Synthesis of N-heterocyclic nitrenium (NHN) ions and related donor systems: Coordination with d10-metal ions

Article abstract of DOI:10.1016/j.ica.2019.01.024

The synthesis of three new NNN- and CNC type N-heterocyclic nitrenium (NHN) ion based pincer ligands is reported from 1,3-di-(2′-bromoethyl)-triazolium bromide (5). The reaction of 5 with ammonium hexafluorophosphate followed by two equivalent of pyrrolid

Full text of DOI:10.1016/j.ica.2019.01.024

Accepted Manuscript
Research paper
Synthesis of N-heterocyclic nitrenium (NHN) ions and related donor systems:
Coordination with d10-metal ions
Sangeeta Yadav, Rajesh Deka, Saravanan Raju, Harkesh B. Singh
PII:
S0020-1693(18)31598-6
https://doi.org/10.1016/j.ica.2019.01.024
ICA 18747
DOI:
Reference:
Inorganica Chimica Acta
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13 October 2018
25 December 2018
19 January 2019
Please cite this article as: S. Yadav, R. Deka, S. Raju, H.B. Singh, Synthesis of N-heterocyclic nitrenium (NHN)
ions and related donor systems: Coordination with d10-metal ions, Inorganica Chimica Acta (2019), doi: https://
doi.org/10.1016/j.ica.2019.01.024
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Synthesis of N-heterocyclic nitrenium (NHN) ions and related donor systems: Coordination
with d10-metal ions
Sangeeta Yadav,a Rajesh Deka,a Saravanan Raju,a Harkesh B. Singha*
aDepartment of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076,
India
(E-mail: chhbsia@chem.iitb.ac.in)
Keyword
N-heterocyclic carbene, nitrenium ion, pincer ligand, selone, tellurium
Abstract
The synthesis of three new NNN- and CNC type N-heterocyclic nitrenium (NHN) ion
based pincer ligands is reported from 1,3-di-(2´-bromoethyl)-triazolium bromide (5). The
reaction of 5 with ammonium hexafluorophosphate followed by two equivalent of
pyrrolidine/diethylamine afforded NHN ions (10a and 10b). The reaction of 5 with N-
butylbenzimidazole (6) afforded nitrenium ion 7, where the chelating arms have benzimidazole
based carbene carbons. In an attempt to synthesize hybrid NHN ligand containing soft tellurium
donor in the chelating arm, 1-(2´-bromoethyl)-benzotriazole, was first reacted with in situ
generated NaTePh to afford tellurated benzotriazol (13). However, when compound 13 was
treated with methyl iodide, an unexpected methylation underwent at tellurium center to afford
compound 14. Reaction of 7 with Hg(OAc)2 and 10a with CuI afforded complex 8 and 11
respectively. Both these complexes are characterized by NMR (1H, 13C), HRMS and CHN
analysis. The Natural Bond Order (NBO) calculations and Atoms in Molecules (AIM) analyses
sufficiently substantiate the presence of interaction between triazolium N atom with metal centre.
The reaction of N,N´-disubstituted benzimidazoles, 17a-17b with in situ generated Na2Se2 in the
presence of potassium tert-butoxide at room temperature afforded two novel benzimidazoline-2-
chalcogenones (18a and 18b). Nitrenium ion (10a-10b), tellurated benzotriazole (13 and 14) and
selone 18a are authenticated by single crystal X-ray diffraction studies.

Introduction
Carbenes, after the pioneering work by Wanzlick1 and successful isolation of the first stable N-
heterocyclic carbene (NHC) by Arduengo,2 have garnered significant attention and become an
important class of compounds with respect to their intriguing and uncommon bonding and
structural properties.3 Carbenes are defined as neutral compounds containing a divalent carbon
atom with a six-electron valence shell, which consequently make them highly reactive in nature.
With their unambiguous role as ancillary ligands for complexation with metals, the coordination
chemistry of carbenes and their reactivity have reached enviable position across many fields of
organic and organometallic chemistry.4 The extraordinarily expanded portfolio displayed by
NHC motivated the researchers to urge for the exploration of its isovalent analogous forms.
Consequently, main-group carbene analogues, like NHC, have flourished in almost all aspects of
organometallic chemistry and they have been ubiquitously used in various metal based
chemistry.5 In both NHC and main-group carbene analogues, it possess one lone pair of electron
which can take part in -bonding during coordination with metal (Figure 1a). At the same time,
empty p-orbital in carbenoid center can accept electron from the metal (Figure 1b).
Figure 1. Bonding picture of NHC and analogues with metals
However, despite close analogy, the nitrogen analogue of NHC, known as N-heterocyclic
nitrenium (NHN) ion and their metal complexes remained elusive for a long time and are still not
well-explored.6 The main stumbling block of NHN as a ligand is the presence of positive charge
at the periphery i.e. triazolium ion, which in turn offers poor coordination to the metal center.
Although not prevalent, there is limited literature available which deals with the ligation of
cationic ligand to a transition metal.7 In these complexes, the bonding between the metals and

ligands can be best explained by solely considering the metal to ligand -back donation (M→L*)
(Figure 1b) in to account. However, in the case of NHN, the weaker -acceptor ability of
cationic N atom makes this kind of bonding theoretically less feasible. Gandelman et al. in
2011,8 pioneered the coordination chemistry of NHN by reporting Rh(I) and Ru(II) complexes,
1-3 (Chart 1) of nitrenium ion-based PNP-pincer ligand wherein they have incorporated two
phosphine chelating arms to a triazolium ring, which eventually bring the metal close to the
nitrogen center, thus allowing the otherwise unconventional coordination mode possible.
Subsequently, they have expanded the coordination chemistry of nitrenium ions to Pd, Pt, Mo
and Ag metals.9 From the Density Functional Theory (DFT) calculations, they inferred that the
nitrenium ions are relatively weak -donors and reasonably -acceptor. Ray and co-workers10
have studied the redox properties of nickel(I) complex of nitrenium ion, 4. Interestingly, in the
complex they have observed a bent coordination mode of the nitrenium ion to the Ni(I) center,
similar to a nitrosyl ion. This is caused by the presence of a nonbonding electron pair in the sp2
hybrid orbital of nitrenium nitrogen. While still in its infancy, the novel chemistry of nitrenium
ion sincerely demands design and development of new ligand family to get detail insight into
their unusual bonding facets with metals and probable applications in contemporary coordination
chemistry.
Chart 1. Examples of nitrenium ions and their coordination complexes.
As it is abundantly clear that most of the literature reports on coordination chemistry of
nitrenium ions are based on PNP-type ligands and variation of nitrenium ion based ligands are
rather scarce. In this context, we have envisaged to develop new NNN, CNC- type NHN ligands
which contain, in particular, pyrrole, N,N-dimethylamine, imidazole based carbenes as auxiliary
arms. We have further attempted to explore the ligation behavior of the synthesized nitrenium
ions with transition metal, in particular with d10 metal precursors (vide infra). While trying to

synthesize ‘hybrid’ NHN ligand where the auxiliary arms contain soft donor atom such as
tellurium, the reaction did not proceed as desired and resulted in unexpected ternization at
tellurium center (vide infra).
Like other carbene analogues/derivatives, the group 16 (chalcogens) derivatives of NHC,
commonly known as chalcogenones (Chart 2), have also gained significant attention in
complementary organometallic chemistry. The first chalcogenone, benzimidazolin-2-selone was
reported by Warner in 1963 by reacting o-phenylenediamine with carbon diselenide.11a The
corresponding sulphur analogues (thiones) and tellurium analogues (tellones) were introduced by
Ansell et al. and Arduengo et al. respectively.11b-c Similar to parent NHCs, the corresponding
chalcogen adducts are also expected to contribute to the metal-selenium bond by their both -
77
donating as well as -acceptor properties. Ganter et al. have recently incorporated Se NMR
spectroscopy as an efficient method for the assessment of the π-acceptor strength of selones.11d
77
By covering a wide range of Se chemical shifts of a series of selone derivatives, they have
reported that with an increase of -acidity led to the downfield shifts of the 77Se NMR signals. It
is worth mentioning that, with various modified synthetic protocols and with their interesting
bonding properties and versatile reactivity, selones have become an important ancillary ligand in
metal based chemistry with respect to their catalysis, antithyroid activity, demercuration activity,
and sensing toward transition metal ions.11e-r
Chart 2. Group 16 adducts of NHC.
Our group has long standing interest on the coordination chemistry and reactivity of
selones.12 In a recent development, we have synthesized a series of selone metal complexes and
demonstrated that these complexes could act as excellent transmetallating agent with stronger σ-
donating ligands like phosphines.12j As an extension of our previous work on selones, this article
also features the synthesis of two new selone based pincer compounds.

Results and Discussion
In order to synthesize the NHN based pincer ligands, N, N´-disubstituted benzotriazolium
bromide salt, 5 was first prepared from benzotriazole by following the reported procedure.8
Synthesis of 5 involved multi-step reaction sequences. In detail, benzotriazole was first treated
with potassium tert-butoxide to afford potassium benzotriaazolate. In subsequent steps,
potassium benzotriaazolate was treated with two equivalents of 2-bromoethanol followed by the
reaction with HBr in presence of acetic acid to afford 1,3-di-(2´-bromoethyl)-triazolium bromide,
5. When compound 5 was treated with N-butylbenzimidazole, 6 (synthesized by the reaction of
benzimidazole with n-butyl bromide in presence of 30% NaOH and TBAB),12a it resulted in the
formation of the desired NHN-based pincer ligand 7, where the chelating arms were
benzimidazole based carbenes (Scheme 1). When the free NHN ligand 7 was treated with
mercuric acetate [Hg(OAc)2], it resulted in the isolation of metal complex 8. From the optimized
geometry (Figure S1, Supporting Information), it was observed that there is no interaction
between the nitrenium ion and Hg centre (vide infra). It is probably due to the large size of the
chelating ring. In an attempt to synthesize NHN ligands which can form six-membered chelating
ring after metalation compound 5 was first treated with ammonium hexafluorophosphate to give
compound 9. Compound 9 was then treated with pyrrolidine/dimethylamine to afford NHN
derivatives 10a and 10b. To explore the coordination chemistry of synthesized NHN pincer
ligand with transition metals, compound 10 was reacted with equimolar amount of copper(I)
iodide in dry dichloromethane. This immediately yielded a precipitate of compound 11. Quantum
chemical computations confirmed the coordination between nitrenium ion and Cu metal centre in
complex 11 (vide infra).

Scheme 1. Synthesis of nitrenium ion based pincer ligands and complexes.
In the 1H NMR spectrum of compound 7, the singlet resonance at 9.37 ppm corresponded
to the two carbene protons. The two multiplets observed in the aromatic region corresponded to
the four benzotriazole protons and eight benzimidazole protons. The two signals observed at 5.61
and 5.27 ppm could be assigned to methylene spacers (-CH2-CH2-) spacer between benzotriazole
and benzimidazole rings. The four signals for n-butyl group were observed in the expected
aliphatic region. In 1H NMR spectrum of compound 8, the disappearance of characteristic signal
for carbene proton at 9.37 ppm indicated the ligation of the free ligand 7 with the metal. The
13
signal for carbene carbon appeared at 141.38 ppm in C NMR spectrum of compound 7. A
13
slight downfield shift (142.96 ppm) was observed in the C NMR spectrum of compound 8
which might be due to the de-shielding effect caused by the σ-donation from the carbene carbon
to the metal center. The CH2 protons attached to nitrenium moiety did not show any change in
chemical shifts for ligand 7 as well as its metal complex 8 (5.61 ppm for 7 and 5.62 ppm for 8).
However, a considerable downfield shift was observed in the chemical shift for CH2 attached to
the carbene moiety of complex 8 (5.50 ppm) as compared to the free ligand, 7 (5.27 ppm). In the
1H NMR spectra of compound 10a and 10b, two sets of peaks were observed in the aromatic
region corresponding to the benzotriazole ring protons. The chemical shifts at 5.00 ppm and 3.18

ppm for compound 10a could be assigned to the methylene spacers. The corresponding chemical
shifts for compound 10b were observed at 5.41 ppm and 3.99 ppm respectively. For compound
10a, the pyrrolidine protons showed two resonances at 2.53 ppm and 1.67 ppm. The
corresponding –NCH3 protons for compound 10b were observed as a single resonance at 2.94
ppm. In compounds 10a and 10b, the anionic entity i.e., the potassium hexafluorophosphate
19

(PF6 ) ion showed two set of F NMR resonances at (-71.31, -72.82 ppm) and (-72.03, -73.54
pp) respectively. The corresponding 31P NMR resonance showed a septet centered at -141.16 and
-144.64 ppm respectively. In the 1H NMR spectrum of metal complex 11, all the signal appeared
broad, which might be attributed to the coordination of the ligand to the metal. All the aliphatic
protons showed considerable downfield shift (5.33, 3.55, 2.94 and 1.78 ppm) as compared to free
19

ligand 10a (5.00, 3.18, 2.53 and 1.67 ppm). The F NMR spectrum for complex 11, PF6 ion
31
showed resonance at -69.21 and -71.10 ppm. The corresponding P NMR resonance showed a
septet centered at -144.24 ppm.
The identity of the new ligands and the corresponding metal complexes could be established by
High Resolution Electrospray Ionization Mass Spectrometry (HRMS). In the mass spectra, taken
in the positive ion mode, the molecular ion peaks at m/z 173.6139 ([M-3Br]3+) (7), 882.1231
(Calc. 882.1235 [M-Br]+) (8), 314.2339 (Calc. 314.2339 [M-PF6]+), (10a) 262.2027 (Calc.
262.2027 [M-PF6]+), (10b), 504.0684 (Calc. 504.0680 [M-PF6]+), (11) substantiated the
formation of the respective compounds. It is worth mentioning that the observed patterns in
HRMS for the compounds were in agreement with the simulated isotopic patterns.
In an attempt to synthesize hybrid NHN ligand where the chelating arm contained soft Te
donor, benzotriazole was treated with 1,2-dibromoethane in presence of NaOH and TBAB to
afford 1-(2´-bromoethyl)-benzotriazole, 12. Compound 12 on reaction with in situ generated
NaTePh afforded tellurated benzotriazol, 13 (Scheme 2). To synthesize NHN ligand, when the
second N-alkylation of compound 13 was attempted with methyliodide, an unexpected
ternisation takes place at tellurium center to afford compound 14 instead of expected hybrid
NHN pincer ligand.

Scheme 2. Attempted synthesis of Te containing hybrid, NHN based pincer ligand and synthesis
of tellurated benzotriazole derivatives, 13 and 14.
1
In the H NMR spectra of compounds 13 and 14, the chemical shifts were in agreement
with the expected values. In detail, the chemical shifts for the benzotriazole ring protons and
phenyl protons for both the compounds appeared in the region 8-7 ppm. For compound 13, the
methylene protons showed resonances at 4.95 and 3.36 ppm respectively. The corresponding
signals for compound 14 were observed at 5.01 and 3.42 ppm respectively. The methyl protons
for compound 14 showed resonance at 2.18 ppm. In 13C NMR spectrum of compound 13,
tellurium satellites are observed for CH2CH2Te at 6.54 and 5.13 ppm (2JC-Te = 705 Hz). The 125Te
NMR (proton coupled) spectrum for 13 showed a triplet at 483.9 ppm (3JTe-H = 95 Hz) because of
13
the coupling with neighboring -CH2- protons. In the C NMR spectrum of 14, a highly shielded
resonance was observed at -22.84 ppm corresponding to Te-CH3. The 125Te NMR signal for
compound 14 is significantly downfield shifted than that of compound 13 and appeared at 606.3
ppm due to the presence of positive charge on the tellurium atom. In the HRMS spectrum of
compound 13, the molecular ion peak observed at m/z 376.0062 corresponded to [M+Na]+
species (Calc. 376.0064). In the HRMS spectrum of compound 14, the molecular ion peak
observed at m/z 368.0405 corresponded to the [M-I]+ species (Calc. 368.0402).
X-ray Crystallographic Studies
The molecular structure of 10a is shown in figure 2(a). The asymmetric unit contains two
molecules of 10a with one additional water of crystallization. Out of the two molecules present
in the asymmetric units, one of the pyrroldine nitrogen atoms of one molecule undergoes
protonation while other nitrogen atoms are unaffected. The protonation might be occurred due to
the presence of traces of HBr from the previous reaction step. The molecule with protonated

pyrrolidine side arm has been considered here for discussion. In the molecular structure of 10a,
the benzotriazole ring and two the methylene carbons attached to the triazole nitrogen atoms
reside in the same plane. Interestingly, the molecule adopts a conformation in which the two
flanking arms are directed in the same direction with respect to the central benzotriazoline ring.
A water molecule was observed to be trapped between both the flanking arms wherein the one of
its H-atoms was involved in H-bonding to one of the pyrrolidine N-atom with a distance of 1.999
Å. At the same time, oxygen atom is involved in hydrogen bonding with N4A-H hydrogen with a
distance of 1.769 Å.
(b)
(a)
Figure 2. ORTEP diagrams of (a) compound 10a and (b) compound 10b plotted with 50%
probability thermal ellipsoids.
The molecular structure of compound 10b is shown in Figure 2(b). The molecular structure of
10b is similar to 10a with respect to the orientation of the flanking arms around the central plane.
However, both the amine nitrogen atoms from the side arms undergo protonation and the total of
three positive charges on the molecule are balanced by one bromide and two hexafluorophospate
counter anions. Like compound 10a, there is also a water of crystallisation present in compound
10b. The bromide ion is involved in hydrogen bonding to both -N-H atoms of the side arms with
distance of 2.489 Å (N4-H···Br) and 2.425 Å (N5-H···Br). Again, the bromide ion is also
involved in hydrogen bonding with one of the hydrogen atoms of the water molecule with a
distance of 2.616Å.

The ORTEP views of compounds 13 and 14 are shown in Fig 3(a) and Fig 3(b) respectively.
Like the previous two compounds, in the molecular structures of 13 and 14, the benzotriazole
ring and the methylene carbon from the side arm are positioned in the same plane. In compound
13, the geoemtry around Te center is V-shaped with C8-Te1-C9 bond angle of 92.6(2)°. The Te-
C9 bond distance is 2.124(6) Å, which is significantly shorter than the Te-C8 bond distance of
2.153(4) Å. Both these distnaces are in good agreement with related compound, namely 1-(4-
methoxyphenyltelluromethyl)-1H-benzotriazole[Te-C(aryl) = 2.117(3)Å; Te-C(alkyl) = 2.159(3)
Å].13 In case of compound 14, the geometry around Te atom is distorted trigonal pyramidal
with C8-Te1-C15, C8-Te1-C9 and C15-Te1-C9 bond angle of 90.79(13)°, 97.67(13)° and
97.05(12)° repectively. The Te-C9 bond distance is 2.129(3) Å, whereas the Te-C8 bond
distance is 2.165(3) Å. Both distances are comparable with the corresponding distances observed
in 13. The Te1-C15 distance is observed to be 2.137(3) Å. Interestingly, in compound 14, two
week interactions from Te center; one intramolecular interactions with triazolium nitrogen, N2
with Te1···N2 distance of 2.919(3) Å and one intermolecular interaction with iodide anion with
Te1···I1 distance of 3.5010(4) Å, are observed.
(a)
(b)
Figure 3. ORTEP diagram of (a) compound 13 and (b) compound 14 plotted with 50%
probability thermal ellipsoids.
Computational Studies
Since single crystals could not be obtained for the complexes of nitrenium ions, to get a better
understanding of the nature of the nitrenium ion-metal bond, electronic structure calculations

have been carried out using Gaussian09 package 14 by employing DFT method. Geometry
optimizations were carried out using MPW1PW91 method,15 6-311g(d)16 basis set for C, H, N,
Br, P, F and Se, Lanl2dz17 basis set for Hg and TZVP18 basis set for Cu. In the optimized
structure of compound 8, the carbene to mercury coordination is observed, however, there is no
interaction between nitrenium ion and Hg centre (Figure S1, Supporting Information). In the
optimized structure of compound 11, N8-Cu, N12-Cu and N15-Cu bond lengths are 2.17920,
2.19028 and 2.19989 Å respectively, which are shorter than the sum of covalent radii of copper
(1.52 Å) and nitrogen (0.68 Å). It indicates that there is a proper coordination between nitrenium
ion and copper metal center (N→Cu) (Figure 4a). To further support the presence of N→Cu
bond, Atom in Molecule (AIM) analysis was carried out by using AIM200019 on the wave
function file generated from Gaussian09. Topological properties of electron density at the N···M
bond critical point (bcp) were investigated using Bader’s theory of atoms in molecule (AIM) as
implemented in AIM2000 package. Distinct bond critical points associated with N-M interaction
were identified in all compounds, thus indicating the presence of N-M interaction. The
parameters obtained from AIM are in full agreement with those obtained from NBO analysis.20
The values of bond critical point (ρ), Laplacian (∇2) and total energy density (H) and of the
N→Cu are given in Table 1. In compound 11, the total electron density at N8···Cu bond critical
point is 0.054, which is very close to N12···Cu (0.057) and N15···Cu (0.059) indicating that
N8···Cu, N12···Cu and N15···Cu bonds are real coordination bonds. This observation is further
supported by NBO analysis. From NBO analysis, it can be observed that in compound 11 there is
donation of lone pair from N8, N12 and N15 to LP* of Cu to form formal coordination bonds.
The energies associated with these interactions are 14.6, 10.4 and 12.6 kcal/mol respectively.
These indicate the presence of similar bonds between all three nitrogens and copper. The energy
values indicating the possible interaction of N8, N12 and N15 with Cu, are given in Table
S2(SI).

Table 1. Total electron density (ρbcpN···M), Laplacian value (∇2bcpN···M) and total energy density
(HbcpN···M) at bond critical points of N-M bonds in compound 11.
2
Bond ρbcpN···M
HbcpN···M
0.0044
0.0076
0.0083
∇
bcpN···M
N8-Cu
0.054
-0.071
-0.065
-0.067
N12-Cu 0.057
N15-Cu 0.059
(a)
(b)
Figure 4. (a) Optimized structure and (b) molecular Graph of compound 11 showing the bond
critical points.
Selones 18a-18b were synthesised in ca. 70-75% yield by following the reported
procedure (Scheme 3). First benzimidazole (15) was N-alkylated by 2-bromo-1-ethanol/3-bromo-
1-propanol in presence of 30% NaOH solution and
(tetrabutylammonium bromide, TBAB). Subsequent quaternization of 16a-16b by another
equivalent of 2-bromo-1-ethanol/3-bromo-1-propanol afforded N,N´-disubstituted
a
phase-transfer catalyst
benzimidazole, 17a-17b. These benzimidazolium salts when reacted with in situ generated
Na2Se2 in presence of potassium tert-butoxide at room temperature, afforded selones, 18a-18b.

Scheme 3. Synthesis of selones 22 -23.
1
Compounds 18a-18b were characterized by 1H NMR spectroscopy. The H NMR signal for the
acidic NCHN proton present in salts 17a and 17b were absent in the corresponding chalcogenone
77
derivatives. In Se NMR spectrum, compound 18a showed a single resonance at 66.4 ppm,
while a chemical shift of 33.2 ppm was observed for compound 18b. Both these chemical shifts
are in agreement with the values reported for similar benzimidazole based selone derivatives.12a-b
The single crystals of compound 18a were obtained by slow evaporation of a chloroform/hexane
solution of the compound. In the molecular structure of 18a (Figure 4), the benzimidazole ring,
selenium atom and the methylene carbon connected to the N atoms of the imidazole ring, are in
the same plane. The C and Se atom sit on the crystallographically imposed C2 axis of symmetry,
wherein the two O-atoms of the flanking arms are trans-oriented with respect to the core plane.
The geometry around the carbene carbon is planar trigonal. The C-Se distance is found to be
1.834 (4) Å, which is in accordance with C-Se bond length of similar compounds reported in the
literature.12a This bond distance is on the longer side for a double bond but shorter than expected
for a C-Se single bond. However, a detailed DFT calculation performed by Manjare et al.,12a
wherein Wiberg bond indexes and Natural Population Analysis (NPA) have been taken in to
account, unambiguously inferred that the donor-acceptor bonding mode in C-Se bond not only
comprises of a σ donation from the carbene, but also significant π back-bonding from selenium,
which confirmed the double bond character of C-Se bond.

Figure 4. Molecular structure of selone, 18a.
Conclusion
In summary, we have successfully synthesized new NNN- and CNC type N-heterocyclic
nitrenium ion (NHN) within a tridentate pincer scaffold. However, when the synthesis of hybrid
NHN ligand where the chelating arm contains soft Te donor is attempted, methylation took place
at Te center instead of at triazole nitrogen and afforded telluronium cation. The molecular
structure of the synthesized NHN ligands reveal that in both the cases, the triazole ring and the
methylene carbons connected to the triazole nitrogen atoms are in the same plane, while both the
flanking arms rest in the same side of the core plane. The reactions of the synthesized nitrenium
ions with d10 metal precursors have also been explored. The common spectroscopic techniques
13
(1H, C NMR), mass spectrometry authenticated the ligation of the nitrenium ions to the metal
centre. However, due to the unavailability of the single crystal structures of the same, the direct
coordination of the metal to triazolium centre remains obscure. Nevertheless, Natural Bond
Order (NBO) calculations and Atoms in Molecules (AIM) analyses adequately substantiate the
presence of interaction between triazolium N with the Cu metal centre.
Experimental Section
All the manipulations were executed under a nitrogen or argon atmosphere using standard
Schlenk techniques unless otherwise noted. Solvents were purified and dried by standard

1
11
13
procedures and were distilled prior to use. H (400 MHz, 500 MHz), B NMR (128 MHz), C
19
31
77
NMR (100.56 MHz, 126 MHz), F NMR (376 MHz), P NMR (161 MHz, 202 MHz), Se
NMR (76 MHz, 95 MHz) and 125Te (126 MHz, 158 MHz) nuclear magnetic resonance spectra
were recorded on Bruker AV 400 and/or Bruker AV 500 spectrometers at 25 °C. Chemical shifts
1
31
are cited with respect to Me4Si as an internal standard for H and 13C, 85% H3PO4 for P,
19
77
tetrafluorotoluene for F, Me2Se for Se and Me2Te for 125Te as external standards. Elemental
analyses were performed on a Carlo Erba Model 1106 elemental analyser. The ESI mass spectra
were recorded on a Q-tof micro (YA-105) mass spectrometer. The single crystal X-ray
diffraction measurements were performed on a Rigaku Saturn 724 diffractometer and an Oxford
Diffraction Gemini diffractometer. The data were corrected for Lorentz, polarization, and
absorption effects. The structures were determined by routine heavy-atom methods using
SHELXS 9721 and Fourier methods and refined by full-matrix least squares with the anisotropic
non-hydrogen atoms and hydrogen atoms with fixed isotropic thermal parameters of 0.07 Å2
using the SHELXL 9722 program. The hydrogens were partially located from difference electron
density maps, and the rest were fixed at predetermined positions. Scattering factors were from
common sources.23
Synthesis of compound 7 A mixture of compound 5 (1.00 g, 2.42 mmol) and n-
butylbenzimidazole (6) (0.84 g, 4.83 mmol) in 30 mL dry 1,4-dioxane was stirred at 90 oC for 24
h. A white precipitate of compound 7 appeared. The precipitate was washed with ethyl acetate
and diethyl ether. The product was purified by recrystallization from methanol. Yield: 1.76 g
1
(96%). H NMR (400 MHz, D2O):  (ppm) 9.37 (s, 2H), 7.93-7.86 (m, 6H), 7.77-7.64 (m, 6H),
5.61 (t, J = 5.44 Hz, 4H), 5.27 (t, J = 5.44 Hz, 4H), 4.35 (t, J = 7.30 Hz, 4H), 1.77 (q, J = 7.42
13
Hz, 4H), 1.21 (sext, J = 7.56 Hz, 4H), 0.87 (t, J = 7.36 Hz, 4H); C NMR (100 MHz, D2O): 
(ppm) 141.38 (NCN), 135.36, 133.10, 131.28, 130.73, 127.94, 127.80, 114.17, 112.83, 112.50,
50.43, 47.40, 45.44, 30.54, 19.16, 12.84; ESI-MS (positive mode): [(C32H40N7)-H]3+ m/z =
173.6139 (observed), 173.7750 (calculated).
Synthesis of compound 8 Compound 7 (0.20 g, 0.26 mmol) was dissolved in dry ethanol and to
this was added to a solution of mercuric acetate (0.08 g, 0.26 mmol) in dry ethanol. A white
precipitate appeared soon after the addition. The reaction mixture was kept for stirring for 12 h.
The precipitate was filtered and washed with ethanol to get pure compound 8 Yield: 0.18 g

1
(72%). H NMR (400 MHz, DMSO):  (ppm) 8.44-8.42 (m, 2H), 8.04-8.01 (m, 4H), 7.77-7.68
(m, 4H), 5.62 (t, J = 5.93 Hz, 4H), 5.50 (t, J = 5.93 Hz, 4H), 4.59 (t, J = 7.52 Hz, 4H), 1.56 (q, J
13
= 7.57 Hz, 4H), 1.31 (sext, J = 7.61 Hz, 4H), 0.87 (t, J = 7.25 Hz, 6H); C NMR (100 MHz,
DMSO):  (ppm) 142.96 (NCN), 135.10, 131.60, 130.90, 130.60, 126.92, 113.89, 113.71,
113.67, 49.96, 46.58, 44.95, 30.56, 19.01, 13.44; ESI-MS (positive mode): [C32H38N7Br2Hg]+
m/z = 882.1231 (observed), 882.1234 (calculated).
Synthesis of compound 9 Compound 5 (1.00 g, 2.42 mmol) was dissolved in 5 ml water and
ammonium hexaflorophosphate (0.43 g, 2.66 mmol) was added to it. An immediate precipitation
of compound 9 occurred, which was separated by filtration followed by washing with 2 ml
water. Yield: 1.16 g (94%). 1H NMR (400 MHz, CDCl3):  (ppm) 8.52-8.50 (m, 2H), 8.07-8.05
13
(m, 2H), 5.59 (t, J = 5.40 Hz, 4H), 4.19 (t, J = 5.40 Hz, 4H); C NMR (100 MHz, CDCl3): 
(ppm) 134.86, 131.57, 114.29, 52.87, 29.81; 19F NMR (100 MHz, CDCl3):  (ppm) -73.05, -
74.58; 31P NMR (100 MHz, CDCl3):  (ppm) -140.70 (sep), ESI-MS (positive mode):
[C10H12N3Br2]+ m/z = 333.9374 (observed), 333.9372 (calculated).
Synthesis of compound 10a Compound 9 (0.50 g, 1.04 mmol) was suspended in toluene and
pyrrolidine (0.19 g, 2.61 mmol) was added to it. Slowly compound 9 gets dissolved and the color
of the solution turns yellow. After stirring at rt for 24 h a light yellow precipitate of pure
1
compound 10a appeared, which was separated by filtration.Yield: 0.48 g (67%). H NMR (400
MHz, CDCl3):  (ppm) 8.08-8.03 (m, 2H), 7.84-7.80 (m, 2H), 5.00 (t, J = 5.85 Hz, 4H), 3.18 (t, J
13
= 5.85 Hz, 4H), 2.53 (t, J = 3.16 Hz, 6H), 1.67 (t, J = 3.16 Hz, 4H); C NMR (100 MHz,
19
CDCl3):  (ppm) 135.54, 131.91, 113.98, 54.27, 54.14, 51.62, 24.04; F NMR (100 MHz,
CDCl3):  (ppm) -72.31, -72.82; 31P NMR (100 MHz, CDCl3):  (ppm) -141.16 (sep), ESI-MS
(positive mode): [C18H28N5]+ m/z = 314.2339 (observed), 314.2339 (calculated).
Synthesis of compound 10b Compound 10b was prepared using the method similar to that used
for compound 10a. The reagents used were compound 9 (0.50 g, 1.04 mmol) and diethylamine
1
(0.12 g, 2.61 mmol). Yield: 0.23 g (53%). H NMR (400 MHz, CDCl3):  (ppm) 8.29-8.28 (m,
13
2H), 8.09-8.08 (m, 2H), 5.41 (t, J = 5.85 Hz, 4H), 3.99 (t, J = 5.85 Hz, 4H), 2.94 (s, 12H); C
NMR (100 MHz, CDCl3):  (ppm) 137.11, 133.60, 118.32, 114.63, 55.03, 48.05, 43.86; 19F
NMR (100 MHz, CDCl3):  (ppm) -72.03, -73.54; 31P NMR (100 MHz, CDCl3):  (ppm) -144.64
(sept), ESI-MS (positive mode): [C14H24N5]+ m/z = 262.2027 (observed), 262.2026 (calculated).

Synthesis of compound 11 Compound 10a (0.50g, 1.09 mmol) was dissolved in dry
dichloromethane and to it was added cuprous iodide (0.21g, 1.09 mmol). A yellow precipitate of
the product appeared after stirring the reaction mixture at rt for 30 min. The precipitate was
1
soluble in CH3CN and DMSO. Yield: 0.48 g (68%). H NMR (400 MHz, CH3CN):  (ppm)
8.48-8.46 (m, 2H), 8.06-8.04 (m, 2H), 5.33 (broad, 4H), 3.55 (broad, 4H), 2.94 (broad, 8H), 1.78
(broad, 8H); 13C NMR (100 MHz, CH3CN):  (ppm) 134.03, 131.44, 113.17, 51.83, 30.10,
19
19.03, 12.71; F NMR (100 MHz, CDCl3):  (ppm) -69.21, -71.10; 31P NMR (100 MHz,
CDCl3):  (ppm) -144.24 (sep), ESI-MS (positive mode): [C18H28N5CuI]+ m/z = 504.0684
(observed), 504.0680 (calculated).
Synthesis of compound 13 Diphenyl ditelluride (0.45g, 1.11 mmol) was dissolved in dry
ethanol in N2 atmosphere. Two equivalents of NaBH4 (0.09g, 2.22 mmol) were added to it. The
reaction mixture started to become colorless and it was stirred at rt for 30 min. Then compound
12 (0.50g, 2.22 mmol) was added to the colorless reaction mixture. The reaction mixture was
further stirred at rt for 2 hr, worked up with dichloromethane to get pure compound 13. Yield:
0.54 g (76%). 1H NMR (400 MHz, CDCl3):  (ppm) 8.02-8.01 (m, 1H), 7.74-7.73 (m, 2H), 7.45-
7.42 (m, 1H), 7.35-7.31 (m, 3H), 7.23-7.20 (m, 2H), 4.95 (t, J = 7.85 Hz, 4H), 3.36 (t, J = 7.85
Hz, 4H); 13C NMR (100 MHz, CDCl3):  (ppm) 146.01, 139.13, 132.70, 129.62, 128.51, 127.40,
124.00, 120.17, 110.33, 109.18, 50.25, 6.54, 5.84, 5.13; 125Te NMR (126 MHz, CDCl3):  (ppm)
484.9 (t); ESI-MS (positive mode): [(C14H13N3Te)+Na]+ m/z = 376.0062 (observed), 376.0064
(calculated).
Synthesis of compound 14 Compound 13 (0.20g, 0.57 mmol) was dissolved in diethyl ether.
Methyl iodide (0.08g, 0.57 mmol) was added to it. The reaction mixture was stirred in closed
vessel for 48 h. The white precipitate was filtered off followed by the washing with
dichloromethane to remove the unreacted starting material. The product was further purified by
1
recrystallization from methanol. Yield: 0.26 g (91%). H NMR (400 MHz, CDCl3):  (ppm)
7.94-7.92 (m, 1H), 7.76-7.63 (m, 2H), 7.59-7.52 (m, 1H), 7.51-7.43 (m, 1H), 7.36-7.33(m, 1H),
13
7.28-7.26 (m, 3H), 5.01(m, 4H), 3.42 (m, 4H), 2.18 (s, 3H); C NMR (100 MHz, CDCl3): 
(ppm) 139.22, 130.29, 128.90, 128.10, 124.84, 120.23, 118.25, 111.00, 50.74, 7.12; 125Te NMR
(126 MHz, CDCl3):  (ppm) 606.2 (s); ESI-MS (positive mode): [C15H16N3Te]+ m/z = 368.0405
(observed), 368.0402 (calculated).

Synthesis of compound 16a To a round-bottomed flask containing benzimidazole (15) (10.00 g,
84.75 mmol), was added 30% aq. NaOH (66 mL) and tetrabutylammonium bromide 1.0 g
followed by 2- bromoethanol (6 mL, 6.00 mol) at rt. The mixture was stirred at rt for 3 h. Then it
was poured in to 100 ml water and extracted with chloroform (40 mL × 3), The organic layer
was separated, dried over anhydrous Na2SO4 and was evaporated to dryness to give a red
1
coloured liquid. H NMR (500 MHz, CDCl3):  (ppm) 7.73 (s,1H), 7.48(d, 1H), 7.33(d, 1H),
13
7.19(m, 2H), 4.2 (t,3H), 4.0 (t,3H); C NMR (125MHz, CDCl3):  (ppm) 130.8, 130.3, 120.3,
110.9, 110.6, 110.0, 140.4., 60.0, 40.8.
Synthesis of compound 17a A solution of 2-bromoethanol (2.9 mL, 5.07 g, 40.00 mmol) and
compound 16a (6.5 g, 40.00 mmol) in 1, 4-dioxane (40 mL) were refluxed under nitrogen
atmosphere for 3 h. After the completion of reaction, the solvent was removed and the solid
residue was washed with ethyl acetate ( 3×20 mL) to get compound 17a as a white solid and was
used for the next step without any further purification.
Synthesis of selone 18a: To salt 17a (1.13 g, 3.80 mmol) in THF, was added in situ generated
Na2Se2 at rt under nitrogen atmosphere and the reaction mixture was stirred for 2h at rt. Solid
KOtBu (0.43 g, 3.80 mmol) was added to the reaction mixture and stirred further for additional
5-7 h. After completion of reaction, the reaction was quenched by adding water (50 mL), and
extracted with dichloromethane (3×25 mL), dried over Na2SO4, and the solvent is removed in
1
vacuo to afford selone 18a. H NMR (500 MHz, CDCl3):  (ppm) 7.38 (m, 2H), 7.30 (m, 2H),
77
4.64 (t, 2H), 4.11 (t, 2H); Se NMR (76MHz, CDCl3): δ (ppm) 66.4 ppm. ESI-MS (positive
mode): [(C11H14N2O2Se)+Na]+ m/z = 309.0121 (observed), 309.0118 (calculated).
Synthesis of compound 17b: In a round-bottom flask containing benzimidazole (15) (5.00 g,
42.37 mmol), was added 30% aq. NaOH (33 mL) and tetrabutylammonium bromide (0.50 g),
followed by the addition of 3- bromopropanol (3.75 mL, 42.37 mol) at rt. The mixture was
stirred at rt for 3 h, henceforth the reaction mixture was poured in to 100 ml water and extracted
with chloroform (40 mL × 3). The organic layer was separated, dried over anhydrous Na2SO4
and was evaporated to dryness to give a red colored liquid of compound 16b. The compound was
used further without purification. A solution of 3-bromopropanol (3.15 g, 22.71 mmol) and

compound 16b (4.00 g, 22.71 mmol) in 1, 4-dioxane (40 mL) was refluxed under nitrogen
atmosphere for 3 h. After the completion of reaction, the solvent was removed and the solid
residue was washed with ethyl acetate ( 3×20 mL) to get compound17b as a white solid and was
used for the next step without any further purification.
Synthesis of selone 18b: To salt 17b (1.37 g, 4.00 mmol) in THF, was added in situ generated
Na2Se2 at rt under nitrogen atmosphere and the reaction mixture was stirred for 2h at rt. KOtBu
(0.60 g, 4.00 mmol) was added to the reaction mixture and stirred further for additional 5-7 h.
After completion of reaction, the reaction was quenched by adding water (50 mL), and extracted
with dichloromethane (3×25 mL), dried over Na2SO4, and the solvent was removed in vacuo
1
which afforded the title compound as an off white solid. H NMR (500, MHz, MeOD):  (ppm)
13
8.2(s, 1H), 6.8(m, 2H), 6.4(m, 2H), 3.5(2H), 2.3(4H), 1.9(4H), 0.9(4H); C NMR (125MHz,
CDCl3):  (ppm) 141.03, 131.47, 126.98, 113.28, 58.24, 44.39, 30.76, 77Se NMR (76MHz,
CDCl3): δ (ppm) 33.2 ppm. ESI-MS (positive mode): [(C13H18N2O2Se)+Na]+ m/z = 337.0437
(observed), 337.0431 (calculated).
Supporting Information
NMR spectra, ESI-MS spectra, single crystal X-ray analysis are given as Supporting
Information; X-ray structural parameters are given in Table S1 (10a and 10b, 13, 14 and 18a).
CCDC 1870798 - 1870802 (Compounds 10b, 18a, 13, 10a and 14 respectively) contain the
supplementary crystallographic data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre.
Author Information
Corresponding Author * chhbsia@chem.iitb.ac.in
ORCID
Harkesh B. Singh: 0000-0002-0403-0149
Sangeeta Yadav: 0000-0001-5203-7073

Rajesh Deka: 0000-0002-9460-1784
Acknowledgements
H. B. S. is grateful to the Department of Science and Technology, New Delhi for J. C. Bose
Fellowship.
Notes
The authors declare no conflict of interest.
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Highlights


New NNN- and CNC type N-hetrocyclic nitrenium ions (NHN) within tridentate pincer scaffold
are reported.
The attempted synthesis of hybrid NHN ligand containing soft Te atom in the auxiliary arms
results in the formation of telluronium cation where the N atom from the triazole ring makes five
membered chelating ring by intramolecular N···Te secondary bonding interaction.
The Natural Bond Order (NBO) calculations and Atoms in Molecules (AIM) analyses on


the metal complexes adequately substantiate the presence of interaction between
triazolium N with metal centre.
Synthesis of two new selone based OSeO type pincer ligands is reported.