Ferrocenylated Chalcogen (Se and Te)-containing N-heterocyclic carbenes: Selenones, silver and palladium complexes

Article abstract of DOI:10.1016/j.ica.2020.119531

New Ferrocenylated Chalcogen (Se and Te)-Containing imidazolium salts have been synthesized. These imidazolium salts have been used as precursors for the synthesis of ferrocenyl-NHC selenones, silver NHC and ionic palladium (II) complexes where the imidaz

Full text of DOI:10.1016/j.ica.2020.119531

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Research paper
Ferrocenylated Chalcogen (Se and Te)-Containing N-Heterocyclic Carbenes:
Selenones, Silver and Palladium Complexes
Rodary Gonzalez, Ramón Azpiroz, Pankaj Sharma, Claudia P. Villamizar C,
Bertin Anzaldo, Francisco J. Pérez-Flores, Ruben Alfredo Toscano
PII:
S0020-1693(19)32002-X
https://doi.org/10.1016/j.ica.2020.119531
ICA 119531
DOI:
Reference:
Inorganica Chimica Acta
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Revised Date:
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19 December 2019
12 February 2020
12 February 2020
Please cite this article as: R. Gonzalez, R. Azpiroz, P. Sharma, C.P. Villamizar C, B. Anzaldo, F.J. Pérez-Flores, R.
Alfredo Toscano, Ferrocenylated Chalcogen (Se and Te)-Containing N-Heterocyclic Carbenes: Selenones, Silver
and Palladium Complexes, Inorganica Chimica Acta (2020), doi: https://doi.org/10.1016/j.ica.2020.119531
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Ferrocenylated Chalcogen (Se and Te)-Containing N-Heterocyclic Carbenes: Selenones, Silver and
Palladium Complexes
Rodary Gonzalez,a Ramón Azpiroz,a Pankaj Sharma,a* Claudia P. Villamizar C,a Bertin Anzaldo,a Francisco J. Pérez-Flores,a
Ruben Alfredo Toscano a
[a] Instituto de Química Universidad Autónoma de México UNAM, Cd., Universitaria, PO Box 04510, Ciudad de México, México. E-mail:
pankajsh@servidor.unam.mx
Keywords: Ferrocenyl Chalcogen • N-Heterocyclic Carbene• Selenones
Abstract: New Ferrocenylated Chalcogen (Se and Te)-Containing imidazolium salts have been synthesized. These imidazolium
salts have been used as precursors for the synthesis of ferrocenyl-NHC selenones, silver NHC and ionic palladium (II)
complexes where the imidazolium ligand act as the cation. For the synthesis of Pd NHC(Se, CNHC) complex from appropriate
imidazolium salts, the route of the silver carbene transfer reaction has been adopted and the ligand shows bidentate
coordination through (Se, CNHC) atoms. All the compounds have been fully characterized by multinuclear NMR, mass
spectrometry and X-ray diffraction. Molecular structures of ferrocenyl chalcogenide imidazolium salts present intra and inter
cation/anion interactions. Interestingly, 77Se NMR studies of ionic palladium complexes with ferrocenyl chalcogenide
imidazolium cation do not present Se coordination to Palladium in solution. The bond distance between CNHC and selenium
atom in both the selenones is similar to other reported imidazolium selenones where this bond has a double bond character.
Introduction
N-Heterocyclic carbenes (NHCs) and their main group element adducts have been the subject of extensive investigations for
the last three decades in coordination chemistry and homogenous catalysis.1,2 The great interest on NHCs as ligands in
comparison to classical phosphines is due to their easy accessibility and modulation of their substituents which modify their
electronic and steric properties.3 Recently, the functionalization of imidazole ring with donor atoms such as N,4 P5 O,6 and
relatively less explored with donor atoms S7 or Se8, provide new interesting bidentate4a, 4c, 5b, 5c, 5d, 5f, 6, 7 and tridentate4b, 4d, 5a,
5e, 7
ligands. The presence of donor groups on the pendant arm with free conformational arrangement around the metal
stimulates hemilabile or labile interactions. Hemilability is an important concept in catalysis to stabilize intermediates and
promote catalytic transformations by generating coordination sites that lead to interaction with substrates.9 In the family of
NHCs, the functionalization of the imidazole moiety with ferrocenyl substituents shows unique properties due to sterically
cylindrical shape and its donor capacity to stabilize and increase the electronic properties of the NHCs.10 Precedent for the
introduction of additional heteroatom donors (sulfonate, carbonate, pyranyl and pyridyl groups) on the side-arm of
ferrocenyl substituted-NHCs structures are very scarce.11 To our knowledge, there is no report available on ferrocenyl
substituted-NHC ligands based on organo- selenium and tellurium, so it appears interesting to explore in this area. Recently,
the use of heavier organochalcogens as ligands in organometallic chemistry has received special attention in comparison to
organophosphorus ligands because of their low toxicity, air and moisture sensitivity, higher thermal stability and their
capacity to stimulate intra- and intermolecular interactions.12 In particular organoselenium ligands present comparable
electron-donating ability as organophosphorus ligands and led to the synthesis of many transition metal complexes, which
can serve as catalysts for a variety of C-C cross-coupling reactions.13
The selection of a carbene for a specific purpose requires detailed knowledge of its stereoelectronic properties. Recently,
reports have appeared on Se-N-Heterocyclic Carbene (Se-NHC) adducts (selenoureas or selones) to observe the donor
abilities of NHC ligands.14 The assessment of the ligand properties of NHCs, Tolman electronic parameter (TEP) has become
the most frequently used parameter which reflects the overall ligand properties.15 However, this parameter does not give
much idea of the σ-donating and π-accepting nature of a particular NHC. NMR methods also have been used that provide an
insight into the π-acceptor strength of NHCs. The π-acceptor strengths of the NHCs within the NHC–Se adducts or NHC–
phosphinidene adducts were determined by measuring the 31P NMR chemical shifts and the 77Se NMR chemical shifts.16 In
principle, N-heterocyclic carbenes nucleophilic character is transferred onto the exocyclic selenium atom which affords Se-
donor ligands, that can act themselves as ligands toward main group elements and transition metal complex fragments.
These N-heterocyclic carbene selenone derivatives have also received increasing attention because of their structural
relevance to methimazole and selenoneine.
Apart from this, a vast variety of NHC-transition.metal complexes bearing different substituents on the side-arm of imidazole
fragment have been prepared using different synthetic methods including a) the isolation of free NHCs prior to the reaction
with transition metal,17 or metalloid,18 b) in situ generation via reaction of imidazolium salt with an external base,19 c) the use
of imidazolium salts with suitable basic transition metal20 and d) transmetallation with other organometallic species.21 The

use of well explored [(NHC)Ag)] complexes as transmetalating agents have become the most popular methods for the
preparation of transition metal NHCs complexes.
In continuation to our search for new organoselenium and tellurium ligands,22 herein we describe the synthesis of some new
ferrocenyl-NHCs salts (2a-c) containing organochalcogen donor (Se and Te) on the side-arm of NHC moiety, their selones
derivatives and complexation with Ag(I) and Pd(II) metals.
Results and Discussion
Synthesis of N-PhXCH2CH2ImH and N-FcXCH2CH2ImH (1a-d). Synthesis of N-PhXCH2CH2ImH {X= Se (1a) and Te (1b)} and N-
FcXCH2CH2ImH {Fc = ferrocene, X = Se, (1c) and Te (1d)} was carried out starting from 1-chloroethylimidazole and sodium
organoselenide (NaSePh for 1a and NaSeFc for 1c), or sodium organoteluride (NaTePh for 1b and NaTeFc for 1d) in ethanol
which was obtained in situ and under nitrogen atmosphere by the reduction and consecutive cleave of PhX-XPh or FcX-XFc (X
= Se, Te), respectively. The desired compounds were obtained as a yellow oil. N-PhSeCH2CH2ImH (1a) has already been
reported earlier in the literature,8b however N-PhTeCH2CH2Im (1b), N-FcSeCH2CH2ImH (1c) and (1d) are unknown.
AgI
iv)
Se
Pd
N
R
PdCl2(CH3CN)2
X
R´
N
N
Fe
Cl
Cl
N
N
N
(4a) X = Se, R´ = Ph R = CH2Fc
(4b) X = Te, R´ = Ph R = CH2Fc
(4c) X = Se, R´ = Fc R = Me
Cl
Me
(6c)
Ag2O
NaBH4, R´2X2
ii)
+
iii)
I
[FcCH2N(Me)3]+I-
R´ or MeI
R
R
-2
X
X
X
R´
PdCl2(CH3CN)2
2
R´
N
N
N
N
N
N
PdCl2I2
(1a) X = Se, R´ = Ph
(1b) X = Te, R´ = Ph
(1c) X = Se, R´ = Fc
(1d) X = Te, R´ = Fc
(2a) X = Se R´ = Ph R = CH2Fc
(2b) X = Te R´ = Ph R = CH2Fc
(2c) X = Se R´ = Fc R = Me
(5a) X = Se, R´ = Ph R = CH2Fc
(5b) X = Te, R´ = Ph R = CH2Fc
i)
K2CO3, Se
Fc = ferrocenyl
Se
R
N
X
R´
N
(3a) X = Se, R´ = Ph R = CH2Fc
*(3b) X = Se, R´ = Ph R = Me
(3c) X = Se, R´ = Fc R = Me
Scheme 1. Synthetic methodology for the preparation of new ferrocenyl imidazolium chalcogenide salts (2a-c) from starting
precursors (1a-d). Compounds (2a-c) resulted excellent reactants for the preparation of: i) new selenones (3a-c) (*Compound
3b was synthesized from an imidazolium salt as reported in the literature 8b) ii) new silver NHC complexes (4a-c) and iii) new
ionic palladium imidazolium complexes (5a,b). iv) new palladium NHC complex (6c).
The 1H NMR spectra of 1a, b in CDCl3 and 1c,d in acetone-d6 at room temperature show the proton NCHN at ~ δ 7.4 ppm as a
singlet and =CHN protons at ~ δ 7.0 and δ 6.8 ppm as broad signals. The N-CH2 and X-CH2 (X = Se, Te) protons appear at ~ δ 4
ppm and at ~ δ 3 ppm respectively, as triplets (JH-H  7 Hz). Additionally, for compound 1a 77Se NMR shows a broad singlet at δ
284.0 ppm which is in accordance with selenium atom connected to alkyl fragment.23 For compound 1c, the resonance
corresponding to the selenium atom appears a higher field (δ 180.0 ppm), which is due to the higher electron donating ability
of the ferrocenyl group. 13C NMR spectra of these compounds are in accordance with the proposed structure.
Synthesis of ferrocenyl imidazolium chalcogenide salts. The imidazolium salts (2a-c) were prepared by the reaction of 1-
substituted imidazoles (1a-c) with N-trimethylaminomethyl ferrocenium iodide or with methyliodide and were isolated as
yellow solids in good yields. In general, the 1H NMR spectra of 2a-c at room temperature showed characteristic resonances of
NCHN proton at ~ δ 9.5 ppm, suggesting the high acidity of this proton.25 All compounds showed three signals corresponding
to the ferrocenyl moiety at ~ δ 4.5-4.0 ppm, two doublets of doublets for 4H protons of linked cyclopentadienyl fragment and
one singlet for symmetrical 5H protons of ferrocene. Also, a signal at ~ δ 5.2 ppm corresponds to methylene protons of 2a,b
and a singlet at δ 4.07 ppm for methyl group of 2c. Interestingly, a slightly downfield shift ~ Δδ = 0.3 ppm was observed for N-
CH2 and X-CH2 group (X = Se, Te) protons for the imidazolium salts (2) in comparison to their precursors (1). This observation
suggests the presence of C-H···I interactions, as reported earlier in the literature.26 A similar downfield shift was observed in
13C spectra. This downfiled shift is also due to the formation of imidazolium salt with a deprotected N-CH2 carbon.

Single crystals of [(N-PhTeCH2CH2)(N´-CH2Fc)ImH]+ I- (2b) were obtained by slow diffusion of hexane into a concentrated
solution in acetonitrile and the solid-state structure was determined by single crystal X-ray diffraction studies. Figure 1
reports the ORTEP view along with selected bond lengths and angles of the imidazolium compound. To the best of our
knowledge, this is the first structurally characterized imidazolium compound bearing an aliphatic chain containing
telluroether fragment as a substituent. The imidazolium cation 2b presents N(1)-C(2)-N(3) angle of 109.5(4)°. In addition, the
skeleton involving the Te1 displays C(19)-Te(1)-C(18) angle of 96.32(19)°. The other bond lengths and bond angles observed
are of similar magnitude as reported earlier for other imidazolium salts and organochalcogen compounds.8b, 27
Figure 1. Molecular structure of 2b depicted with 30% thermal ellipsoids. Hydrogens atoms have been omitted for clarity. Selected Bonds
lengths (Å): Te(1)-C(19), 2.121(5); Te(1)-C(18), 2.138(5); N(1)-C(2), 1.314(7); N(1)-C(16), 1.484(7); N(3)-C(2), 1.330(6); N(3)-C(17), 1.478(7);
N(1)-C(5), 1.367(7); N(3)-C(4), 1.370(7); C(6)-C(16), 1.487(7); C(17)-C(18), 1.493(7); Bond angles(°): C(19)-Te(1)-C(18), 96.3(2); C(2)-N(1)-
C(16), 124.8(4); C(2)-N(3)-C(17), 125.8(4); N(1)-C(16)-C(6), 112.7(4); Te(1)-C(18)-C(17), 113.2(3); N(3)-C(17)-C(18), 111.6(4); N(1)-C(2)-N(3),
109.4(4); Bond torsion (°): Te(1)-C(18)-C(17)-N(3), 178.6(3); C(19)-Te(1)-C(18)-C(17), -64.2(4); C(6)-C(16)-N(1)-C(2), 90.7(6).
26
When considering the 3D packing of 2b, intra and inter cation/anion interactions were detected.6e, A shorter intra
cation/anion interaction involving imidazolium ring and iodide atom {H(1)···I(1), 2.867 Å} were observed and, the positive
charge is localized around the imidazole (Figure 2A) ring. In accordance with NMR observations, intra cation/anion
interactions between µ-CH2 and aromatic ring with iodide atom were detected {H(18)···I(1), 3.141 Å; H(24)···I(1), 3.132 Å}. It
is to be noted that the presence of inter cation/anion CH···I interactions generate chains of molecules growing parallel to
{H(7)···I(1), 3.028 Å} axis (Figure 2B). In addition, these chains are joined together by CH···C interactions rendering chains
affording the 3D packing {H(8)···C(20), 2.859 Å; H(17)···C(10), 2.874 Å} (Figure 2C). These interactions are driven by the
packing and electrostatic effect of acidic protons that stabilize the structure.

Figure 2. (A) Representation of intra cation/anion CH···I interactions (green) of 2b. (B) CH···I inter cation/anion interactions
(blue) between adjacent molecules forming chains along an {H(7)···I(1), 3.028 Å}. (C) View of CH-C contacts (red) detected in
3D packing structure {H(8)···C(20), 2.859 Å; H(17)···C(10), 2.874 Å}.
Synthesis of ferrocenyl NHC selenones. New selenones (3a-c) were obtained as yellow solids, in good isolated yields by the
reaction of imidazolium salts (2a,c) with elemental selenium and potassium carbonate in anhydrous acetonitrile at room
temperature. The disappearance of acidic NCHN proton in 1H NMR and the appearance of chemical shift at ~δ 156 ppm in 13
C
NMR for compounds 3a,c confirms the formation carbene bonded to Selenium. Moreover, the presence of two chemical
shifts in 77Se NMR spectra confirmed the presence of two different selenium atoms (see supporting information).
The structures of (N-PhSeCH2CH2)(N´-CH2Fc)ImSe (3a) and (N-FcSeCH2CH2)(N´-CH3)ImSe (3c) were confirmed by X-ray
diffraction studies and crystals were obtained by slow evaporation of acetonitrile solution of the title compounds (Figures 3
and 4). The asymmetric unit of selenone 3c contains two crystallographically independent molecules showing similar bond
angles and lengths, thus only one of the two molecules is discussed herein (see Supporting Information). Both selenones
(3a,c) present similar angles between the carbene atom and the nitrogen atoms of imidazole {N(1)-C(12)-N(2), 105.7(2)°;
N(4)-C(31)-N(3), 106.1(2)°} and between selenium atom and adjacent carbon atoms of pendant arm fragment {C(17)-Se(2)-
C(16), 101.58(9)°; C(19)-Se(3)-C(29), 97.2(3)}. The distance between carbene and selenium atom in both the selenones {Se(1)-
C(12), 1.840(2); Se(4)-C(31), 1.847(7) Å} are similar to other reported imidazolium selenones14 This bond distance is similar to
the distances observed in alkylidenes with a more doble bond character and not with single bond character as observed for
organometallic NHC carbenes.28

Figure 3. Molecular structure of 3a depicted with 30% thermal ellipsoids. Hydrogens atoms have been omitted for clarity.
Bonds lengths (Å): Se(2)-C(17), 1.917(2); Se(2)-C(16), 1.955(2); Se(1)-C(12), 1.840(2); N(2)-C(15), 1.460(3); N(1)-C(11),
1.473(3); C(1)-C(11) 1.494(3); C(12)-N(1) 1.356(3); C(12)-N(2), 1.362(3); N(1)-C(13), 1.383(3); N(2)-C(14), 1.381(3); C(15)-
C(16), 1.512(3); Bond angles (°): C(17)-Se(2)-C(16), 101.58(9); Se(1)-C(12)-N(2), 126.8(2); Se(1)-C(12)-N(1), 127.5(2); C(12)-
N(1)-C(11), 124.2(2); C(12)-N(2)-C(15), 126.0(2); N(2)-C(15)-C(16); 111.0(2); C(15)-C(16)-Se(2), 111.8(1); N(1)-C(11) C(1),
111.5(2); N(1)-C(12)-N(2), 105.7(2); Bond torsion(°): Se(2)-C(16)-C(15)-N(2) -169.7(1); C(1)-C(11)-N(1)-C(12), 170.0(2); C(17)-
Se(2)-C(16)-C(15), -91.6(2); Se(1)-C(12)-N(1)-C(11), -2.4(3); Se(1)-C(12)-N(2)-C(15), -2.8(3).
Figure 4. Molecular structure of 3c depicted with 30% thermal ellipsoids. Hydrogens atoms have been omitted for clarity.
Bond lengths (Å): Se(3)-C(19), 1.900(1); Se(3)-C(29), 1.952(9); Se(4)-C(31), 1.847(7); N(3)-C(30), 1.447(9); N(4)-C(34), 1.459(4);
C(31)-N(4), 1.348(9); C(31)-N(3), 1.348(8); N(4)-C(32), 1.372(9); N(3)-C(33), 1.382(9); C(30-C(29), 1.51(1); Bond angles(°):
C(19)-Se(3)-C(29), 97.2(3); Se(4)-C(31)-N(3), 127.0(5); Se(4)-C(31)-N(4), 126.8(5); C(31)-N(4)-C(34), 125.3(6); C(15)-N(1)-C(14),
125.0(6); N(3)-C(30)-C(29), 109.9(6); C(30)-C(29)-Se(3), 112.6(5); N(4)-C(31)-N(3), 106.1(2) Bond torsion (°): Se(3)-C(29)-C(30)-
N(3), 173.3(4); C(19)-Se(3)-C(29)-C(30), 64.7(5); Se(2)-C(15)-N(2)-C(18), 2(1); Se(2)-C(15)-N(1)-C(14), -9(1).
Synthesis of Silver NHC complexes. The yellow monocarbene silver iodides (4a-c) complexes were synthesized by the
reaction of imidazolium iodides 2a-c with silver (I) oxide in dry CH2Cl2. These complexes are stable in air and moisture, but
their dichloromethane solutions are slightly sensitive. Molecular ion peak (M-I; m/z = 607) observed in the mass spectra of 4b
1
confirms the presence of the ferrocenyl-NHC silver complex. In H NMR spectra, disappearance of NCHN proton signal for
silver-NHC complexes(4) in comparison to their imidazolium salts (2) precursors confirm the formation silver-NHC complexes
Additionally, a slight upfield shift was observed for olefinic =CHN protons at ~ δ 6.8 and 6.7 ppm in comparison to their
precursor imidazolium salts (~ δ 7.4 and 7.2 ppm). In 13C NMR spectra for these complexes, a characteristic signal at ~ δ 182
ppm was observed for the silver carbene carbon. Finally, no significant difference was observed in 77Se NMR spectra between
4a and 4c (δ 274.1 and 173.4 ppm respectively) and imidazolium salt 2a and 2c (δ 277.4 and 175.4 ppm respectively) which
confirm the non-coordination of selenium to the central silver atom.

Figure 5. 1H NMR spectra of 2a,b and 4a,b.
Synthesis of Palladium NHC complexes. On adding the imidazolium salts (2a,b) to a solution of palladium (II) acetate, the
desired palladium carbene complex could not be obtained which may be due to the strong steric hindrance of ferrocenyl
moiety of the imidazolium with iodo ligands. However, reaction of imidazolium salts (2a,b) with PdCl2(CH3CN)2 in 2:1 ratio,
allowed the preparation of the corresponding air stable ionic palladium complexes [(N-PhXCH2CH2)(N´-CH2Fc)ImH]+ [(PdCl2I2)]-
2
1
{X = Se (5a) , Te (5b)}29 in good yields. These ionic complexes were isolated as red solids. The H NMR spectrum of 5a-b
1/2
showed NCHN proton resonance at ~ δ 10.2 ppm, which is slightly downfield (Δδ = 0.3) in comparison to NCHN proton of 2a-
b (Figure 6). The opposite chemical shift trend was observed in the 13C NMR spectrum where NCHN carbon of 5a-b, appears
at δ 134.3 and 138.3 ppm, respectively. These chemical shift differences may be due to the type of counter anion and the
interactions involved between PdCl2I22- and imidazolium ring. Interestingly, there is no difference in the 77Se NMR spectra of
2a and 5a, showing the non-coordination of the selenium atom to palladium. On the other hand in the mass spectra of 5a,
the detected ion peak at m/z = 305 and at m/z = 451 confirm the presence of palladate anion (MS (FAB-) m/z: 305 [PdCl2I2]-
and imidazolium cation (HRMS (FAB) found m/z 451.0376) and is in agreement with the ionic structure.
For the synthesis of Pd complex 6 from appropriate imidazolium salts (4c), the route of the silver carbene transfer reaction
has been adopted and thereby, the reaction of (N-FcSeCH2CH2)(N´-Me)ImAgI 4c with PdCl2(CH3CN)2 in anhydrous acetonitrile
1
resulted in the formation of FcSeEtImMePdCl2 (6) as a red solid. H NMR spectra of palladium complex showed four
diastereotopic protons at δ 4.56, 3.52, and 2.32 ppm as a multiplet chemical shift. In the 77Se NMR spectra, selenium atom
appears at δ 162.3 ppm as a broad signal, ~10-20 ppm at the higher field in comparison to the selenium chemical shift of
organoselenium compounds 2-4. These all evidence suggests the ligand coordinate to palladium with selenium and carbene
1
and thus forming a six-membered chelate ring. Moreover in H NMR and 13C NMR spectra, the cyclopentadienyl moiety of
ferrocene linked to selenium display four signals at δ 4.28, 4.28, 4.09, and 3.73 ppm as multiplets and δ 70.7, 70.2, 69.8, and
69.3 ppm respectively. The asymmetry of the cyclopentadienyl ring suggests the presence of intramolecular Pd-Se
coordinative bond.30
The molecular structure of 6 was determined by X-ray crystallography (Figure 7). The palladium atom presents a slightly
distorted square planar geometry {Se(1)-Pd(1)-Cl(2), 86.06(4); Se(1)-Pd(1)-C(15), 89.7(2); Cl(1)-Pd(1)-C(15), 92.0(2); Cl(2)-
Pd(1)-Cl(1), 93.07(6)} with four coordination sites occupied by carbene and selenium atom precedent of bidentate ligand and
two chlorine atoms in cis positions, respectively. Only one intramolecular interaction was detected between the H(5) proton
of the ferrocene with the CNCN carbon of the imidazole, {H(5) ··· C(15), 2,814 Ǻ}, which could also be the reason for the loss of
1
the symmetry of the Cp ring observed in H and 13C NMR spectra (Figure 8). Palladium-Selenium bond lengths of complex 6
{Se(1)-Pd(1), 2.3808(7) Å} and the distance between palladium atom and carbene {C(15)-Pd(1 ), 1.970(6) Å} are consistent
with earlier reported values.23
Conclusions
New imidazolium species containing the ferrocenyl and the organochalcogenide fragment as pendant arm (2) have been
revealed as the efficient precursors for the synthesis of new ferrocenyl NHC selenones (3), silver NHC (4) and ionic palladium
complexes containing imidazolium species as cations (5). Moreover, silver NHC complexes (4) have been efficient
transmetallating agents to afford new palladium NHC complex (6). The solid-state structure of ferrocenyl chalcogenide
imidazolium salts presents intramolecular interactions between acidic NCHN and µ-CH2 protons with iodide atom which are

in accordance with downfield shift observed in NMR data (~ Δδ = 0.3 ppm). Additionally, cation-anion interactions generate
polymeric chains of alternating cations and anions, are described. 77Se NMR spectra of ionic palladium complexes species
showed a unique chemical shift similar to imidazolium salts (2 vs 5). However, in palladium NHC complex 6 selenium atom
appeared ~ 10-20 ppm a higher field. This is clear evidence of coordination of selenium atom to palladium center in
comparison to non-coordination of selenium pendant arm fragment into ionic palladium species. The stereochemistry of 6,
was finally confirmed by X-ray structural analysis which is in agreement with NMR studies. These new silver and palladium
complexes bearing the ferrocenyl NHC and chalcogenide pendent arm fragments are potentially catalyst in many organic
transformations so they will be studied in future studies.
Figure 6. 1H, 13C and 77Se NMR spectra for compounds 2a and 5a in CDCl3.
Figure 7. Molecular structure of 6c with 30% thermal ellipsoids. Hydrogens atoms have been omitted for clarity. Bond lengths
(Å): C(15)-Pd(1 ), 1.970(6); Pd(1)-Cl(2), 2.374(2); Se(1)-Pd(1), 2.3808(7); Pd(1)-Cl(1), 2.338(2); C(1)-Se(1), 1.901(8); Se(1)-C(11),
1.961(5); C(15)-N(1), 1.344(7); C(15)-N(2), 1.348(9); N(1)-C(12), 1.462(8); C(13)-C(14), 1.333(9); C(12)-C(11), 1.511(8); C(16)-
N(2), 1.465(7); Bond angles(°): C(1)-Se(1)-C(11), 96.6(3); N(1)-C(15)-Pd(1), 125.5(4); N(2)-C(15)-Pd(1), 128.8(4); N(1)-C(15)-
N(2), 105.6(5); C(15)-N(1)-C(12), 123.9(5); C(15)-N(2)-C(16), 126.2(5); Se(1)-Pd(1)-C(15), 89.7(2); Cl(2)-Pd(1)-Cl(1), 93.07(6);
Se(1)-Pd(1)-Cl(2), 86.06(4); Cl(1)-Pd(1)-C(15), 92.0(2).

Figure 8. Representation of intramolecular interaction between H(5)···CNCN C (15) of 6c.
Experimental
General Information. All reactions and manipulations were carried out by using Schlenk-type techniques.
Dimethylaminomethyl ferrocene, Ph2X2 (X = Se, Te) and silver (I) oxide were purchased from commercial sources and were
used as received. (Ferrocenylmethyl)trimethylammonium iodide and PdCl2(CH3CN)2 were synthesized according to the
1
literature.31 Organic solvents were dried by standard procedures and distilled under nitrogen prior to use. H and 13C{1H}
spectra were recorded either on a Bruker 300 MHz instrument. Chemical shifts (expressed in parts per million) are
referenced to residual solvent peaks (1H, 13C{1H}). All chemical shifts (δ) are reported in ppm and coupling constants, J, are
given in Hz to apparent peak multiplications. Spectral assignments were achieved by a combination of 1H-1H COSY, and 1H-13C
HSQC/HMBC experiments. The splitting patterns are indicated as follows abbreviations: singlet (s), doublet (d), doublet of
doublet (dd), triplet (t), quartet (q), multiplet (m) and broad (br). Mass spectra were obtained using a JEOL JMS-SX102A
instrument with m-nitrobenzyl alcohol as the matrix (FAB+ mode), and a JEOL JMS-AX505-A (EI mode at 70 eV). DART
analyses were recorded on a Jeol AccuTOF JMS-T100LC mass spectrometer. Elemental compositions were calculated within
an uncertainty of 5 ppm by using the program installed in the computer system.
The X-ray diffraction data collection and refinement parameters for compounds 2b, 3a, 3c and 6c were recorded by Bruker
Smart APEX spectrometer using graphite monochromated MoKα radiation (0.71073 Å) at 298°K. Data reduction was carried
out with the APEX2 software.32 The structures were solved by SHEXS and refined using SHELX-2016 and 2018.33 Non-
hydrogen atoms were refined anisotropically. H atoms were positioned geometrically and refined with isotropic
displacement parameters according the riding model.). Crystal data for the structural analysis is given in Table 1. The CIF file
containing complete information on the studied structure was deposited in Cambridge Crystallographic Data Centre
deposition number:1983258, 1956452, 1950575 and 1928553 (E-mail: deposit@ccdc.cam.ac.uk), and is freely available upon
request from the following web site: www.ccdc.cam.ac.uk/data_request/cif.
Synthesis of N-PhSeCH2CH2ImH.(1a) A solution of diphenyldiselenide (0.624g, 2.0 mmol) in ethanol (30 mL) was treated with
sodium borohydride (0.151g, 4.0 mmol) and the mixture was further stirred for 30 min. When it became colorless, a solution
of 1-(2-chloroethyl)-1H-imidazole (0.522g, 4.0 mmol) in ethanol (10 mL) was added with constant stirring for 12 h under
nitrogen. Water was added to the solution (40 mL) and was extracted with dichloromethane (4 x 25 mL). The extract was
washed with water (2 x 25 mL), dried over anhydrous sodium sulphate and evaporated under reduced pressure to afford the
desired compound as yellow oil. Yield (0.956g, 95%). 1H NMR (300 MHz, CDCl3, 298 K) δ 7.46 (d, JH-H = 8.0, 2H, Ho-Ph), 7.40 (s,
1H, NCHN), 7.28 (t, JH-H = 6.8, 1H, Hp-Ph), 7.26 (dd, JH-H = 8.0, 6.8, 2H, Hm-Ph), 7.00 and 6.85 (both br, 2H, =CHN), 4.10 (t, JH-H
=
7.0, 2H, N-CH2), 3.11 (t, JH-H = 7.0, Se-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ 137.0 (s, NCHN), 133.4 (s, Co-Ph), 129.6 (s, Cp-
Ph), 129.5 (s, Cm-Ph), 128.3 (s, Cq-Ph), 127.8 and 118.6 (both s, =CHN), 46.9 (s, N-CH2), 28.0 (s, Se-CH2). 77Se NMR (57 MHz, CDCl3,
298 K): δ 284.0. MS (DART) m/z: 253 [M+H]+, 225, 185. HRMS (DART) m/z calcd for C11H13N2Se [M+H]+ 253.0244, found
253.0241.

Synthesis of N-PhTeCH2CH2ImH.(1b) A solution of diphenylditelluride (0.818g, 2.0 mmol) in ethanol (30 mL) was treated with
sodium borohydride (0.151g, 4.0 mmol) and the mixture was further stirred for 30 min. When it became colorless, a solution
of 1-(2-chloroethyl)-1H-imidazole (0.522g, 4.0 mmol) in ethanol (10 mL) was added under nitrogen and was heated with
constant stirring for 3 h at 90 °C. Water was added to the solution (40 mL) and was extracted with dichloromethane (4 x 25
mL). The extract was washed with water (2 x 25 mL), dried with anhydrous sodium sulphate and evaporated under reduced
pressure to afford the desired compound as yellow oil. Yield (1.056g, 87%). 1H NMR (300 MHz, CDCl3, 298 K) δ 7.66 (d, JH-H
=
7.7, 2H, Ho-Ph), 7.37 (s, 1H, NCHN), 7.27 (t, JH-H = 6.7, 1H, Hp-Ph), 7.16 (dd, JH-H = 7.7, 6.7, 2H, Hm-Ph), 6.95 and 6.80 (both br, 2H,
=CHN), 4.18 (t, JH-H = 7.4, 2H, N-CH2), 3.07 (t, JH-H = 7.4, 2H, Te-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ 139.0 (s, Co-Ph),
136.7 (s, NCHN), 129.7 (s, Cp-Ph), 129.5 (s, Cm-Ph), 128.4 and 118.2 (both s, =CHN), 110.2 (s, Cq-Ph), 48.9 (s, N-CH2), 7.9 (s, Te-
CH2). ). 125Te NMR (94.67 MHz, acetone-d6, 298 K): δ 455.13. MS (DART) m/z: 303 [M+H]+, 275, 235. HRMS (DART) m/z calcd
for C11H13N2Te [M+H]+ 303.0141, found 303.0149.
Synthesis of N-FcSeCH2CH2ImH. (1c) A solution of diferrocenyldiselenide (0.15g, 0.2841 mmol) in ethanol (40 mL) was
treated with sodium borohydride (0.0434g, 1.1364 mmol) and the mixture was further stirred at 90°C for 1 h. When the color
changes, a solution of 1-(2-chloroethyl)-1H-imidazole (0.0739g, 0.5682 mmol) in ethanol (5 mL) was added with constant
stirring for 6 h at 90°C under nitrogen. Water was added to the solution (40 mL) and was extracted with dichloromethane (4 x
25 mL). The extract was dried with anhydrous sodium sulfate and evaporated under reduced pressure to afford the desired
compound as an orange oil. Yield (0.1442g, 70.5%). ¹H NMR (300 MHz, acetone-d6, 298 K): δ 7.41 (s, 1H, NCHN), 6.94 and 6.76
(both br, 2H, =CHN), 4.19 and 4.12 (both br, 4H, FcA), 4.06 (t, JH-H = 7.0, 2H, N-CH2), 4.05 (s, 5H, FcB), 2.82 (t, JH-H = 7.0, 2H, Se-
CH2). ¹³C NMR (75 MHz, acetone-d6, 298 K): δ 137.1 (s, NCHN), 128.7 and 118.7 (both s, =CHN), 75.1 and 69.8 (both s, FcB),
69.7 (s, Cq-Fc), 69.1 (s, FcA), 46.7 (s, N-CH2), 29.3 (s, Se-CH2). ⁷⁷Se NMR (57 MHz, acetone-d6, 298 K): δ 180.07. MS (DART) m/z:
361 [M+H]+, 265. HRMS: Found 360.9904 calcd. For C15H17FeN2Se 360.9906.
Synthesis of N-FcTeCH2CH2ImH. (1d) A solution of diferrocenylditelluride (0.15g, 0.2381 mmol) in ethanol (30 mL) was
treated with sodium borohydride (0.0367g, 0.9526 mmol) and the mixture was further stirred for 1 h. When the color
changes, a solution of 1-(2-chloroethyl)-1H-imidazole (0.0619g, 0.4763 mmol) in ethanol (5 mL) was added under nitrogen
and was heated with constant stirring for 5 h at 90 °C. Water was added to the solution (40 mL) and was extracted with
dichloromethane (4 x 25 mL). The extract was dried with anhydrous sodium sulfate and evaporated under reduced pressure
to afford the desired compound as yellow solid. Yield (0.156g, 80%). ¹H NMR (300 MHz, acetone-d6, 298 K): δ 7.51 (s, 1H,
NCHN), 7.05 and 6.88 (both br, 2H, =CHN), 4.36 and 4.27 (both dd, JH-H = 1.8, 1.8, 4H, FcA), 4.28 (t, JH-H = 7.8, 2H,N-CH2), 4.16
(s, 5H, FcB), 2.97 (t, JH-H = 7.8, 2H,Te-CH2). ¹³C NMR (100 MHz, acetone-d6, 298 K): δ 136.8 (s, NCHN), 128.8 and 118.4 (both s,
=CHN), 79.3 and 71.3 (both s, FcA), 69.05 (s, FcB), 48.6 (s, N-CH2), 42.4 (s, Cq-Fc), 8.23 (s, Te-CH2). 125Te NMR (94.67 MHz,
acetone-d6, 298 K): δ 289.85. MS (DART) m/z: 409 [M+H]+ HRMS: Found .410.9817 calcd. For C15H17N2Te 410.9803. Elemental
Analysis Calcd for C15H16FeN2Te: C, 44.18; H, 3.96; N, 6.87. Found: C, 44.39; H, 4.04; N, 6.38.
General
procedure
for
the
synthesis
of
ferrocenyl-chalcogen-imidazolium
salts.
A
solution
of
(ferrocenylmethyl)trimethylamonium iodide (6.50 mmol) was reacted with the appropriate 1-substituted imidazole
derivative (7.00 mmol) in anhydrous MeCN (20 mL) and the reaction mixture was refluxed for 24 h. After this period, the
cooled solution was poured into water (10 mL) and extracted with chloroform (4 x 25 mL). The organic phase was washed
with water (2 x 20 mL), dried with MgSO4 and evaporated under reduced pressure to give an orange oil.
Synthesis of (N-PhSeCH2CH2)(N´-CH2Fc)ImH+I-.(2a). This compound was prepared according to the general procedure and it
was isolated as orange oil. Yield (3.46 g, 85%). 1H NMR (300 MHz, CDCl3, 298 K) δ 9.74 (s, 1H, NCHN), 7.43 (dd, JH-H = 7.5, 2.2,
2H, Ho-Ph), 7.33 and 7.15 (both t, JH-H = 2.0, 2H, =CHN), 7.24 (dd, JH-H = 7.5, 6.3, 2H, Hm-Ph), 7.23 (t, JH-H = 6.3, 1H, Hp-Ph), 5.29 (s,
2H, Fc-CH2), 4.54 (t, JH-H = 6.5, 2H, N-CH2), 4.45 and 4.25 (both dd, JH-H = 1.5, 1.5, 4H, FcA), 4.24 (s, 5H, FcB), 3.39 (t, JH-H = 6.5,
2H, Se-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ 135.7 (s, NCHN), 133.3 (s, Co-Ph), 129.7 (s, Cm-Ph), 128.0 (s, Cp-Ph), 127.6 (s,
Cq-Ph), 122.3 and 121.2 (both s, =CHN), 78.2 (s, Cq-Fc), 69.9 and 69.7 (both s, FcA), 69.3 (s, FcB), 50.1 (s, Fc-CH2), 50.0 (s, N-CH2),
27.2 (s, Se-CH2). 77Se NMR (57 MHz, CDCl3, 298 K): δ 277.4. HRMS (FAB) m/z calcd for C22H23N2FeSe [M-I]+ 451.0376, found
451.0376.
Synthesis of (N-PhTeCH2CH2)(N´-CH2Fc)ImH+I-.(2b). This compound was prepared according to the general procedure and it
1
was isolated as orange oil. Yield (3.82 g, 80%). H NMR (300 MHz, CDCl3, 298 K) δ 9.64 (s, 1H, NCHN), 7.61 (d, JH-H = 7.4, 2H,
Ho-Ph), 7.40 and 7.26 (both br, 2H, =CHN), 7.22 (t, JH-H = 7.1, 1H, Hp-Ph), 7.14 (dd, JH-H = 7.4, 7.1, 2H, Hm-Ph), 5.27 (s, 2H, Fc-CH2),
4.59 (t, JH-H = 6.8, 2H, N-CH2), 4.46 and 4.20 (both br, 4H, FcA), 4.20 (s, 5H, FcB), 3.32 (t, JH-H = 6.8, 2H, Te-CH2). 13C{1H} NMR (75
MHz, CDCl3, 298 K): δ 138.6 (s, Co-Ph), 134.9 (s, NCHN), 129.7 (s, Cm-Ph), 128.3 (s, Cp-Ph), 122.1 and 121.6 (both s, =CHN), 110.9
(s, Cq-Ph), 78.6 (s, Cq-Fc), 69.8 (s, FcA), 69.2 (s, FcB), 51.8 (s, N-CH2), 50.0 (s, Fc-CH2), 7.9 (s, Te-CH2). HRMS (FAB) m/z calcd for
C22H23N2FeTe [M-I]+ 501.0273, found 501.0278.

Synthesis of (N-FcSeCH2CH2)(N´-CH3)ImH+I-.(2c). A solution of methyl iodide (6.50 mmol) was treated with the appropriate 1-
substituted imidazole derivative (7.00 mmol) in anhydrous MeCN (20 mL) and the solution was refluxed for 24 h. After this
period, the cooled solution was poured into water (10 mL) and extracted with chloroform (4 x 25 mL). The organic phase was
washed with water (2 x 20 mL), dried with MgSO4 and evaporated under reduced pressure to give orange solid.¹H NMR (300
MHz, acetone-d6, 298 K): δ 9.44 (t, JH-H = 1.6, 1H, NCHN), 7.80 and 7.70 (both dd, JH-H = 1.8, 1.6, 2H, =CHN), 4.58 (t, JH-H = 6.9,
2H, N-CH2), 4.36 and 4.25 (both, dd, JH-H = 1.7, 1.9, 4H, FcA), -4.17 (s, 5H, FcB), 4.07 (s ,3H, Me), 3.18 (t, JH-H = 6.9, 2H, Se-CH2).
¹³C NMR (75 MHz, acetone-d6, 298 K): δ 137.8 (s, NCHN), 124.5 and 123.4 (both s, =CHN), 76.2 and 70.7 (both s, FcA), 70.1 (s,
FcB), 69.9 (s, Cq-Fc), 50.9 (s, N-CH2), 36.7 (s, Me), 28.7 (s, Se-CH2) ⁷⁷Se NMR (57 MHz, acetone-d6, 298 K): δ 175.40. FAB MS m/z:
[M+H]+ 375.
General procedure for the synthesis of ferrocenyl NHC selenones. To a solution of the corresponding imidazolium iodide
(1.3332mmol) in anhydrous acetonitrile (10 mL), elemental Se (1.3332mmol) and potassium carbonate (1.3332 mmol) were
added. Then, the mixture was stirred at room temperature for 24 h. After this period, the solution was filtered and the
filtrate was evaporated under reduced pressure and washed with hexane to give yellow solid.
Synthesis of (N-PhSeCH2CH2)(N´-CH2Fc)ImSe.(3a) This compound was prepared according to the general procedure using (N-
PhSeCH2CH2)(N´-CH2Fc)ImH+I-.(2a) as a reactant. The compound (3a) was isolated as a yellow solid Yield 95 % (1.07369 g). ¹H
NMR) (400 MHz, acetone-d6, 298 K): 7.62-7.54 (m, 2H, Hm-Ph), 7.31-7.22 (m, 3H, Ho,p-Ph), 7.15 and 7.08 (both d, 2H, =CHN),
5.08 (s, 2H, Fc-CH2), 4.49 and 4.16 (both dd, 4H, FcA), 4.39 (t, JH-H = 7.15, 2H, N-CH2), 4.23 (s, 5H, FcB), 3.38 (t, JH-H = 7.2, 2H, Se-
CH2). ¹³C NMR (75 MHz, acetone-d6, 298 K): δ: 156.5 (s, CNCN), 132.6 (s,Co-Ph), 130.3 (s, Cq-Ph), 130.1 (s, Cm-Ph), 127.6 (s, Cp-Ph),
120.3 (s, C=CHN), 119.2 (s, C=CHN), 83.7 (s, Cq-Fc), 70.3 and 69.1 (both s, CFcA), 69.5 (s, CFcB), 50.4 (s, N-CH2), 49.1 (s, Fc-CH2), 25.4
(s, Se-CH2). ⁷⁷Se NMR (57 MHz, acetone-d6, 298 K) δ: 268.46 (s, Se-CH2), 14.68 (s, Se-CNHC). DART-MS m/z: 530 [M+H]+. HRMS:
Found 528.9548 calcd. C22H23FeN2Se2 528.9549.
Synthesis of (N-PhSeCH2CH2)(N´-CH3)ImSe.(3b) This compound was prepared according to the general procedure using (N-
PhSeCH2CH2)(N´-CH3)ImH+I-.8b as a reactant. The compound (3b) was isolated as a yellow solid. Yield (0.5640g, 93%) ¹H NMR
(300 MHz, acetonitrile-d3, 298 K): δ 7.53 (d, JH-H =7.4, 2H, Ho-Ph), 7.29-7.20 (m, 3H, Hm,p-Ph), 6.98 and 6.92 (both d, JH-H = 2,3, 2H,
=CHN), 4.30 (t, JH-H = 7.3, 2H, N-CH2), 3.52 (s, 3H, Me), 3.30 (t, JH-H = 7.3, 2H, Se-CH2). ¹³C NMR (75 MHz, acetonitrile-d3, 298 K):
δ 155.94 (s, Se-CNHC), 132.54 (s, Co-Ph), 129.9 (s, Cm-Ph), 127.54 (s, Cp-Ph), 122.3 (s, Cq-Ph), 120.6 and 120.1 (both s, =CHN), 50.3 (s,
N-CH2), 37.0 (s, Se-CH2), 25.5 (s, Me). ⁷⁷Se NMR (57 MHz, acetonitrile-d3, 298 K): δ 268.7 (s, Se-CH2), 32.6 (s, Se-CNHC). DART-
MS m/z: 347 [M+H]+. HRMS: Found 344.9580 calcd. For C12H15N2Se2 344.9573.
Synthesis of (N-FcSeCH2CH2)(N´-CH3)ImSe.(3c) This compound was prepared according to the general procedure using (N-
FcSeCH2CH2)(N´-CH3)ImH+I- (2c) as a reactant. The compound (3c) was isolated as a yellow solid. Yield (0.5640g, 93% ¹H NMR)
(400 MHz, acetone-d6, 298 K): δ 7.08 and 7.06 (both d, JH-H = 2.3, 2H, =CHN), 4.27 and 4.11 (both dd, JH-H = 1.6, 1.8, 4H, FcA),
4.17 (t, JH-H = 7.5, 2H, N-CH2), 4.05 (s, 5H, FcB), 3.47 (s, 3H, Me), 2.91(t, JH-H = 6.9, 2H, Se-CH2). ¹³C NMR (100 MHz, acetone-d6,
298 K): δ 156.2 (s, Ag-CNHC), 119.7 and 119.2 (both s, =CHN), 74.6 and 69.5 (both s, FcA), 70.5 (s, Cq-Fc), 69.2 (s, FcB), 69.17 (s, C-
d), 49.7 (s, N-CH2), 36.0 (s, Me), 26.5 (s, Se-CH2). ⁷⁷Se NMR (57 MHz, acetone-d6, 298 K): δ 170.4 (s, Se-CH2), 11.5 (s, Se-CNHC).
DART-MS m/z: 455 [M+H]+. HRMS: Found 452.9249 Calcd. C12H15N2Se2 452.9236. Elemental Analysis Calcd for C16H19FeN2Se2:
C, 42.51; H, 4.01; N, 6.20. Found: C, 41.97; H, 4.14; N, 5.95.
General procedure for the synthesis of Ag(I)-ferrocenyl-chalcogen-NHC-complexes. A solution of 1-ferrocenylmethyl-3-
(phenyl-chalcogen-ethyl)imidazolium iodide (0.5 mmol) in anhydrous dichloromethane (20 mL) was added Ag2O (0.5 mmol)
and stirred at room temperature in the dark. After this period, the solution was filtered and evaporated under reduced
pressure to yellow-orange oil. The addition of hexane (10 mL) precipitates the desired compound. The corresponding solid
was collected by filtration and dried at room temperature.
Synthesis of (N-PhSeCH2CH2)(N´-CH2Fc)ImAgI (4a). This compound was prepared according to the general procedure and was
1
isolated as yellow solid. Yield (280 mg, 81%). H NMR (300 MHz, CDCl3, 298 K) δ 7.32 (d, JH-H = 6.0, 2H, Ho-Ph), 7.11 (dd, JH-H
=
6.0, 6.0, 2H, Hm-Ph), 7.09 (t, JH-H = 6.0, 1H, Hp-Ph), 6.83 and 6.77 (both br, 2H, =CHN), 5.03 (s, 2H, Fc-CH2), 4.33 (t, JH-H = 5.8, 2H,
N-CH2), 4.26 and 4.07 (both br, 4H, FcA), 4.13 (s, 5H, FcB), 3.22 (t, JH-H = 5.8, 4H, Se-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ
181.5 (s, Ag-CNHC), 132.8 (s, Co-Ph), 129.4 (s, Cm-Ph), 128.9 (s, Cq-Ph), 127.3 (s, Cp-Ph), 121.2 and 120.3 (both s, =CHN), 82.1 (s, Cq-
Fc), 69.4 and 68.9 (both s, FcA), 69.1 (s, FcB), 51.8 (s, N-CH2), 51.6 (s, Fc-CH2), 29.2 (s, Se-CH2). ⁷⁷Se NMR (57 MHz, CDCl3, 298 K):
δ 274.6.
Synthesis of (N-PhTeCH2CH2)(N´-CH2Fc)ImAgI. (4b) This compound was prepared according to the general procedure and
was isolated as yellow solid. Yield (310 mg, 84%). 1H NMR (300 MHz, CDCl3, 298 K) δ 7.72 (d, JH-H = 7.2, 2H, Ho-Ph), 7.24 (t, JH-H
=
7.2, 1H, Hp-Ph), 7.11 (dd, JH-H = 7.2, 7.2, 2H, Hm-Ph), 6.82 and 6.78 (both br, 2H, =CHN), 5.17 (s, 2H, Fc-CH2), 4.65 (t, JH-H = 6.9, 2H,
N-CH2), 4.37 and 4.07 (both br, 4H, FcA), 4.21 (s, 5H, FcB), 3.34 (t, JH-H = 6.9, 2H, Te-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ

182.7 (s, Ag-CNHC), 138.6 (s, Co-Ph), 129.5 (s, Cm-Ph), 128.5 (s, Cp-Ph), 120.3 and 120.2 (both s, =CHN), 111.9 (s, Cq-Ph), 82.3 (s, Cq-
Fc), 69.5 and 68.9 (both s, FcA), 69.1 (s, FcB), 52.4 (s, N-CH2), 51.6 (s, Fc-CH2), 13.6 (s, Te-CH2). MS (FAB) m/z: 607 [M-I]+
Synthesis of (N-FcSeCH2CH2)(N´-Me)ImAgI. (4c) This compound was prepared according to the general procedure and it was
isolated as yellow solid. Yield (280 mg, 73%)¹H NMR (300 MHz, acetone-d6, 298 K): δ 7.38 and 7.32(both br, 2H, =CHN), 4.46
(t, JH-H = 6.9, 2H, N-CH2), 4.34 and 4.18 (both dd, JH-H = 1.6, 1.8, 4H, FcA), 4.16 (s, 5H,FcB), 3.91 (s, 3H, Me), 3.09 (t, JH-H = 6.9,
2H, Se-CH2). ¹³C NMR (75 MHz, acetone-d6, 298 K): δ 182.46 (s, Ag-CNHC), 123.5 and 122.4 (both s, =CHN), 75.8 and 70.5 (both
s, FcA), 71.1 (s, Cq-Fc), 70.1 (s, FcB), 52.7 (s, N-CH2), 39.0 (s,Me), 30.9 (s, Se-CH2), ⁷⁷Se NMR (57 MHz, acetone-d6, 298 K): δ
173.4.
General procedure for the synthesis of palladate ferrocenyl-chalcogen-NHC complexes. A solution of the corresponding
ferrocenyl-chalcogen-NHC (6.50 mmol) was treated with PdCl2(CH3CN)2 (3.25 mmol) in anhydrous CHCl3 (5 mL). The crude
reaction mixture was evaporated under reduced pressure to give red oil.
-2
Synthesis of [(N-PhSeCH2CH2)(N´-CH2Fc)ImH]+ PdCl2I2
(5a) This compound was prepared according to the general
1/2
procedure and it was isolated as red oil. Yield (3.91 g, 91%). 1H NMR (300 MHz, CDCl3, 298 K) δ 10.09 (s, 1H, NCHN), 7.38 (dd,
JH-H = 7.5, 2.2, 2H, Ho-Ph), 7.31 and 7.09 (both t, JH-H = 2.0, 2H, =CHN), 7.18 (dd, JH-H = 7.5, 6.3, 2H, Hm-Ph), 7.16 (t, JH-H = 6.3, 1H,
Hp-Ph), 5.23 (s, 2H, Fc-CH2), 4.52 (t, JH-H = 6.5, 2H, N-CH2), 4.38 and 4.16 (both dd, JH-H = 1.5, 1.5, 4H, FcA), 4.17 (s, 5H, FcB), 3.38
(t, JH-H = 6.5, 2H, Se-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ 134.3 (s, NCHN), 133.3 (s, Co-Ph), 127.6 (s, Cm-Ph), 125.9 (s, Cp-
Ph), 125.8 (s, Cq-Ph), 120.5 and 119.0 (both s, =CHN), 76.6 (s, Cq-Fc), 67.8 and 67.6 (both s, FcA), 67.3 (s, FcB), 48.1 (s, Fc-CH2), 48.0
(s, N-CH2), 27.9 (s, Se-CH2). 77Se NMR (57 MHz, CDCl3, 298 K): δ 277.3. MS (FAB) m/z: 430 [PdCl2I]-.HRMS (FAB) m/z calcd for
C22H23N2FeSe [M-PdCl2I2]+ 451.0376, found 451.0376.
-2
Synthesis of. [(N-PhTeCH2CH2)(N´-CH2Fc)ImH]+ PdCl2I2
(5b) This compound was prepared according to the general
1/2
procedure and was isolated as orange oil. Yield (4.06 g, 87%). 1H NMR (300 MHz, CDCl3, 298 K) δ 10.23 (s, 1H, NCHN), 7.82 (d,
JH-H = 7.6, 2H, Ho-Ph), 7.58 and 7.18 (both br, 2H, =CHN), 7.32 (t, JH-H = 7.2, 1H, Hp-Ph), 7.21 (dd, JH-H = 7.6, 7.2, 2H, Hm-Ph), 5.28 (s,
2H, Fc-CH2), 4.75 (t, JH-H = 6.8, 2H, N-CH2), 4.45 and 4.22 (both br, 4H, FcA), 4.23 (s, 5H, FcB), 3.70 (t, JH-H = 6.8, 2H, Te-CH2).
13C{1H} NMR (75 MHz, CDCl3, 298 K): δ 138.3 (s, Co-Ph), 135.8 (s, NCHN), 129.7 (s, Cm-Ph), 129.4 (s, Cp-Ph), 122.3 and 121.2 (both
s, =CHN), 114.6 (s, Cq-Ph), 78.7 (s, Cq-Fc), 69.8 and 69.7 (both s, FcA), 69.2 (s, FcB), 50.3 (s, N-CH2), 49.9 (s, Fc-CH2), 17.9 (s, Te-
CH2).
Synthesis of (N-FcSeCH2CH2)(N´-CH3)ImPdCl2 (6c). A solution of (N-FcSeCH2CH2)(N´-Me)ImAgI (4c) (3.25 mmol) was treated
with PdCl2(CH3CN)2 (3.25 mmol) in anhydrous acetonitrile (5 mL). The crude reaction mixture was evaporated under reduced
pressure to give red oil which was purified on a celite column using a 95/5 ethyl acetate-hexane (95:5) mixture. The resulting
1
solid was filtered and dried at room temperature. H NMR (300 MHz, acetonitrile-d3, 298 K) δ 7.16 and 7.10 (both d, JH-H
=
1.9, 2H, =CHN), 4.56 (m, 2H, N-CH2), 4.28, 4.28, 4.09, and 3.73 (all m, 4H, FcA), 4.47 (s, 5H, FcB), 4.11 (s, 3H, Me), 3.53 and 2.32
(both m, 2H, Se-CH2). 13C{1H} NMR (75 MHz, CDCl3, 298 K): δ 151.3 (s, Pd-CNHC), 125.0 and 123.3 (both s, =CHN), 72.9 (s, Cq-Fc),
70.7, 70.2, 69.8, and 69.3 (all s, FcA), 69.3 (s, FcB), 52.1 (s, N-CH2), 39.2 (s, Me), 37.4 (s, Se-CH2). ⁷⁷Se NMR (57 MHz,
acetonitrile-d3, 298 K): δ 162.3. DART-MS m/z: 589 [M+H+Cl]+. HRMS: Found 551.8519 Calcd. C16H18Cl2FeN2PdSe 551.8529.
Table 1. Crystallographic data for compounds 2b, 3a, 3c and 6c
Compound
Moiety formula
Mr
2b
3a
(3c)
C16H18FeN2Se2
452.09
6c
C22H23FeN2Te1I
625.77
298 k
C22H22FeN2Se2
528.19
150 K
C16H18Cl2FeN2PdSe
635.36
250 K
Temp
150 K
0.71073
0.71073
0.71073
0.71073
 (Å)
Crystal system
Space group
Monoclinic
P21/c
a = 8.8989(14) Å
b = 23.167(4) Å
c = 11.1057(16) Å
 = 90°
Monoclinic
P21/c
a = 14.0188(6) Å
b = 10.0612(4) Å
c = 14.3661(5) Å
 = 90°
Monoclinic
C2
a = 38.635(2) Å
b = 7.5167(4) Å
c = 11.6786(6) Å
 = 90°
Monoclinic
P21/c
a = 191490(8) Å
b = 8.1857(4) Å
c = 14.8480(5) Å
 = 90°
Cell
 = 101.824(5)°
 = 97.348(1)°
 = 104.075°
 = 112.553(2)°
 =90°
2241.0 (6)
4
1.855
3.335
 = 90°
2009.64 (14)
4
1.746
4.382
 = 90°
3289.7 (3)
8
1.826
5.337 mm-1
 = 90°
2149.41 (16)
4
1.963
3.707
Volume (Å3)
Z
Dcal (g/cm3)
Μ (mm-1)

GOF
R1[I>2σ(I)]
1.111
0.0481
1.045
0.0228
1.133
0.0380
1.183
0.0481
Transmission factor
min = 0.294
max = 0.417
6297
min = 0.2096
max = 0.286
3680
min = 0.625
max = 0.726
5964
min = 0.313
max = 0.752
3937
reflns number total
reflns number gt
4249
3339
5236
2879
Conflicts of interest
There are no conflicts to declare.
Acknowledgments
We thank DGAPA-UNAM for financial support (PAPIIT IN209020) and CONACyT (Fellowship 915760).
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Ferrocenylated Chalcogen (Se and Te)-Containing N-Heterocyclic Carbenes: Selenones,
Silver and Palladium Complexes
Rodary Gonzalez,a Ramón Azpiroz,a Pankaj Sharma,a* Claudia P. Villamizar-Caballero,a Bertín Anzaldo,a
Francisco J. Pérez-Flores,a Alfredo Ruben. Toscano a
[a] Instituto de Química Universidad Autónoma de México UNAM, Cd., Universitaria, PO Box 04510, Ciudad de México,
México. E-mail: pankajsh@servidor.unam.mx México. E-mail: pankajsh@servidor.unam.mx
Conflicts of interest
There are no conflicts to declare.
CRediT author statement
Rodary Gonzalez: Methodology, validation, Writing - Review and editing; Ramón Azpiroz.:
Methodology, validation, Writing- Original draft preparation a Pankaj Sharma,: conceptualization,
Investigation, supervision; Claudia P. Villamizar C: investigation, methodology, Writing - Review
and editing; Bertin Anzaldo: methodology, Validation; Francisco J. Pérez-Flores: data curation;
Ruben Alfredo Toscano: data curation.
Highlights

New Ferrocenylated Chalcogen (Se and Te)-Containing imidazolium salts.
 Molecular structures of ferrocenyl-NHC selenones, silver NHC and ionic palladium
(II) complexes
 New palladium(II)- Ferrocenylated Chalcogen containing NHC complex by silver
carbene transfer reaction