Platinum-Mediated Activation of Coordinated Organonitriles by Telluroethers in Tetrahydrofuran: Isolation, Structural Characterization, and Density Functional Theory Analysis of Intermediate Complexes

Article abstract of DOI:10.1021/acs.inorgchem.5b02024

The reactions of [PtCl₂(NCR)₂] with telluroethers (ArAr′Te) in organic solvents have been investigated. The reactions in dichloromethane yield [PtCl₂(TeArAr′)₂], while those in tetrahydrofuran (THF) give different products depending on the steric demands of the aryl groups on tellurium, the molarity of the reactants, and the reaction conditions. The reactions between [PtCl₂(PhCN)₂] and TeArAr′ in 1:1 molar ratio at room temperature in THF yield several products, like [PtCl₂(TeArAr′)₂] (Ar/Ar′ = Ph/Ph, o-tol/Mes, Mes/Mes), [PtCl₂(PhCN){NC(O)Ph[TeMes(o-tol)]}], and [PtCl₂{NC(O)Ph(TeMes₂)}₂]. The reaction with TeMes₂ in refluxing THF gave [PtCl₂{NC(Ph)C₄H₇O}{NC(O)Ph(TeMes₂)}] and [PtCl(TeMes₂){Te(Mes)CH₂C₆H₂Me₂}], depending on the duration of heating. Reaction of [PtCl₂(PhCN)₂] with TeArMes afforded [PtCl₂(TeArMes)₂] (Ar = Ph, o-tol, and Mes), the formation of which decreased with increasing steric demand of the Ar group, together with [PtCl₂{NC(O)Ph(TeArMes)}₂]. The telluroether in the latter binds to nitrogen, and tellurium exists in the formal oxidation state of +4 (from XPS). The tellurium in these complexes exhibits secondary interactions with platinum (J(¹⁹⁵Pt-¹²⁵Te) = 309-347 Hz) and with the carbonyl oxygen. These complexes slowly dissociate in solution to give [PtCl₂(TeMesAr){NC(O)Ph(TeMesAr)}], finally leading to the formation of [PtCl₂(TeMesAr)₂]. Molecular structures of trans-[PtCl₂(PhCN){NC(O)Ph[TeMes(o-tol)]}], trans-[PtCl₂{NC(O)Ph(TeMes₂)}₂], trans-[PtCl₂{NC(Ph)C₄H₇O}{NC(O)Ph(TeMes₂)}], trans-[PtCl₂{NC(O)Ph[TeMes(o-tol)]}₂], trans-[PtCl₂(TeMes₂){NC(O)Ph(TeMes₂)}], trans-[PtCl₂{NC(O)Me(TeMes₂)}₂], and [PtCl(Te-o-tol){NC(O)Ph}₂] have been unambiguously established by single-crystal X-ray diffraction analyses. Density functional theory calculations for some of the complexes were performed, and geometrical parameters are in good agreement with the values obtained from X-ray analyses.

Full text of DOI:10.1021/acs.inorgchem.5b02024

Article
pubs.acs.org/IC
Platinum-Mediated Activation of Coordinated Organonitriles by
Telluroethers in Tetrahydrofuran: Isolation, Structural
Characterization, and Density Functional Theory Analysis of
Intermediate Complexes
Siddhartha Kolay,† Amey Wadawale,† Sandeep Nigam,† Mukesh Kumar,‡ Chiranjib Majumder,†
Dasarathi Das,† and Vimal K. Jain*,†
†Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India
‡Solid State Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India
S
* Supporting Information
ABSTRACT: The reactions of [PtCl2(NCR)2] with telluroethers
(ArAr′Te) in organic solvents have been investigated. The reactions in
dichloromethane yield [PtCl2(TeArAr′)2], while those in tetrahydro-
furan (THF) give different products depending on the steric demands
of the aryl groups on tellurium, the molarity of the reactants, and the
reaction conditions. The reactions between [PtCl2(PhCN)2] and
TeArAr′ in 1:1 molar ratio at room temperature in THF yield several
products, like [PtCl2(TeArAr′)2] (Ar/Ar′ = Ph/Ph, o-tol/Mes, Mes/
Mes), [PtCl2(PhCN){NC(O)Ph[TeMes(o-tol)]}], and [PtCl2{NC-
(O)Ph(TeMes2)}2]. The reaction with TeMes2 in refluxing THF gave
[PtCl2{NC(Ph)C4H7O}{NC(O)Ph(TeMes2)}] and [PtCl(TeMes2)-
{Te(Mes)CH2C6H2Me2}], depending on the duration of heating.
Reaction of [PtCl2(PhCN)2] with TeArMes afforded [PtCl2-
(TeArMes)2] (Ar = Ph, o-tol, and Mes), the formation of which decreased with increasing steric demand of the Ar group,
together with [PtCl2{NC(O)Ph(TeArMes)}2]. The telluroether in the latter binds to nitrogen, and tellurium exists in the formal
oxidation state of +4 (from XPS). The tellurium in these complexes exhibits secondary interactions with platinum
(J(195Pt−125Te) = 309−347 Hz) and with the carbonyl oxygen. These complexes slowly dissociate in solution to give
[PtCl2(TeMesAr){NC(O)Ph(TeMesAr)}], finally leading to the formation of [PtCl2(TeMesAr)2]. Molecular structures of trans-
[PtCl2(PhCN){NC(O)Ph[TeMes(o-tol)]}], trans-[PtCl2{NC(O)Ph(TeMes2)}2], trans-[PtCl2{NC(Ph)C4H7O}{NC(O)Ph-
(TeMes2)}], trans-[PtCl2{NC(O)Ph[TeMes(o-tol)]}2], trans-[PtCl2(TeMes2){NC(O)Ph(TeMes2)}], trans-[PtCl2{NC(O)Me-
(TeMes2)}2], and [PtCl(Te-o-tol){NC(O)Ph}2] have been unambiguously established by single-crystal X-ray diffraction
analyses. Density functional theory calculations for some of the complexes were performed, and geometrical parameters are in
good agreement with the values obtained from X-ray analyses.
Telluroether complexes of platinum group metals have been
known for nearly a century, [PtCl2(TeBz2)2] being the first
complex isolated by Fritzmann14 in 1915, and later Chatt and
co-workers15,16 investigated with Et2Te and Pr2Te complexes.
The palladium/platinum complexes are usually isolated either
by reaction between M′2MCl4 and a telluroether in water (eq
1)17−20 or by treatment of [MCl2(R′CN)2] (R′ = Me or Ph)
with a telluroether in an organic solvent (dichloromethane,
DCM (CH2Cl2), or tetrahydrofuran, THF)20−23 (eq 2). The
substitution reaction in the latter is believed to involve attack of
the telluroether at the metal center.23
INTRODUCTION
■
During the past two decades or so, organotellurium chemistry
has made great strides in diverse areas, with applications in
organic synthesis1 and organocatalysis,2 as metal complexes in
catalysis,3 in ligand chemistry,4−7 as precursors for metal
tellurides,8 and in pharmacology.9−11 Recent developments in
the coordination chemistry of tellurium ligands have defied the
general belief that it would be similar to that of sulfur and
selenium.12 Of late, not only have several dissimilarities
between tellurium coordination chemistry and that of sulfur/
selenium been recognized, but also numerous unprecedented
results have been reported. Isolation of [Pt(Te)-
(TeC5H4N)2(PPh3)], containing bare Te0 as a ligand, from
the reaction of Pt(PPh3)4 with py2Te2 is an example of
unprecedented formation of such complexes.13
H2O
M′2MCl4 + 2TeAr2 ⎯⎯⎯→ [MCl2(TeAr2)2] + 2M′Cl
(1)
Received: September 1, 2015
© XXXX American Chemical Society
A
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Scheme 1. Reactions between [PtCl2(PhCN)2] and Te(Ar)Mes in 1:1 Stoichiometry in THF
Scheme 2. Reactions between [PtCl2(PhCN)2] and Te(Ar)Mes in 1:2 Stoichiometry in THF at Room Temperature
earlier,20−23 to our surprise, with a bulky telluroether (e.g.,
TeMes2) formation of other intermediate complexes could be
detected by 125Te NMR spectroscopy. This led us to examine
these reactions systematically by varying solvent, molarity of the
reactants, steric demands of the organic groups on tellurium,
and temperature. The results of this work are reported herein.
[MCl2(R′CN)2] + 2TeAr2
organic solvent
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ [MCl2(TeAr2)2] + 2R′CN
(2)
To study cycloplatination of telluroether ligands, recently we
have isolated [PtCl2(TeArAr′)2] complexes by employing the
reaction between an aqueous solution of K2PtCl4 and
telluroether in an acetone mixture (eq 1).24 Since the
separation of the final products from the biphasic reaction
medium was a tedious process, we thought to employ a
reaction route involving [PtCl2(PhCN)2] (eq 2) and telluro-
ether in an organic solvent. While the reaction with simple
telluroethers gave the desired products, as has been reported
RESULTS AND DISCUSSION
■
Reactions of [PtCl2(PhCN)2] (1a) with telluroethers TeArAr′
(2) in 1:2 stoichiometry in DCM over 48 h afforded the
expected cis/trans-[PtCl2(TeArAr′)2] (3) in 60−83% yield as
isolated from the reaction of K2PtCl4 with the telluroether in
water−acetone mixture. With asymmetric telluroethers, dia-
B
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Figure 1. 125Te NMR spectra of a reaction between [PtCl2(PhCN)2] and TeMes2 in 1:2 molar ratio in THF monitored with time: (a) 24 h, (b) 3 d,
and (c) 7 d. Spectra were recorded in CDCl3.
stereomers are formed. As the steric demand of organic group
on tellurium increases, the reactions tend to be slower. Thus, in
the case of TeMes2, unreacted [PtCl2(PhCN)2] was noted in
solution by 195Pt NMR spectroscopy even after 48 h of
reaction.
benzonitriles, trans-[PtCl2{NC(O)Ph(TeMes2)}2] (5), as a
major fraction (see later for structure). When this reaction was
carried out in refluxing THF, different products were isolated,
depending on the duration of refluxing. The reaction mixture
on refluxing for 30 min yielded a single product, trans-
[PtCl2{NC(Ph)C4H7O}{NC(O)Ph(TeMes2)}] (6; see later
for structure) wherein one of the coordinated benzonitrile is
activated by THF molecule (C−H ortho to oxygen) while the
other coordinated benzonitrile is attacked by the telluroether.
When refluxing prolonged for 3 h, a mixture of products were
formed which were separated using diethyl ether. The ether
soluble component was characterized by NMR spectroscopy as
cycloplatinated complex [PtCl(TeMes2){Te(Mes)-
CH2C6H2Me2}] (7) while the ether insoluble part contained
[PtCl2(PhCN)2] (1a) and [Pt2Cl2(μ-Cl)2(TeMes2)2] (8) as
confirmed by 125Te and 195Pt NMR spectroscopy. Recently we
have described the formation of 7 from 3e in refluxing THF.24
Having examined the reactions of [PtCl2(PhCN)2] (1a) with
TeArMes in 1:1 stochiometry, it was imperative to assess the
reactivity with 1:2 Pt to Te ratio (Scheme 2). The reaction of
[PtCl2(PhCN)2] with TePhMes in 1:2 stoichiometry in THF at
room temperature afforded expected complex 3b. The reaction
of Te(o-tol)Mes with [PtCl2(PhCN)2] gave two products, viz.
[PtCl2{Te(o-tol)Mes}2] (3d) as a minor fraction and a
complex formed by the attack of telluroether on both the
coordinated benzonitrile trans-[PtCl2{NC(O)Ph{Te(o-tol)-
Mes}}2] (9; see later for structure) as a major constituent.
The 9 decomposes slowly in solution. Thus, when 9 was left for
Since the reactions involving bulky telluroethers were
sluggish in DCM, another commonly used solvent, viz. THF
was used. Surprisingly the reactions were more complex giving
several products formed by the initial attack of telluroether on
the coordinated benzonitrile rather than the platinum center.
To understand the reaction profile, reactions between [PtCl2-
(PhCN)2] and telluroethers in 1:1 and 1:2 stoichiometry in
THF were examined under different reaction conditions.
Reactions of [PtCl2(PhCN)2] (1a) with TeArMes (Ar =
mesityl, o-tolyl, phenyl) in 1:1 ratio in THF afforded different
products depending on the steric demand of the Ar group
(Scheme 1). When Ar was phenyl, expected mononuclear
complex trans-[PtCl2{Te(Ph)(Mes)}2] (3b) was formed
exclusively. When the steric demand of the Ar group increased
from phenyl to o-tolyl, two products were isolated, viz. trans-
[PtCl2{Te(o-tol)(Mes)}2] (3d) as a minor fraction and trans-
[PtCl2(PhCN){NC(O)Ph(Te(Mes)o-tol)}] (4; see later for
structure), formed by the attack of telluroether on one of the
coordinated benzonitrile, as a major fraction. On further
increasing the steric demand of Ar group from o-tolyl to
mesityl, again two products were isolated, trans-[PtCl2-
(TeMes2)2] (3e) as a minor fraction and a product formed
by the attack of telluroether on both the coordinated
C
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recrystallization in acetone at room temperature along with the
crystals of 9, 3d was also formed as precipitate together with
the colorless crystals of [PtCl(Te-o-tol){NC(O)Ph}2] (11).
This indicates that in the reaction medium initially the complex
9 is formed, which is converted gradually into the more stable
3d via the cleavage of Pt−N bond with concomitant formation
of stable Pt−Te linkage. All the three complexes (3d, 9, and
11) were separated manually. Interestingly the reaction of
[PtCl2(PhCN)2] with TeMes2 yielded different products
depending on the duration of the reaction which was
monitored by 125Te NMR spectroscopy (Figure 1). Initially a
complex generated by telluroether attack on coordinated
benzonitrile, was formed in 24 h, although other products,
viz. 3e and 10, also existed in solution (Figure 1). When this
reaction continued for 72 h, in addition to this complex and 3e,
the concentration of trans-[PtCl2(TeMes2){NC(O)Ph-
(TeMes2)}] (10) increased significantly, and 10 could be
isolated from solution (see later for structure). On prolonging
the reaction for a week, bis-telluroether complex 3e existed in
more than 90% yield (Figure 1). Therefore, from the above
time dependent complexation history it is clear that initial
reaction of telluroether takes place at the coordinated
benzonitrile rather than at platinum center followed by stepwise
rearrangement. All these intermediate complexes could be
isolated and characterized with sterically demanding telluro-
ether, whereas with non-steriaclly hindered telluroethers, such
intermediates, which might have formed, could not be detected,
and only the substitution products, trans-[PtCl2(TeArAr′)2],
were isolated.
In order to assess generality of the reaction, organonitriles
differeing in the nature of organic substituents were examined.
Thus, the reactions between [PtCl2(RCN)2] (R = Me, 4-
MeC6H4, 4-CF3C6H4) with two equivalents of TeMes2 in THF
at room temperature were carried out and were monitored by
125Te NMR spectroscopy. In every case reaction proceeds in a
manner similar to benzonitrile. In the 125Te NMR spectra
resonances due to trans-[PtCl2{NC(O)R(TeMes2)}2] and
trans-[PtCl2(TeMes2){NC(O)R(TeMes2)}] (Supporting In-
formation, Figures S1−S3) were observed and even in one
case trans-[PtCl2{NC(O)Me(TeMes2)}2] (12) was isolated
and structurally characterized.
THF32 as noted for 6 and extrusion of oxygen from THF33,34 is
well documented in literature.
Spectroscopy. The NMR spectral data (1H, 125Te, and
195Pt) for [PtCl2(TeArAr′)2] and for 7 are in accord with those
reported recently by us.24 The H NMR spectra of 4−10
1
displayed resonances and peak multiplicities as expected. Both
the ortho protons of phenyl of benzonitrile resonances are
significantly deshielded (δ ∼8.25 ppm, ∼7.2 Hz). The 13C
NMR spectra exhibited, in addition to the expected resonances,
a signal at ∼180 ppm due to CO group. The 125Te NMR
spectra of the complexes containing “NC(O)Ph(TeAr′Mes)”
(4, 5, 6, 9, and 10) as a ligand exhibited a resonance in the
region, δ 907−959 ppm and were flanked by 195Pt satellites
with J(195Pt−125Te) in the range 309−347 Hz. The 125Te NMR
resonances are significantly deshielded from the corresponding
signal for both coordinated telluroethers as well as cyclo-
metalated telluroether ligands. The magnitude of platinum−
tellurium coupling is comparable to the trans-[PtCl2-
(TeArAr′)2]. The observed 125Te NMR chemical shift range
for 4, 5, 6, 9, and 10 is indicative of tellurium in a higher formal
oxidation state, as has been noted for organotellurium(IV)
complexes,35 such as (Et2NCOCH2)2TeCl2 (δ 125Te = 806
ppm);36a (5,7-Cl2-8-Me2NC10H4)2TeCl2 (δ 125Te = 1031.3
ppm).36b Recently, Lin and Gabbai described several platinum
̈
complexes of Te(o-C6H4PPh2)2 (δ 125Te = 580 ppm) in which
tellurium undergoes oxidation with formal oxidation state III/
IV and showed 125Te NMR chemical shift >1000 ppm.37 The
195Pt NMR resonances for these complexes are also deshielded
with respect to the corresponding signal for [PtCl2(TeArAr′)2].
The X-ray photoelectron spectra of trans-[PtCl2{NC(O)Ph-
(TeMes2)}2] (5) was recorded with an aim to find out the
chemical state of tellurium and platinum. Figure 2 shows the
To compare the reactivity of bulky telluroether with
palladium benzonitrile complex, a reaction of [PdCl2(PhCN)2]
with TeMes2 in 1:2 molar ratio in THF at room temperature
afforded expected product trans-[PdCl2(TeMes2)2] as revealed
20
1
by H and 125Te NMR spectroscopy.
Activation of C−N bond of metal ligated organonitriles by a
variety of nucleophiles, and to a lesser extent with electrophiles,
have been investigated extensively during the past two decades
or so.25−31 Both protic (e.g., ROH, RSH, oximes, etc.) and
aprotic nucleophiles have been shown to react with coordinated
organonitrile to yield a variety of compounds containing new
C−C and C−X (X = N, P, O, S) bonds. Activation of nitriles by
telluroethers in THF to give kinetically labile imide complexes,
described here, represents the first example of the formation of
NTeR2 linkage. A possible route could be the initial attack of
telluroether on nitrile carbon atom to give TeCNPt
linkage. The latter is attacked by THF oxygen on carbon and
simultaneous migration of TeArAr′ to nitrogen leads to Pt
N(TeArAr′)C(O)R linkage. This has been reaffirmed by
DFT calculations (Figure S4). Since PtN(TeArAr′)C(
O)R linkage does not form in moist DCM, the source is
attributed to THF. The C−H activation of the ortho-position of
Figure 2. Te(3d) and Pt(4f) X-ray photoelectron spectrum of trans-
[PtCl2{NC(O)Ph(TeMes2)}2] (5).
core-level Te 3d and Pt 4f spectra. Two groups of peaks at
575.1 and 585.5 eV were assigned to Te(3d5/2) and Te(3d3/2),
respectively. Similarly, the peaks for Pt(4f7/2) and Pt(4f5/2
)
were observed at 72.4 and 75.7 eV, respectively. The binding
energies of Te(3d) and Pt(4f) indicate that the chemical states
of tellurium and platinum are Te(IV)38 and Pt(II),39
respectively.
Crystallography. The molecular structures of trans-[PtCl2-
(PhCN)[NC(O)Ph{TeMes(o-tol)}] (4), trans-[PtCl2{NC-
(O)Ph(TeMes2)}2] (5), trans-[PtCl2{NC(Ph)C4H7O}{NC-
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(O)Ph(TeMes2)}] (6), trans-[PtCl2{NC(O)Ph(TeMes-o-
tol)}2] (9), trans-[PtCl2(TeMes2){NC(O)Ph(TeMes2)}]
(10), [PtCl(Te-o-tol){NC(O)Ph}2] (11), and trans-[PtCl2-
{NC(O)Me(TeMes2)}2] (12) were established unambiguously
by single-crystal X-ray diffraction analyses. ORTEP drawing are
shown in Figures 3−9, while the selected inter-atomic
parameters are summarized in Tables S1−S7.
Figure 5. ORTEP drawing of trans-[PtCl2{NC(Ph)C4H7O}{NC(O)-
Ph(TeMes2)}] (6) with atomic numbering scheme (drawn with 25%
probablility ellipsoids; H atoms are omitted for clarity).
Figure 3. ORTEP drawing of trans-[PtCl2(PhCN){NC(O)Ph-
(TeMes-o-tol)}] (4) with atomic numbering scheme (drawn with
25% probablility ellipsoids; H atoms are omitted for clarity).
Figure 6. ORTEP drawing of trans-[PtCl2{NC(O)Ph{Te(o-tol)-
Mes}}2] (9) with atomic numbering scheme (drawn with 25%
probablility ellipsoids; H atoms are omitted for clarity).
{Te(CH2SiMe3)2}2] (2.309(2) Å)23 and trans-[PtCl2(Te-
{(CH2CH2)O}2)] (2.3169(9) Å).40 The Pt−N distances
(1.966(13)−2.06(2) Å) are in accord with the values reported
for [Pt2(μ-Br)2(diimine)2]2+ (Pt−N = 1.992(2), 2.001(2) Å,41
but are longer than those found in complexes in which nitrogen
is trans to the strong trans influencing ligands, e.g., [PtCl-
(ECH2CH2NMe2)(PR3)] (E/PR3 = Se/PEt3, 2.160(7) Å; Te/
PMePh2, 2.182(4) Å).42 The Pt−Te distance (2.520(2) Å) is
well in agreement with those found in trans-[PtCl2(TeRR′)2].24
The Te−C distances (2.08(3)−2.183(13) Å) are as
expected.24,40,43 The Te−N bond lengths (1.97−2.06 Å) in
these complexes can be compared with those reported in
diorganotellurimides (R2TeNR′).44 The observed distances
indicate dipolar character as is usually observed in tellurium
imides.44 These distances are significantly shorter than those
found for intramolecular Te···N secondary bonding inter-
actions.45 The Te−O distances (2.510(13)−2.690(12) Å) are
significantly longer than those expected for single tellurium−
Figure 4. ORTEP drawing of trans-[PtCl2{NC(O)Ph(TeMes2)}2]·
4H2O (5·4H2O) with atomic numbering scheme (drawn with 25%
probablility ellipsoids; H atoms and solvent molecules are omitted for
clarity).
The two trans chloride and two neutral donor (N or/and Te)
ligands define the coordination environment around platinum.
There is slight deviation of various angles involving platinum
from idealized square planar configuration of central platinum
atom in these complexes. The Pt−Cl distances (2.281(6)−
2.318(7) Å) are well in agreement with those reported in
mononuclear trans-PtCl2L2 complexes, such as trans-[PtCl2-
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Figure 7. ORTEP drawing of trans-[PtCl2(TeMes2){NC(O)Ph-
(TeMes2)}] (10) with atomic numbering scheme (drawn with 25%
probablility ellipsoids; H atoms are omitted for clarity).
Figure 8. ORTEP drawing of trans-[PtCl2{NC(O)Me(TeMes2)}2]·
2CH2Cl2 (12·2CH2Cl2) with atomic numbering scheme (drawn with
25% probablility ellipsoids; H atoms are omitted for clarity).
Figure 9. (a) ORTEP drawing of [PtCl(o-tolTe){NC(O)Ph}2]·
CH2Cl2 (11·CH2Cl2) (drawn with 25% probablility ellipsoids; H
atoms and solvent molecules are omitted for clarity). (b)
Intermolecular interaction in 11.
oxygen bond lengths but are indicative of intramolecular
secondary Te···O bonding interactions.45 The Pt---Te distances
fall in the range 3.320(3)−3.5150(13) Å which are shorter than
the sum of van der Waals radii of platinum and tellurium (3.81
Å). This suggests that there is platinum−tellurium nonbonding
interaction which facilitates the formation of Pt-telluroether
linkage.
The C−Te−C angles (94.4−100.2°) are reduced from the
free telluroether (e.g., TeMes2, 101.0(1)°).46 This angle is little
influenced on coordination with platinum.24 The Te−N−C
angles show little variation (101.6−104.1°), and the Pt−N−C
angles fall in a rather large range (120(2)−130.4(12)°). The
carbon−oxygen bond lengths (1.23(4)−1.30(2) Å) are of
double bond character.
The complex [PtCl(Te-o-tol){NC(O)Ph}2] (11, Figure 9)
comprises a distorted square-planar platinum atom with a
“N2ClTe” coordination core. The two nitrogen atoms of the
amide group are mutually trans. The deviations of the N1−
Pt1−N2 and Cl1−Pt1−Te1 angles from linearity are rather
small. The two five- membered chelate rings “Pt1Te1O1C1N1”
and “Pt1Te1O2C8N2” are coplanar. The phenyl rings of the
amide groups are slightly out of the plane and are little tilted in
the opposite directions from this plane. The coplanarity of the
two chelate rings and short bite angle of the amide ligands
appear to be responsible for unusually short Pt−Te distance
(2.4503(10) Å) reported thus far.12 The other bond distances
involving platinum (Pt−N and Pt−Cl) are normal. The
tellurium atom adopts a distorted trigonal bipyramidal
configuration defined by the platinum, o-tolyl ring and a lone
pair of electrons at the equatorial positions while the two
oxygen atoms occupying the axial sites. The Te−C and Te−O
distances are as expected. Tellurium(IV) as a ligand has been
described recently and complexes in general have Te−Cl
linkages.37,47 The present complex represents the first example
where organotellurium(IV) acetoxy compound acts as a ligand.
Recently Singh and co-workers have isolated a palladium
complex [{(o-tol-Te)2O}Pd(μ-OAc)2] containing tellurenic
anhydride as a ligand.48 The X-ray crystallographic structural
parameters of [PtCl(Te-o-tol){NC(O)Ph}2] are in accordance
with the data obtained from the DFT calculations. Interstingly,
electron density contours/charge density distribution (Figures
S5 and S6) reveals that there is an extensive delocalization of
electron density along the “PtCl(Te){NC(O)Ph}2” unit and
leads to π−π stacking with the separation of 3.56 Å (Figure 9b).
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Density Functional Theory Calculations. The optimized
geometry of trans-[PtCl2(TeArAr′)2] (4, 5, 9) is given in Figure
S7. The calculated geometrical parameters (bond lengths and
bond angles) show good agreement with those obtained from
X-ray crystallographic data (Tables S1−S7). The reaction
between [PtCl2(PhCN)2] and telluroether may lead to the
formation of tellurium amides and/or imides. In order to assess
the possibility of formation of tellurium amides, an amide
analogue of trans-[PtCl2{NC(O)Ph(TeMes2)}2] was also
optimized and the relaxed geometry is shown in Figure S8.
The amide analogue shows larger separation between tellurium
and the nitrogen center (Te−N, 2.93 Å) than the tellurium
imide (Te−N, 2.09 Å) derivative. The C−Te−C angle in
tellurium imide and amide structure is 94.8° and 99.5°,
respectively. This indicates that amide structure has C−Te−C
angle close to that of free telluroether. Based on the
comparison between crystallographic data and theoretical
results, it can be inferred that the reactions between
[PtCl2(PhCN)2] and telluroethers would result in the
formation of tellurium imide rather than a tellurium amide
linkage. The relative charge density for the plane >TeN
CO unit of 5 is shown in Figure 10. The remarkably high
Figure 11. Total electron density contours (contour value 0.1) for the
trans-[PtCl2{NC(O)Ph(TeMes2)}2].
appearing in LUMO+1 molecular orbital. Since the molecular
arrangement of 4, 6, and 9 are similar to 5, it could be inferred
that the formal charge on tellurium and platinum in all these
complexes are +4 and +2 along with the above-described
delocalization of charge, respectively.
It is worth mentioning that in the present study, the reactions
between [PtCl2(PhCN)2] and TeMes2, addition of telluroether
to PhCN ligand take place with the formation of imide complex
5. However, Vigo and co-workers23 reported that the recation
between [PtCl2(PhCN)2] and Te(CH2SiMe3)2}2 yields cis-
[PtCl2{Te(CH2SiMe3)2}2] by substitution of PhCN ligand.
Therefore, in order to access the likewise possibility of any
ligand substitution product (instead of addition product, i.e.,
amide or imide complex) in the reaction of [PtCl2(PhCN)2] with
TeMes2, a substituted counterpart products were considered
and optimized without any constraint and the optimized
relaxed geometry is shown in Figure S10. It is found that
formation of addition product, i.e., amide/imide complex, is
thermodynamically more favorable in comparison to the
formation of substitution product PtCl2(TeMes)2.
Figure 10. Relative charge density for the plane having >TeN
CO unit in the trans-[PtCl2{NC(O)Ph(TeMes2)}2]. Inset picture
shows the plane from another angle.
formal positive charge on tellurium is found in the Mullikan
and Lowdin charge analysis and further reconfirmed from the
plot of total electron density contours (Figure 11). The
theoretical calculation (Figure 10) and the single-crystal X-ray
analysis (Figure 4) indicate that the TeNCO unit is
coplanar, with a dihedral angel of ∼2° (O1−C1−N1−Te1,
−2.1(15)°). The relative charge density calculation (Figure 10)
suggests that the electron cloude is delocalized throughout the
Te−N−C−O bond. The delocaloization is further extended
into the phenyl ring due to its planarity with the TeNC
O unit. The above delocalization is also supported by O1−C1,
C1−N1, and N1−Te1 bond distances which are intermediate
to the corresponding single and double bond distances. It is
clear from Figure 11 that the valence electron density around
tellurium is negligible indicating significant positive charge on
tellurium which is in agreement with the X-ray photoelectron
spectroscopy (XPS) results indicating +4 oxidation state of
tellurium. Molecular orbital (MO) analysis for the frontier
MOs of trans-[PtCl2{NC(O)Ph(TeMes2)}2] (5) shows that
HOMO and LUMO have major contributions from platinum
metal atom (Figure S9). Tellurium atomic orbitals are
EXPERIMENTAL SECTION
■
Solvents were dried and distilled under a nitrogen atmosphere prior to
use according to a literature method.49 All the reactions were carried
out under an argon atmosphere. Diaryltellurides, ArTeAr′, were
prepared by the reaction of ArTeBr, obtained in situ by bromination of
diarylditellurides (Ar2Te2) with bromine in THF, with an appropriate
aryl magnesium bromide (see Supporting Information for details).50
Elemental analyses were carried out on a Thermo Fischer Flash EA
1112 CHNS microanalyzer. Melting points were determined in
capillary tubes and are uncorrected. 1H, 13C{1H}, 125Te{1H}, and
195Pt{1H} NMR spectra were recorded on a Bruker Avance-II 300
(300.1, 75.5, 94.7, and 64.5 MHz, respectively) and Bruker Ascend
TM-400 (400, 100.61, 126.24, 86.02 MHz, respectively) NMR
spectrometers. The chemical shifts are relative to internal chloroform
1
peak (δ 7.26 ppm for H and 77.0 ppm for 13C) and external Me2Te
for 125Te (secondary reference Ph2Te2, δ 421 ppm in C6D6) and
external Na2PtCl6 in D2O for 195Pt. X-ray photoelectron spectrum of
trans-[PtCl2{NC(O)Ph(TeMes2)}2] (5) was recorded on a SPECS
instrument with 385 W, 13.85 kV, and 175.6 nA (sample current) Al
Kα (1486.6 eV) duel anode, with a PHOBIOS 100/150 Delay Line
G
DOI: 10.1021/acs.inorgchem.5b02024
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Detector (DLD), and with pass energy of 50. The C 1S peak (284.6
eV) was used as an internal reference for the absolute binding energy
calculation.
X-ray Crystallography. Single-crystal X-ray data on trans-
[PtCl2(PhCN){NC(O)Ph(Te(Mes)o-tol)}] (4), trans-[PtCl2{NC-
(O)Ph(TeMes2)}2] (5), trans-[PtCl2{NC(Ph)C4H7O}{NC(O)Ph-
(TeMes2)}] (6), trans-[PtCl2{NC(O)Ph{Te(o-tol)Mes}}2] (9)
trans-[PtCl2(TeMes2){NC(O)Ph(TeMes2)}] (10), [PtCl(Te-o-tol)-
{NC(O)Ph}2] (11), and trans-[PtCl2{NC(O)Me(TeMes2)}2] (12)
were collected on Agilent Super Nova CCD and Rigaku AFC7S
125Te{1H} NMR (CDCl3): δ 959 (J(195Pt−125Te) = 347 Hz) ppm.
195Pt{1H} NMR (CDCl3): δ −3079 ppm.
(b) Refluxed for 30 min: The reaction between [PtCl2(PhCN)2]
(100 mg, 0.21 mmol) and dimesityl telluride (79 mg, 0.21 mmol) was
carried out similar to the above under reflux for 30 min in THF. After
drying under vacuum, the residue was washed with hexane and
extracted with diethyl ether. The solvent was evaporated in vacuum to
give a pale yellow powder of trans-[PtCl2{NC(Ph)C4H7O}{NC(O)-
Ph(TeMes2)}] (6, yield 70 mg, 35%, mp 179−180 °C). Anal. Calcd
for C36H39Cl2N2O2PtTe: C, 46.68; H, 4.25; N, 3.02%. Found: C,
1
diffractometers at room temperature (298
2 K). Crystallographic
47.00; H, 4.20; N, 2.85%. H NMR (CDCl3): δ 2.21, 2.27 (each s,
data, together with data collection and refinement details, are given in
Table S8. All the data were corrected for Lorentz and polarization
effects. The structures were solved by direct methods51 and expanded
using Fourier technique.52 Hydrogen atoms were added to the parent
atom with idealized geometry and refined isotropically. Molecular
structures were drawn using ORTEP.53
Density Functional Theory Calculations. Theoretical calcu-
lations on 4, 5, 9, and 11 were carried out using the ab initio molecular
orbital theory-based LCAO approach as implemented in the GAMESS
software.54 Geometry optimization (without any symmetry constraint)
was done using the hybrid exchange correlation energy functional
commonly known as B3-LYP.54−56 The notation B3 implies three-
parameter Becke exchange functional, and LYP indicates correlation
functional as described by Lee, Yang, and Parr. Selected calculations
were also carried out using the PBE0 functional, and the results were
found to be analogous (Table S9). To ensure the local minima,
frequency calculations were carried out. While a standard split-valence
with polarization functions (6-31G(d)) was employed as basis set for
all low-Z elements, the SBKJC standard basis set was used for
platinum and tellurium.
Me), 2.60 (br), 3.54−3.78 (m), 5.18 (br, C4H7O), 6.95 (s, C6H2Me3),
7.28−7.50 (m), 8.58−8.65 (m, aryl) ppm. 125Te{1H} NMR (CDCl3):
δ 946 ppm. 195Pt{1H} NMR (CDCl3): δ −1861 ppm.
(c) Refluxed for 3 h: The reaction between [PtCl2(PhCN)2] (100
mg, 0.21 mmol) and dimesityl telluride (79 mg, 0.21 mmol) was
carried out similar to the above under reflux for 3 h in THF. The
solvent was evaporated under vacuum, and the residue was extracted
from diethyl ether, leaving behind an insoluble part which was soluble
in acetone.
The diethyl ether extract on evaporation gave an orange powder,
[PtCl(TeMes2){Te(Mes)CH2C6H2Me2}] (7), which could be recrys-
tallized from an acetonitrile−diethyl ether mixture at room temper-
ature (yield 29%, mp 180 °C). Anal. Calcd for C36H43ClPtTe2: C,
1
44.97; H, 4.51%. Found: C, 45.01; H, 4.53%. H NMR (CDCl3): δ
2.02, 2.19, 2.24, 2.27, 2.34, 2.53 (each s for Me), 4.0 (JAX = 16.8, ΔνAX
= 105.8 Hz; metalated CH2), 6.66 (s, 3,5-CH of Mes of metalated),
6.71 (s, 3,5-CH of TeMes2), 6.86, 7.04 (CH of metalated ring) ppm.
125Te{1H} NMR (CDCl3): δ 336 (1J(195Pt−125Te) = 622 Hz), 592
(1J(195Pt−125Te) = 1545 Hz), 598 (∼5% due to dimer), 259 (TeMes2)
ppm.
Synthesis. Reactions between [PtCl2(PhCN)2] and ArTeAr′ in 1:2
The acetone extract on evapaoration gave a yellow powder
comprising [Pt2Cl2(μ-Cl)2(TeMes2)2] (8) and [PtCl2(PhCN)2] (1a)
as inferred from NMR data. 125Te{1H} NMR (CDCl3): δ 425
(1J(195Pt−125Te) = 1052 Hz) ppm (due to 8). 195Pt{1H} NMR
(CDCl3): δ −3083 (due to 8) and −2336 (due to 1a) ppm.
Reactions between [PtCl2(PhCN)2] and TeArMes in 1:2 Ratio in
THF. (i). Reaction with TePhMes. The reaction was carried out in a
manner similar to that of [PtCl2(PhCN)2] and TePhMes described
above using [PtCl2(PhCN)2] (100 mg, 0.21 mmol) and mesityl phenyl
telluride (140 mg, 0.43 mmol) in THF at room temperature. The
product after recrystallization was characterized as [PtCl2{Te(Ph)-
Mes}2] (3b, yield 153 mg, 77%).
ratio in DCM are given in the Supporting Information.
Reactions between [PtCl2(PhCN)2] and TeArMes in 1:1 Ratio in
THF. (i). Reaction with TePhMes. To a THF solution of [PtCl2-
(PhCN)2] (100 mg, 0.21 mmol) was added mesityl phenyl telluride
(72 mg, 0.22 mmol), and the reaction mixture was stirred for 6 h at
room temperature. The solution was dried and washed with diethyl
ether. The complex was extracted with DCM and recrystallized from a
DCM−hexane (5:1) mixture, which on slow evaporation afforded
[PtCl2{Te(Ph)Mes}2] (3b) in 38% (75 mg) yield. Microanalysis and
NMR data are consistent with those of the sample prepared in DCM
(Supporting Information).
(ii). Reaction with Te(o-tol)Mes. The reaction was carried out by a
method similar to that described above for reaction with TePhMes.
The residue was extracted with diethyl ether, and the insoluble part
was identified as [PtCl2{Te(o-tol)Mes}2] (3d, yield ∼5%, by NMR
data). The ether extract on evaporation afforded trans-[PtCl2(PhCN)-
{NC(O)Ph[Te(o-tol)Mes]}] (4, yield 41%) which was recrystallized
from acetone−hexane mixture as light yellow crystals. Anal. Calcd for
C30H28Cl2N2OPtTe: C, 43.61; H, 3.42; N, 3.39%. Found: C, 43.52; H,
(ii). Reaction with Te(o-tol)Mes. The reaction was carried out in a
manner similar to that of [PtCl2(PhCN)2] and Te(o-tol)Mes
described above. The residue was extracted with diethyl ether, and
the insoluble part was identified as [PtCl2{Te(o-tol)Mes}2] (3d, yield
∼10%, NMR data were consistent with those of the sample prepared
in DCM).The ether extract on evaporation afforded trans-[PtCl2(NC-
(O)Ph{Te(o-tol)Mes})2] (9) and was recrystallized from acetone−
hexane (8:1) mixture at room temperature as orange crystals (yield
67%, mp 179 °C). Anal. Calcd for C46H46Cl2N2O2PtTe2: C, 46.82; H,
3.93; N, 2.37%. Found: C, 46.77; H, 4.00; N, 2.40%. 1H NMR
(CDCl3): δ 2.13 (s, 4-Me of Mes), 2.18 (s, 2-Me of tol), 2.43 (s, 2,6-
Me of Mes), 6.64 (s, 3,5-CH of Mes), 7.09−7.23 (m), 7.30−7.35 (m),
7.90 (d, 7.8 Hz), 8.18 (d, 7.5 Hz, tol) ppm. 125Te{1H} NMR (CDCl3):
δ 907 ppm. 195Pt{1H} NMR (CDCl3): δ −1525 ppm.
When 9 was left in acetone−hexane at room temperature in open
for recrystallization, colorless crystals of [PtCl(Teo-tol){NC(O)Ph}2]
(11) were isolated. Anal. Calcd for C21H17ClN2O2PtTe: C, 36.69; H,
2.49; N, 4.07%. Found: C, 36.43; H, 2.53; N, 3.99%. 1H NMR
(CDCl3): δ 2.93 (s, 2-Me), 7.32, 7.38 (t, 7.5 Hz), 7.49 (t, 6.9 Hz, 4-
CH of Ph and tol), 7.72 (d, 8.1 Hz, 2,6-CH of Ph), 8.22 (d, 7.8 Hz, 6-
CH of tol) ppm. 125Te{1H} NMR (CDCl3): δ 633 ppm. 195Pt{1H}
NMR (CDCl3): δ −3188 ppm.
1
3.41; N, 3.45%. H NMR (CDCl3): δ 2.29 (s, 4-Me of Mes), 2.38 (s,
2-Me of tol), 2.64 (s, 2,6-Me of Mes), 6.98 (s, 3,5-CH of Mes), 7.38−
7.86 (m), 8.73−8.77 (m, aryl) ppm. 125Te{1H} NMR (CDCl3): δ 937
(J(195Pt−125Te) = 317 Hz) ppm.
(iii). Reaction with TeMes2. This reaction on stirring at room
temperature gave different products depending on the duration of the
reaction.
(a) At room temperature: The reaction was carried out by a method
similar to that described above, and the residue was recrystallized from
an acetone−hexane mixture. The orange crystals of trans-[PtCl2{NC-
(O)Ph(TeMes2)}2] (5, yield 28%) were separated out, and the mother
liquor on further reduction of the solvent afforded crystals of trans-
[PtCl2(TeMes2)2] (3e, yield <5%, mp >200 °C, characterized from
NMR). Characterization data for 5: Anal. Calcd for
C50H54Cl2N2O2PtTe2: C, 48.58; H, 4.40; N, 2.27%. Found: C,
48.25; H, 4.33; N, 2.30%. 1H NMR (CDCl3): δ 2.21 (s, 4-Me), 2.39 (s,
2,6-Me2), 6.70 (s, 3,5-CH), 7.16 (t, 7.8 Hz), 7.36 (m), 8.24 (d, 7.2 Hz)
ppm. 13C{1H} NMR (CDCl3): 21.0, 22.4 (s, Me), 127.4, 128.6, 130.2,
130.3, 130.7, 133.9 (56 Hz), 140.6, 143.6, 182.3 (CO) ppm.
(iii). Reaction with TeMes2. This reaction on stirring at room
temperature gave different products depending on the duration of the
reaction.
(a) 24 h reaction time: The reactants [PtCl2(PhCN)2] (100 mg, 0.21
mmol) and dimesityl telluride (158 mg, 0.43 mmol) in THF were
H
DOI: 10.1021/acs.inorgchem.5b02024
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
stirred for 24 h at room temperature. The solvent was evaporated
under vacuum and the residue was extracted with diethyl ether from
which trans-[PtCl2{NC(O)Ph(TeMes2)}2] (5, yield 37%) was isolated
and characterized by NMR spectroscopy. The supernantant exhibited
125Te NMR spectrum showing resonance due to 3e, 5, and 10,
together with a small amount of TeMes2.
AUTHOR INFORMATION
Corresponding Author
*E-mail: jainvk@barc.gov.in. Tel.: +91 22 2559 5095. Fax: +91
22 2550 5151.
■
Notes
(b) 72 h reaction time: The contents of another reaction were stirred
for 72 h followed by evaporation of the solvent. The residue was
washed with diethyl ether and extracted with acetone. The acetone
extract on drying gave trans-[PtCl2(TeMes2){NC(O)Ph(TeMes2)}]
(10) and was recrystallized from acetone−hexane (10:1) as colorless
crystals (yield: 39%), mp 190 °C. Anal. Calcd for C43H49Cl2NOPtTe2:
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors thank Dr. (Smt). S. R. Bharadwaj and Dr. K.
Bhattacharyya, Chemistry Division, BARC, for recording the X-
ray photoelectron spectra.
1
C, 46.23; H, 4.42; N, 1.25%. Found: C, 46.31; H, 4.41; N, 1.27%. H
NMR (CDCl3): δ 2.21 (s, 2,4,6-Me of NTeMes2), 2.29 (s, 4-Me of
TeMes2), 2.59 (br, s, 2,6-Me of TeMes2)), 6.70 (s, 3,5-CH of
NTeMes2), 6.91 (s, 3,5-CH of TeMes2), 7.41−7.54 (m, 3,4,5-CH of
Ph), 8.49 (d, 7.2 Hz, 2,6-CH of Ph) ppm. 13C{1H} NMR (CDCl3): δ
20.8, 21.0, 22.8, 26.1, 127.8, 128.9, 129.3, 130.2, 130.7, 134.7, 139.3,
141.5, 143.4, 183.4 (CO) ppm. 125Te{1H} NMR (CDCl3): δ 418
(1J(195Pt−125Te) = 1638 Hz), 939 (J(195Pt−125Te) = 309 Hz) ppm.
195Pt{1H} NMR (CDCl3): δ −2701 ppm.
(c) 7 d reaction time: The contents of another reaction were stirred
for 7 days followed by evaporation of the solvent. The residue was
washed with hexane−diethyl ether (1:1) mixture and extracted with
diethyl ether. The ether extract after drying under vacuum affored 3e
as characterized by 125Te NMR spectroscopy: δ 467 ppm
(1J(195Pt−125Te) = 377 Hz).
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DOI: 10.1021/acs.inorgchem.5b02024
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