol–1) calcd: C 57.30, H 4.49, N 6.68 %;
found: C 57.04, H 4.32, N 6.73 %.
2.2.6. Preparation of [Cd{4,5-(P(Se)Ph2)2tz}3](8).
A similar method as for 4 was used starting from 2 (0.60 g, 1.00 mmol), KOH (0.06 g, 1.00
mmol) and CdCl2 (0.09 g, 0.50 mmol). Colorless crystals were obtained with 84 % yield
–1
1
~
(0.61 g, 0.42 mmol). Mp 314–315 ºC. IR (ATR, cm ): v 584 [P=Se], 497 [P–Se(Cd)]. H
NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 1.87 [m, 4H, O(CH2CH2)2], 3.77 [m, 4H,
O(CH2CH2)2], 7.34 [m, 4H, (p-C6H5)], 7.46 [m, 8H, (m-C6H5)], 7.67 [m, 8H, (o-C6H5)].
31P NMR (121.6 MHz, CDCl3, 25 °C, ppm): δ 18.6 [J1P–Se = 750 Hz, P=Se], 23.4 [J1
=
P–Se
610 Hz, P–Se(Cd)]. Elemental analysis for C60H56N6P4O2Se4Cd (1445.27 g·mol–1) calcd: C
49.86, H 3.91, N 5.81 %; found: C 49.59, H 3.87, N 5.76 %.
2.2.7. Preparation of [Pd{4,5-(P(S)Ph2)2tz}2](9)
To a solution of 1 (0.30 g, 0.60 mmol) in 30 mL of a mixture THF/CH3CN/methanol
(6:3:1) was added KOH (0.034 g, 0.60 mmol). After stirring for 15 minutes, a solution of
Pd(AcO)2 (0.07 g, 0.30 mmol) was added to the reaction mixture and the resulting solution
was allowed to stir for 1.5 h at ambient temperature. The reaction mixture was then filtered
and the solid was extracted with CHCl3 and filtered through Celite. After removal of the
solvent, the solid residue was recrystallized from CHCl3 to give bright yellow crystals.
–1
~
Yield 60 % (0.20 g, 0.18 mmol). Mp 353–354 ºC. IR (ATR, cm ): v 710 [P=S], 594 [P–
1
S(Pd)]. H NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 7.29 [m, 4H, (p-C6H5)], 7.55 [m, 8H,
31
(m-C6H5)], 7.84 [m, 8H, (o-C6H5)]. P NMR (121.6 MHz, CDCl3 25 °C, ppm): δ 27.3
6

[P=S], 31.4 [P–S(Pd)]. Elemental analysis for C52H40N6P4PdS4 (1107.49 g·mol–1) calcd: C
56.39, H 3.64, N 7.59 %; found: C 55.85, H 3.60, N 7.51 %.
2.2.8. Preparation of [Pd{4,5-(P(Se)Ph2)2tz}2](10)
To a solution of 1 (0.357 g, 0.60 mmol) in 30 mL of a mixture THF/CH3CN/methanol
(5:4:1) was added KOH (0.034 g, 0.60 mmol). After stirring for 15 minutes, a solution of
Pd(AcO)2 (0.067 g, 0.30 mmol) was added to the reaction mixture and the resulting
solution was allowed to stir for 1.5 h at ambient temperature. The reaction mixture was then
filtered and the solid was extracted with CHCl3 and filtered through Celite. After removal
of the solvent, the solid residue was recrystallized from CHCl3 to give light orange crystals.
–1
~
Yield 70 % (0.272 g, 0.21 mmol). Mp 327–328 ºC. IR (ATR, cm ): v 583 [P=Se], 496 [P–
Se(Pd)]. 1H NMR (300 MHz, CDCl3, 25 ºC, ppm): δ 7.34 [m, 4H, (p-C6H5)], 7.55 [m, 8H,
31
(m-C6H5)], 7.92 [m, 8H, (o-C6H5)]. P NMR (121.6 MHz, CDCl3 25 °C, ppm): δ 17.1
[P=Se], 19.9 [P–Se(Pd)]. Elemental analysis for C52H40N6P4PdSe4 (1295.07 g·mol–1) calcd:
C 48.23, H 3.11, N 6.49 %; found: C 47.79, H 3.05, N 6.35 %.
2.3 Crystal structure determination and refinement for 3–10.
Crystallographic data for all the structures were collected on a Bruker SMART APEX
DUO three-circle diffractometer equipped with an Apex II CCD detector using MoKα
(Micro-focus sealed tube with a graphite monochromator). The crystals were coated with a
hydrocarbon oil, picked up with a nylon loop, and immediately mounted in the cold
nitrogen stream of the diffractometer. All structures were solved by direct methods
7

(SHELXS-97) and refined with all data by full-matrix least-square methods on F2 using
SHELXL-97[5] with the SHELXLE GUI[6]. Carbon bound hydrogen atoms were fixed
geometrically in idealized positions and were refined as riding over the atoms to which they
were bonded. Crystallographic data and refinement details for compounds 3, 4, 4a, 5–10
are listed in Tables 1 and 2, whereas selected bond lengths and angles for these compounds
are summarized in Tables 3–5.
3. Results and Discussion
3.1 Synthesis of the complexes
The transition metal complexes [Cu{4,5-(P(S)Ph2)2tz}2(thf)2](3), [Cu[4,5-
{P(Se)Ph2}2tz]2(thf)2](4), [Zn{4,5-(P(S)Ph2)2tz}2(thf)2](5), [Zn2{4,5-(P(Se)Ph2)2(tz)}4](6),
[Cd{4,5-(P(E)Ph2)2tz}2(thf)2] [E = S(7), Se(8)], and [Pd{4,5-(P(E)Ph2)2tz}2] [E = S(9),
Se(10)] were prepared by the metathesis reaction between the potassium salt of the ligands
1 and 2, prepared in situ, and the corresponding MX2 salts (M = Cu, Zn, Cd; X = Cl or M =
Pd, X = AcO) in a 2:1 molar ratio (Scheme 1).
Compounds 3–10 were isolated in good yields (60–82 %) as air and moisture stable
crystalline solids, partially soluble in CHCl3, CH2Cl2 and methanol. The compounds were
unambiguously characterized by analytical and spectroscopic and X-ray diffraction
techniques.
3.2 Spectroscopic characterization
The green color from the copper complex 3 and the red color from 4, arise from the
absorption bands at λ = 398 nm (ε = 16145 M–1 cm–1) and 442 nm (ε = 6134 M–1 cm–1),
8

respectively (Figure 1). These bands are absent in the corresponding ligands and are
ascribed to charge-transfer transitions.
The IR spectra of compounds 3–10 are all devoid of the N–H absorption band in the
range of 3000–3200 cm–1, thus confirming the deprotonation of the ligand. Furthermore,
~
two set of bands are observed for the sulfide derivatives 3, 5, 7 and 9 at v ca. 600 and 710
cm–1 corresponding to the P–S(M) and P=S groups, respectively. On the other hand, a
–1
~
similar pattern of bands is observed for 4, 6, 8 and 10 at v ca. 560 and 590 cm owing to
the P–Se(M) and P=Se groups, respectively. These patterns are consistent with the electron
density delocalization of P=E systems [7].
1
The H NMR spectra (CDCl3) of these compounds exhibit the characteristic signals of
the ligand backbone and in the case of compounds 3, 5, 7 and 8, two multiple signals at ca.
δ 1.87 and 3.77 ppm, corresponding to two coordinated THF molecules, are also observed.
1
In general, the H NMR spectra of compounds 3–10 are strikingly similar, as only slight
deviations in the chemical shifts were observed (see the Experimental Section for details).
31
The P NMR spectra for all the compounds show two signals corresponding to the P=E
and P–E(M) units. Indeed, due to the paramagnetic nature of the copper (II) complexes,
31
their P NMR (CDCl3) spectra show two broad signals at δ 31.0 and 31.3 ppm (3) and δ
17.6 and 21.3 ppm (4) ascribed to the P=E and P–E(M) moieties, respectively. A similar set
of signals is observed at ambient temperature for complexes 5 (δ 29.1 and 34.5 ppm), 6 (δ
19.1 and 21.2 ppm), 7 (δ 30.8 and 31.4 ppm), 8 (δ 19.6 and 20.3 ppm), 9 (δ 27.3 and 31.4
ppm), and 10 (δ 17.1 and 19.9 ppm).
3.3 Molecular Description of Compounds 3–10.
9

The molecular structures of all the compounds were determined by single-crystal X-ray
diffraction studies. Suitable single crystals of 3 were grown from a CH2Cl2/THF mixture
and from a concentrated CHCl3 solution for 4, whereas for 5 crystals were grown from a
CHCl3/THF mixture by the slow evaporation of the solvents. On the other hand, in an
attempt to grow X-ray quality crystal of 4 from a saturated chloroform solution with the
adventitious presence of H2O, precipitation of red selenium was observed. Further
structural analysis of the product revealed the partial replacement of the selenium atoms in
the P=Se moiety by an oxygen atom (77 % occupancy for O and 23 % occupancy for Se),
leading to the formation of a mixed oxygen-selenium complex (4a) (vide infra).
1
The compounds crystallize in the triclinic space group P with one half of the
corresponding molecule and 0.33 molecules of THF and 0.17 molecules of CH2Cl2 (3), one
molecule of chloroform (4a), and 0.44 molecules of THF and 0.06 molecules of CHCl3 (5)
in the asymmetric unit. On the other hand, 4 crystallizes in the monoclinic space group
P21/n with one half of the molecule in the asymmetric unit.
The metal atoms in 3 and 5 are coordinated to two units of the ligand through a N atom
from the triazole group and a S atom, and to two molecules of THF resulting in an
octahedral geometry [angles between 88.8(1)–97.4(1)º for 3 and 87.5(1)–92.5(1)º for 5]
(Figures 2 and 3). The Cu–S bond distance in 3 [2.382(1) Å] is comparable with those
observed
in
the
tetracoordinate
complexes
[Cu{Ph2P(C5H4FeC5H4)PPh2}{H2NC(S)NP(S)(OiPr)2}] [2.358(2), 2.385(2) Å][8] and
[Cu(PPh3)2{PhHNC(S)NP(S)(OiPr)2}] [2.373(2) Å)][9], but significantly more elongated
than those observed in the tricoordinate metal complexes [Cu(PPh3){iPr2P(S)NP(S)R2}2)]3
[R = Ph, iPr, OPh; 2.207(2)–2.286(2) Å][10]. The Zn–S bond distance in 5 [2.532(1) Å] is
in agreement with those in the polymeric hexacoordinate zinc complex
10

[Zn{S2P(OCy)2}2{NC5H4CH=CHC5N4N}]n [2.510(1)–2.574(1) Å][11], albeit longer than
those in the molecular complex [Zn{N(P(S)iPr2)2}2] [2.345(1) Å] [12].
Furthermore, the Cu atoms in 4 and 4a exhibit coordination to two ligand units through
the selenium and nitrogen atoms giving a square-planar geometry (Figures 4 and 5). The
Cu–Se bond lengths in 4 [2.445(1) Å] and 4a [2.435(1) Å] are more elongated than that in
[Cu(PPh3){N(P(Se)Ph2)2}] [2.392(1) Å] [13], but comparable with those in the
tetracoordinate complexes [CuI{H2C(P(Se)Ph2)2}]2 [2.455(1), 2.475(1) Å] [14] and
[Cu{(Ph2(CH2)2Se)2(CH2)2}]+[PF6]– [2.444(1), 2.454(1) Å][15]. In general, the Cu–N
bonds in 3 [1.946(2) Å], 4 [1.947(1) Å] and 4a [1.943(1) Å] are shorter than the sum of
their covalent radii [Σrcov(Cu,N) = 2.03 Å][16] and among the shortest reported for the
related copper complexes: [CuCl2(Mebta)2] (Mebta = 1-methylbenzotriazole) [1.981(2),
1.990(2) Å][17], [CuL2Cl2] (L = 3-(2-pyridyl)triazolo-[1,5-a]-pyridine) [1.988(2), 1.996(2)
Å][18] and [Cu(dppb)L’] (dppb = 1,2-bis(diphenylphospino)benzene; L’ = 2,6-dimethyl-N-
[2-(1-benzyl-1H-1,2,3-triazol-4-yl)phenyl]-aniline) [1.997(1) Å][19].
The endocycle E(1)-M(1)-N(1) angles in these compounds are very similar with
89.9(1)º for 3, 90.4(1)º for 4, 91.6(3)º for 4a and 87.5(1)º for 5. The five-membered
CuSePCN heterocycles in 4 and 4a are close to planarity with a mean deviation (Δ) of 0.02
and 0.06 Å, respectively. On the other hand, in 3 and 5, the MSPCN heterocycle adopts an
envelope conformation with the M(1), N(1), C(1) and E(1) atoms slightly deviated from
planarity and the P(1) atom lies in the out-of-plane position at 0.40 Å and 0.39 Å,
respectively.
It is noteworthy, that the hydrolysis reaction of 4 leading to 4a, takes place on the non-
coordinated P=Se bond instead of the Cu–Se(P) bond, which remains unchanged. This
11

behavior contrasts with that observed in the indium complex [InMe2{4,5-(P(Se)Ph2)2tz}]2,
where the In–Se(P) bond is readily hydrolyzed to give a In–O(P) bond while leaving the
non-coordinate P=Se bond unaltered[2a].
X-ray quality crystals of 6 were obtained from a saturated chloroform solution, this
1
compound crystallizes in the triclinic space group P with one molecule of the complex
and seven molecules of chloroform in the asymmetric unit (Figure 6).
Compound 6 displays a bimetallic arrangement where the Zn(1) atom exhibits a
octahedral geometry by means of a trischelate coordination mode similar to that observed
in the aluminum complex [Al{4,5-(P(Se)Ph2)2tz}3][2b]. The Zn(2) atom is coordinated to
three ligand units through the central N atom of the triazole rings and to a fourth ligand
through a nitrogen and selenium atom. The geometry of the coordination sphere of this
metal center can be described as a distorted trigonal bipyramid where the apical position are
occupied by the N(5) and N(10) atoms, while the N(2), N(8) and Se(7) atoms occupy the
equatorial positions. The Zn–Se bond lengths for the hexacoordinate Zn(1) atom [2.615(1)–
2.688(1) Å] are considerably longer than those of the pentacoordinate Zn(2) atom [2.467(1)
i
Å] and in the tetracoordinate complexes [Zn{N(P(Se)R2)2}2] [R = Pr (2.458(8)–2.467(9)
Å; Ph (2.459(3)–2.484(19) Å][20], [Zn{N(P(Se)Ph2)(P(O)Ph2}] [2.441(2), 2.451(2) Å][21].
The endocyclic Se-Zn-N angles for the Zn(1) atom are significantly more acute [av.
82.0(1)º] than that in the Zn(2) atom [90.4(1)º]. On the other hand, the ZnSePCN rings
involving the hexacoordinate Zn(1) atom exhibit non-planar arrangements with an average
Δ corresponding to 0.21 Å, while the heterocycle containing the pentacoordinate Zn(2)
atom exhibits an almost planar arrangement with Δ = 0.07 Å.
The Zn–N bond lengths in 5 [2.026(2) Å] and 6 [2.045(4)–2.172(4) Å (except the
12

Zn(1)–N(1) bond length)] are larger than the sum of their covalent radii [Σrcov(Zn,N) = 1.93
Å] but in agreement with those in the complexes [Zn(OSO2CF3)2L2 ] [L2=4-(2-pyridyl)-
2
1H-1,2,3-triazol-1-ylferrocene] [2.127(1) Å][22], Zn4(PQCA)4(BTA) (bpy)2] (PQCAH =
4
2-phenyl-4-quinolinecarboxylic acid; BTAH = benzotriazole; bpy = 4,4’-bipyridine)
[2.034(2) Å][23], [Zn(ta)(phen)2] (ta = 1,2,3-triazole-4-carboxylate; phen = 1,10-phen)
[2.084(6) Å][24] and [Zn(L3)(H2O)2(ClO4)2] [L3 = N,N’-dimethyl-N,N’-bis(4-(1-
phenyltriazolyl)methyl)ethane-1,2-diamine] [2.126(2), 2.117(2) Å][25]. However, they are
significantly shorter than the Zn(1)–N(1) [2.260(4) Å] bond in 6.
Suitable single crystals of 7 and 8 were grown from methanol/THF mixtures. The
1
compounds are isomorphous and crystallize in the triclinic space group P with one half of
the complex molecule and one half of a THF molecule in the asymmetric unit. The
cadmium center in 7 and 8 exhibits an octahedral geometry by means of coordination to
two ligand moieties and two THF molecules (Figures 7 and 8).
The Cd–E bond lengths [2.658(6) Å (7) and 2.736(1) Å (8)] are significantly longer
than the sum of the covalent radii of cadmium and the respective chalcogen atoms
[Σrcov(Cd,S) = 2.49 Å; Σrcov(Cd,Se) = 2.64 Å][16] and the corresponding bonds in
[Cd{N(P(S)iPr2)2}2] [2.514(1)–2.531(1) Å][26] and [Cd{N(P(Se)Ph2)2}2] [2.617(1)–
2.645(1) Å][27]. However, these bond lengths are shorter than those in the six-coordinated
cadmium
complexes
[Cd2(L4)2(ClO4)2(H2O)2][(ClO4)2]
[2.664(1)–2.698(1)
[L4
Å][28]
=
3-{2-
(methylsulfanyl)phenyl}pyrazole]
and
[Cd(NCSe)2(pyridazine)3]n [2.800(1)–2.815(1) Å][29]. On the other hand, the Cd–N bond
distances in 7 [2.224(2) Å] and 8 [2.249(3) Å] are in agreement with the sum of their
covalent radii [Σrcov(Cd,N) = 2.25 Å][16] and are among the shortest reported for cadmium
complexes
bearing
1,2,3-triazole
ligands
including
[(CdI2)2(1,2-
13

bis(benzotriazole)ethane)2][2.255(15) Å] and [(CdBr2)3(1,2-bis(benzotriazole)ethane)2]n
[2.236(4) Å] [30]. Furthermore, the CdEPCN rings [E = S(7), Se(8)] exhibit an envelope
conformation with the P(1) atoms laying in the out-of-the-plane position by 0.44 and 0.48
Å, respectively.
Suitable single crystals of 9 and 10 were grown from chloroform solutions by slow
1
evaporation of the solvent. Compound 9 crystallizes in the triclinic space group P with
two halves of two crystallographically independent molecules and two CHCl3 molecules in
the asymmetric unit (Figure S1 and Table S1, supporting information) and represents a
pseudomorph of the [Pd{4,5-(P(E)Ph2)2tz}2(pyridine)2] structure reported by Trofimenko
[4a]. On the other hand, 10 crystallizes in the monoclinic space group P21/n with one halve
of the molecule and two molecules of CHCl3 in the asymmetric unit (Figure 9). The
palladium metal center in complexes 9 and 10 coordinates to two ligand units by means of
the nitrogen and chalcogen atoms giving an almost perfect square-planar geometry.
The Pd–Se bond distance [2.432(1) Å] in 10 is significantly shorter than the sum of its
covalent radii [Σrcov(Pd,Se) = 2.59 Å][16] but comparable with that in [Pd(η3-
allyl){N(P(Se)iPr2)2}][Se, 2.480(1) Å][31] and [Pd{N(P(Se)Ph2)2}2][2.437(1) Å][32].
However the Pd–S bond length is slightly shorter than that in the related complex [Pd(η3-
methylallyl){4,5-(P(S)Ph2)2tz}][2.378(2) Å][4a]. The Pd–N bond lengths [1.994(2)–
2.001(2) Å] for 10 are consistent with those in the palladium triazole complexes [PdCl2{1-
benzyl-4-phenyl-1,2,3-triazole}2] [2.011(2) Å][33], [Pd{1-R-4-(2’-pyridinyl)-1H-1,2,3-
triazole}2][BF4] (R = benzyl, 1.995(1) Å; phenyl, 2.006(1) Å) [34], but somewhat shorter
than the sum of their covalent radii [Σrcov(Pd,N) = 2.10 Å] [16]. Finally, the endocyclic Se-
14

Pd-N angle in 10 corresponds to 89.7(1)º while the PdSePCN heterocycle show only slight
deviations from planarity corresponding to 0.03 Å.
4. Conclusions
A series of coordination complexes based on triazole-chalcogen ligands and divalent metal
cations were successfully prepared and their crystal structures determined by single crystal
X-ray crystallography. The square planar complexes 4a, 9 and 10 and the octahedral copper
complex 3 exhibit the shortest relative M–E (E = S, Se) and M–N bonds lengths of the
series of compounds. On the other hand, complexes 5–8 exhibit the largest relative M–E
and M–N bonds compared with the theoretical values for covalent bonding. This can be
rationalized in terms of the high coordination number exhibited by the metal centers in
these complexes by means of coordination to THF molecules. Furthermore, the structural
arrangement exhibited by the selenium zinc complex 6 can be viewed as scorpionate-type
complex considering the Zn(1) atom as part of the backbone of the metallaligand and the
Zn(2) atom as the chelated metal center. The use of trischelate complexes derived from 4,5-
bis(diphenylphosphoranyl)-1,2,3-triazole as metallaligands, namely scorpionate-type
ligands, is the subject of ongoing research.
Acknowledgement
The authors thank the Centro Conjunto de Investigación en Química Sustentable (CCIQS)
UAEM-UNAM for the use of their facilities and the technical support of A. Núñez, N.
Zavala and L. Triana is gratefully acknowledged.
Appendix A. Supplementary Material
15

Figure S1, Table S1 and the CCDC 940176, 970840, 940177–940183 containing the
supplementary crystallographic data for compounds 3, 4, 4a, 5–10, respectively. These data
can be obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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19

Scheme 1. Synthetic route to compounds 3–10.
Figure 1. UV-vis spectra of compounds 3 and 4 in CHCl3.
20

Figure 2. Molecular structure of 3 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms and non-coordinated solvent molecules are omitted for clarity and only the
main parts of the disordered THF molecules are shown.
Figure 3. Molecular structure of 5 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms and non-coordinated solvent molecules are omitted for clarity and only the
main parts of the disordered THF molecules are shown.
21

Figure 4. Molecular structure of 4 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms and non-coordinated solvent molecules are omitted for clarity.
Figure 5. Molecular structure of 4a with thermal ellipsoids at 50 % probability level. All
hydrogen atoms and non-coordinated solvent molecules are omitted for clarity.
22

Figure 6. Molecular structure of 6 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms and non-coordinated solvent molecules are omitted for clarity.
Figure 7. Molecular structure of 7 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms are omitted for clarity and only the main parts of the disordered THF
molecules are shown.
23

Figure 8. Molecular structure of 8 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms and non-coordinated solvent molecules are omitted for clarity and only the
main parts of the disordered THF molecules are shown.
Figure 9. Molecular structure of 10 with thermal ellipsoids at 50 % probability level. All
hydrogen atoms are omitted for clarity.
24

Table 1. Crystallographic data for the structural analyses of compounds 3, 4a, 5 and 6.
3·0.33thf·0.17
5·0.44thf·0.06
4·4CHCl3
4a·2CHCl3
CH2Cl2
CHCl3
C
62.96H61.93Cl0.69CuN6 C56H44Cl12CuN6P4
C54H42Cl6CuN6
O1.77P4Se2.23
C63.66H63.22Cl0.34N6
O2.89P4S4Zn
Chemical formula
O2.65P4S4
1285.27
Triclinic
Se4
Formula weight
Crystal system
Space group
Temp, K
λ, Å
1729.63
Monoclinic
P 21/n
1379.27
Triclinic
1287.94
Triclinic
P
P
P
1
1
1
100(2)
100(2)
100(2)
100(2)
0.71073
8.9079(3)
13.2829(4)
14.7719(5)
69.398(1)
72.895(1)
73.892(1)
1533.86(9)
0.16 x 0.12 x 0.12
1
0.71073
8.9906(7)
23.0923(17)
16.3121(12)
90
0.71073
0.71073
8.8877(5)
13.3275(8)
14.992(1)
68.500(1)
73.105(1)
73.577(1)
1549.65(16)
0.16 x 0.12 x 0.12
1
a, Å
8.9959(5)
10.3523(6)
17.1671(13)
101.497(1)
92.730(1)
114.528(1)
1409.96(16)
0.27 x 0.16 x 0.04
1
b, Å
c, Å
α, deg
β, deg
97.9734(15)
90
γ, deg
V, Å3
Crystal size, mm3
3353.9(4)
0.39 x 0.13 x 0.06
2
Z
ρcald., g·cm−3
μ, mm−1
F(000)
1.391
1.713
1.624
1.380
0.677
3.112
2.269
0.699
668
1702
689
607
θ range for data
collection, deg
2.44 to 25.11
17670
1.54 to 25.39
30532
2.23 to 25.04
5003
1.87 to 25.07
18344
No. of reflns
No. of indep. reflns
(Rint)
5451 (0.0417)
6140 (0.0331)
5003 (0.045)
5498 (0.0382)
No. of data /
restraints /
parameters
5451 / 553 / 497
6140 / 463 / 488
5003 / 1027 / 490
5498 / 429 / 477
GoF on F2
1.000
1.045
1.285
1.021
R1,a wR2b (I > 2σ(I))
R1,a wR2b (all data)
0.0364, 0.0847
0.0442, 0.0890
0.0202, 0.0482
0.0241, 0.0495
0.0884, 0.2260
0.0967, 0.2295
0.0341, 0.0783
0.0414, 0.0819
Largest diff. peak /
hole, e·Å−3
0.632 / –0.321
0.454 /–0.235
0.877 / –1.325
0.565 / –0.339
aR1 = Σ||Fo| – | Fc||/Σ|Fo|. bwR2 = [Σw (Fo
2
2 2 1/2
Fc2)2/ (Fo ) ]
.
25

Table 2. Crystallographic data for the structural analyses of compounds 7, 8 and 10.
6·7CHCl3
7·thf
8·thf
10·4CHCl3
C64H64CdN6O3P4
Se4
C56H44Cl12N6P4Pd
C
111H87Cl21N12P8
C64H64CdN6O3P4S4
Chemical formula
Se8Zn2
Se
4
3343.56
Triclinic
1772.49
Formula weight
Crystal system
Space group
Temp, K
λ, Å
1329.73
1517.33
Monoclinic
P 1 21/n 1
Triclinic
Triclinic
P
1
P
P
1
1
100(2)
100(2)
100(2)
100(2)
0.71073
0.71073
0.71073
0.71073
9.0139(2)
23.0849(6)
16.3224(4)
90
17.2456(10)
17.7608(10)
24.3644(14)
77.658(1)
86.903(1)
63.753(1)
6531.6(6)
0.24 x 0.15 x 0.12
2
a, Å
8.8625(3)
13.3229(5)
15.1587(5)
68.1930(10)
73.9650(10)
74.3320(10)
1568.74(9)
0.04 x 0.11 x 0.15
1
8.8946(5)
13.3071(8)
15.1415(9)
69.0080(10)
74.8050(10)
74.8050(10)
1590.62
b, Å
c, Å
α, deg
98.2470(10)
90
β, deg
γ, deg
V, Å3
Crystal size, mm3
3361.32(14)
0.24 x 0.15 x 0.12
2
0.05 x 0.06 x 0.14
1
Z
ρcald., g·cm−3
μ, mm−1
F(000)
1.700
1.751
1.408
1.584
3.175
3.056
0.634
2.782
3292
1736
686
758
θ range for data
collection, deg
1.51 to 25.16
97334
1.84 to 25.05
37309
1.66 to 26.44
39780
1.51 to 25.03
29853
No. of reflns
No. of indep. reflns
(Rint)
23258 (0.0651)
5549 (0.0387)
6539 (0.0314)
5942 (0.0266)
No. of data /
restraints /
parameters
23258 / 1622 / 1811
5549 / 256 / 440
6539 / 1069 / 589
5942 / 108 / 413
GoF on F2
R1,a wR2b (I > 2σ(I))
R1,a wR2b (all data)
1.016
1.064
1.061
1.028
0.0408, 0.0968
0.0665, 0.1080
0.0268, 0.0593
0.0319, 0.0620
0.0278, 0.0618
0.0322, 0.0632
0.0193, 0.0438
0.0223, 0.0448
Largest diff. peak /
hole, e·Å−3
aR1 = Σ||Fo| – | Fc||/Σ|Fo|. bwR2 = [Σw (Fo
1.185 / −1.301
0.441/ –0.439
1.092 / −0.847
0.419/ –0.321
2
2 2 1/2
Fc2)2/ (Fo ) ] .
26

Table 3. Selected bond lengths (Å) and angles (º) for compounds 3, 4a, and 5.
3[a]
4[b]
4a[c]
5[d]
M(1)–E(1)
2.382(1)
1.946(2)
2.546(4)
1.994(1)
1.950(1)
180.0
2.445(1)
1.947(1)
–
2.435(1)
1.943(1)
–
2.532(1)
2.026(2)
2.282(6)
1.984(1)
1.951(1)
180.0
M(1)–N(1)
M(1)–O(1)
P(1)–E(1)
2.168(1)
2.445(1)
180.0
2.167(3)
1.483(1)
180.0
P(2)–X
E(1)-M(1)-E(1A)
N(1)-M(1)-N(1A)
E(1)-M(1)-N(1)
180.0
180.0
180.0
180.0
89.9(1)
90.4(1)
91.6(3)
87.5(1)
[a]M = Cu; E = S; X = S(2). [b]M = Cu; E = Se; X = Se(2). [c]M = Cu; E = Se; X =
O(2). [d]M = Zn; E = S; X = S(2).
Table 4. Selected bond lengths (Å) and angles (º) for compound 6.
Zn(1)–Se(1)
Zn(1)–Se(3)
Zn(1)–Se(5)
Zn(2)–Se(7)
Zn(1)–N(1)
Zn(1)–N(4)
Zn(1)–N(7)
Zn(2)–N(2)
Zn(2)–N(5)
Zn(2)–N(8)
Zn(2)–N(10)
P(1)–Se(1)
P(3)–Se(3)
P(5)–Se(5)
P(7)–Se(7)
2.615(1)
2.688(1)
2.655(1)
2.467(1)
2.260(4)
2.137(4)
2.168(4)
2.045(4)
2.172(4)
2.049(4)
2.095(4)
2.147(1)
2.131(1)
2.135(1)
2.151(1)
Se(1)-Zn(1)-Se(3)
Se(1)-Zn(1)-Se(5)
Se(3)-Zn(1)-Se(5)
N(1)-Zn(1)-Se(1)
N(4)-Zn(1)-Se(3)
N(7)-Zn(1)-Se(5)
N(1)-Zn(1)-Se(5)
N(4)-Zn(1)-Se(3)
N(10)-Zn(2)-Se(7)
N(10)-Zn(2)-N(5)
N(2)-Zn(2)-Se(7)
N(2)-Zn(2)-N(8)
N(5)-Zn(2)-N(8)
N(2)-Zn(2)-N(10)
N(8)-Zn(2)-N(10)
91.0(1)
92.7(1)
83.8(1)
80.8(1)
82.8(1)
82.3(1)
170.6(1)
162.3(1)
90.4(1)
177.7(1)
125.4(1)
103.2(1)
88.8(1)
95.4(1)
90.4(1)
27

Table 5. Selected bond lengths (Å) and angles (º) for compounds 7, 8 and 10.
7[a]
8[b]
10[c]
2.432(1)
2.001(2)
–
M(1)–E(1)
2.658(6)
2.224(2)
2.413(6)
1.990(1)
1.951(1)
180.0(1)
180.0(1)
83.3(1)
2.736(1)
2.249(3)
2.447(3)
2.148(1)
2.103(1)
180.0(1)
180.0(1)
84.3(1)
M(1)–N(1)
M(1)–O(1)
P(1)–E(1)
2.182(1)
2.107(1)
180.0(1)
180.0(1)
89.7(1)
P(2)–E(2)
E(1)-M(1)-E(1A)
N(1)-M(1)-N(1A)
E(1)-M(1)-N(1)
[a]M = Cd; E = S. [b]M = Cd; E = Se.[c]M = Pd; E = S.
28

Graphical abstract
29