Tellurium azamacrocycles: Synthesis, characterization and coordination studies

Article abstract of DOI:10.1016/j.jorganchem.2003.12.042

The metal-free condensation of bis(2-formylphenyl) telluride (1) with a series of diamines affords macrocyclic tellurium ligands 2-7. Crystals of the protonated macrocycle 8 are monoclinic, space group P2/n with a=10.890(5), b=7.414(4), c=24.334(13) ?, Z=2. The reaction of tellurium containing macrocyclic Schiff base 2 with Pd(C₆H₅CN)₂Cl₂ gives the expected 1:1 product [Pd(II) 2] Cl₂ (9). Complex 9 was treated with excess of NH₄PF₆ in methanol to give the analogous PF₆^- salt [Pd(II) 2] (PF₆)₂ (10). The crystals of 10 are monoclinic, space group P2₁/n, a=8.2250(10), b=21.280 (4), c=21.150 (4), Z=4. However, the reaction of 2 with Pt(COD)Cl₂ proceeds via novel transmetallation to yield an organoplatinum complex (11). The crystals of 11 are also monoclinic, space group P2₁/n, a=12.3253 (14), b=14.6557 (14), C=13.4054 (11), Z=4. The octahedral Ni(II) complex 12 was prepared by the reaction of NiCl₂·6H₂O with 2 and NH₄PF₆ under an inert atmosphere. For 12: triclinic, space group P1?; Z=2; a=10.800(8), b=13.468(9), c=13.918(11), α=89.67(6)°, β=101.53(7)°, γ=81.49(3)° and V=1961(3). Cyclic voltammetry of 12 in MeCN solution shows a well-behaved quasi-reversible (ΔE=100 mV) Ni(III) ? Ni(II) couple.

Full text of DOI:10.1016/j.jorganchem.2003.12.042

Journal of Organometallic Chemistry 689 (2004) 1452–1463
www.elsevier.com/locate/jorganchem
Tellurium azamacrocycles: synthesis, characterization
and coordination studies q
a
a
a,
b
Saija C. Menon , Arunashree Panda , Harkesh B. Singh *, Rajan P. Patel ,
b
Shailendra K. Kulshreshtha , Willie L. Darby , Ray J. Butcher
c
d
a
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India
b
Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India
c
Department of Chemistry, Hampton University, Hampton, VA 23668, USA
Department of Chemistry, Howard University, Washington, DC 20059, USA
d
Received 8 August 2003; accepted 29 December 2003
Abstract
The metal-free condensation of bis(2-formylphenyl) telluride (1) with a series of diamines affords macrocyclic tellurium ligands 2–
ꢀ
7. Crystals of the protonated macrocycle 8 are monoclinic, space group P2=n with a ¼ 10:890ð5Þ, b ¼ 7:414ð4Þ, c ¼ 24:334ð13Þ A,
Z ¼ 2. The reaction of tellurium containing macrocyclic Schiff base 2 with Pd(C6H5CN)2Cl2 gives the expected 1:1 product [Pd(II) 2]
Cl2 (9). Complex 9 was treated with excess of NH4PF6 in methanol to give the analogous PFꢀ6 salt [Pd(II) 2] (PF6)2 (10). The crystals
of 10 are monoclinic, space group P21=n, a ¼ 8:2250ð10Þ, b ¼ 21:280 (4), c ¼ 21:150 (4), Z ¼ 4. However, the reaction of 2 with
Pt(COD)Cl2 proceeds via novel transmetallation to yield an organoplatinum complex (11). The crystals of 11 are also monoclinic,
space group P21=n, a ¼ 12:3253 (14), b ¼ 14:6557 (14), C ¼ 13:4054 (11), Z ¼ 4. The octahedral Ni(II) complex 12 was prepared by
ꢁ
the reaction of NiCl2 ꢁ 6H2O with 2 and NH4PF6 under an inert atmosphere. For 12: triclinic, space group P1; Z ¼ 2; a ¼ 10:800ð8Þ,
b ¼ 13:468ð9Þ, c ¼ 13:918ð11Þ, a ¼ 89:67ð6Þ°, b ¼ 101:53ð7Þ°, c ¼ 81:49ð3Þ° and V ¼ 1961ð3Þ. Cyclic voltammetry of 12 in MeCN
solution shows a well-behaved quasi-reversible (DE ¼ 100 mV) Ni(III) $ Ni(II) couple.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Tellurium; Macrocycle; Schiff base; Te–C bond; Cleavage; Transmetallation
1. Introduction
ther macrocycles have been shown to have an equally
good potential to serve as ligands [3,4]. Some efforts
have also been directed to extend this chemistry to the
corresponding tellurium macrocycles [5]. The lower
electronegativity and hence the greater r electron-do-
nating properties of Te compared to Se and/or S suggest
that incorporation of telluroether (TeR2) as donors in a
macrocyclic arrangement should yield ligands with rich
coordination chemistry. Recently, we have reported an
easy, high yield synthesis, structure and preliminary
coordination of a novel tellurium azamacrocycle (2)
with Pd(II) and Pt(II) [6]. In continuation to that, in this
full paper we report the synthesis and characterization
of some new related tellurium macrocycles, the crystal
structure of the protonated macrocycle 8 and detailed
ligand chemistry of 2.
The thioether macrocycles have proved to be very
good ligands for a wide range of d- and p-block ions [1].
An important feature of these systems is their ability to
adopt unpredictable geometries and stabilize unusual
oxidation states. In the field of acyclic ligands the sys-
tems bearing heavy chalcogens selenium and tellurium
exhibit a rich coordination chemistry [2]. Polyselenoe-
q Supplementary data associated with this article can be found, in the
online version at doi:10.1016/j.jorganchem.2003.12.042.
* Corresponding author. Tel.: +91-222-576-7190; fax: +91-222-572-
3480.
E-mail address: chhbsia@chem.iitb.ac.in (H.B. Singh).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.12.042

S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
1453
2. Results and discussion
2.1. Ligand synthesis
The macrocyclic tellurium ligands 2–7 were easily
isolated in good yields (32–80%) via one step dipodal
2+2 condensation of bis(2-formylphenyl) telluride (1) [7]
with a series of diamines without recourse to a metal ion
template or high dilution reaction (Scheme 1). There was
no evidence for the formation of the 1+1 condensation
product in EI-MS and 125Te NMR spectra [5h].
The presence of secondary intramolecular Teꢁ ꢁ ꢁN
coordination in the macrocycles plays an important role
in their formation by reducing the unfavorable lone
pair–lone pair repulsion between the nitrogen atoms in
the ring. The macrocycles with varying ring size i.e. from
22 to 34 and donor atoms from 6 to 10 were readily
formed at room temperature by stirring the diamines
and the bis(aldehyde) 1 in acetonitrile. The yields of the
reactions were found to be highly dependent on the
purity of the solvent. In general, all these compounds
show poor solubility in common organic solvents.
However, they were soluble to some extent in chloro-
form and dichloromethane, but insoluble in more polar
solvents like CH3OH and DMSO.
Attempts to synthesize analogous macrocycles by
reacting 1 with o-phenylenediamine, 1,8-diaminonaph-
thalene and hydrazine hydrate were unsuccessful. This is
probably due to the rigid nature of the amines. Attempts
were also made to synthesize these macrocycles in the
presence of metal templates such as lanthanum nitrate.
The bright yellow product formed after refluxing 1 and
o-phenylenediamine with lanthanum nitrate for 2 h in
methanol was found to be soluble in dichloromethane
and chloroform. Although this gave an indication of
formation of the metal free macrocyclic ligand by IR
and elemental analysis, its NMR spectrum was very
complex.
The macrocyclic Schiff base ligands (3–7) show IR
absorption frequencies characteristic of mC@N stretching
around 1640 cmꢀ1. The NMR spectra of the Schiff base
ligands (3–7) were recorded in CDCl3. Due to the poor
solubility, satisfactory 13C NMR spectra of the com-
pounds other than 5 could not be recorded. In the case
1
of 4 and 5, the H NMR spectra obtained were as ex-
pected. The very symmetric NMR spectrum is proba-
bly due to a fast (on NMR time scale) Teꢁ ꢁ ꢁN(1),
Teꢁ ꢁ ꢁN(2) bond scrambling. This leads to a dynamic
equilibrium between the two-topomeric 10-Te-3 struc-
tures, which apparently takes place via a 12-Te-4 tellu-
rane intermediate as reported by Minkin and co-workers
[8].
The CH@N proton signals for the Schiff bases are
observed at ꢂ8.5–8.6 ppm being shifted to 1.5–1.6 ppm
upfield in comparison with the signal of the formyl
proton in the precursor bis(2-formylphenyl) telluride
(10.1 ppm). In the case of 3 although elemental analysis
and mass spectral data suggested the formation of the
2+2 product, the 1H NMR spectrum was complex. This
could be due to the existence of different geometrical and
optical isomeric structures. The CH3 group in the
product can have at least two different positions, thus
giving structures 3a and 3b.
The reduction of 2 with NaBH4 followed by pro-
tonation with hydrogen bromide resulted in the forma-
tion of 8 [6a]. This was obtained in very good yield and
was recrystallized from water/ methanol (1:1) mixture as
colourless needles. This compound should be able to
bind to a variety of anionic substrates and has been
characterized by X-ray diffraction studies (vide infra).
Though the products obtained by the (2+2) Schiff
base condensation of triethylenetetraamine (TRIEN) (6)
and diethylenetriamine (DIEN) (7) with 1 gave satis-
1
factory elemental analysis, their H NMR spectra were
quite complex. A ring contraction of the macrocyclic
cavity of Schiff bases, often leading to the stabilization
of metal free ligands, has been observed when there is a
group such as NH or OH available for addition to the
imine bond in the related macrocycles. Four closely re-
lated examples of such inner ring contractions, where
Schiff base condensation reactions of diethylenetriamine
and dialdehydes 2,6-diacetylpyridine, isophthalaldehyde
and 2,6-diformyl-4-chlorophenol, have been reported by
Drew et al. [9], Menif et al. [10] and Aguiari et al. [11],
Scheme 1. R ¼ CH2CH2 (2) [6a], CH2CH(Me) (3), CH2CH2CH2 (4),
CH2(CH2)4CH2 (5), CH2CH2NHCH2CH2NHCH2CH2 (6), and
CH2CH2NHCH2CH2 (7).

1454
S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
respectively. Very recently NMR evidences for inter-
conversion between two enantiomeric forms of lantha-
nide complexes of this ligand through reversible ring
contraction and expansion has been described [12]. In
our case the product probably consists of a mixture of
the desired macrocycles with the isomers formed by the
[34]–[28]–[22] or [28]–[22] ring contraction as a conse-
quence of the nucleophilic addition of the secondary
amine function (NH) across the imine bond. Here also
metal ions were not involved in the ring contraction and
expansion. Neither chemical analysis nor IR spectra
allow a distinction to be made between the Schiff bases
(6 and 7) and their isomeric forms which were the ex-
pected ring-contracted products [11].
125Te NMR spectra were recorded for CDCl3/
DMSO-d6 solutions of macrocycles. The spectrum of
3 displays four signals, thus again indicating the pres-
ence of more than one tellurium containing species in
solution.
Electron impact (EI) or fast atom bombardment
(FAB) mass spectra of all macrocycles were recorded in
order to confirm the formation of 2+2 cyclocondensa-
tion product. Unfortunately compound 6 does not show
molecular ion peak. The highest recorded peak at m=e
732 was assigned due to loss of C6H4CHNC2H4NHCH2
group (735).
crystallized from methanol as yellow needles of complex
9 by vapour diffusion of diethylether. Crystal structure
of this complex could not be determined due to fact that
the crystals lost it luster on removing it out from the
solvent. The complex was found to be a 1:2 electrolyte in
methanol (KM 142.68 Xꢀ1 cm2 molꢀ1). The IR spectrum
shows mC@N absorption frequency at 1639 cmꢀ1. The
125Te NMR spectrum shows a single signal at 722 ppm,
a deshielded position compared to the free ligand 2 (607
ppm). The elemental analysis data suggested the for-
mation of the 1:1 product. The FAB mass spectrum of
the crystals shows the highest mass peak at m=z 867
(80%) and base peak at m=z 830 which are assignable to
[2+PdCl]þ and [2+Pd]þ. Hence the formulation [Pd
(2)]Cl2 (9) is suggested. Thus a noticeable difference in
behaviour of the products obtained from 2:1 (metal:li-
gand) molar reaction reported [6a] earlier and the 1:1
(metal:ligand) molar reaction has been observed. The
1:1 product is more soluble and ionic in nature com-
pared with the less soluble nonionic 2:1 complex [6a].
In order to get suitable crystal of the palladium
complex (vide supra), we thought of changing the
chloride ions with bulkier PFꢀ6 anions. Complex 9 was
treated with an excess of ammonium hexafluorophos-
phate in methanol to give a yellow precipitate of 10.
Washing the product with methanol followed by re-
crystallization from acetonitrile by vapour diffusion of
diethyl ether afforded yellow needles of 10 [6b]. This
compound was characterized by routine spectroscopic
techniques. The IR spectrum shows a broad absorption
peak at 836 cmꢀ1 which indicates the presence of the
PFꢀ6 ion in addition to the azomethine stretching fre-
quency at 1639.8 cmꢀ1. The 1H, 13C or 125Te NMR data
were very similar to that of 9 with some shifts. The
structure was further confirmed by single crystal X-ray
diffraction studies.
2.2. Complexation studies
1
In view of the excellent yield and simple H NMR
spectra the coordination properties of potential hexad-
entate ligand 2 towards Pd(II), Pt(II) and Ni(II) ions
were studied (Scheme 2).
2.2.1. Reaction with Pd(II) ions
When the reaction of 2 was carried out with one
equivalent of Pd(C6H5CN)2Cl2 in CHCl3, light yellow
precipitate formed immediately after addition. However,
it re-dissolved on stirring for some time to give a clear
reddish yellow solution. The reddish yellow powder of
the complex left after evaporation of the solvent was re-
2.2.2. Reaction with Pt(II) ion
The reaction of Pt(COD)Cl2 with the ligand 2 (metal
ligand ratio 1:1) in dichloromethane at room tempera-
ture gave a reddish brown solution from which a solid
Scheme 2. Reagents and conditions: (i) Pd(C6H5CN)2Cl2, CHCl3, 2 h; (ii) Pt(COD)Cl2, CH2Cl2, 16 h; (iii) NiCl2 ꢁ 6H2O, 0.5 h, MeOH, reflux (iv)
MeOH, NH4PF6, rt.

S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
1455
was obtained by filtration after concentrating the solu-
tion. This was dissolved in methanol by warming and an
excess of ammonium hexafluorophosphate was added.
A reddish brown precipitate of the complex 11 separated
out immediately [6b]. This could be recystallized by slow
evaporation of the acetonitrile solution. In contrast to
the reaction of Pd(II) with 2, in this case the reaction
proceeds via novel transmetallation to yield an or-
ganoplatinum complex 11 [6b]. The elemental analysis,
NMR and FAB mass spectral data suggested the for-
mation of complex. The IR spectra showed peaks con-
sistent with the presence of C@O and C@N stretching
frequencies at 1697 and 1646 cmꢀ1, respectively. The
unexpected organoplatinum complex, presumably, re-
sults from the facile cleavage of one of the Te–C bonds
activated by the Te–N interaction; transfer of electron
density from nitrogen to the rꢃ orbital of trans Te–C
bond leading to significant Te–C bond weakening. The
crystal structure of 11 was further confirmed further by
a single crystal X-ray diffraction study.
behaved
quasi-reversible
(DE ¼ 100
mV)
Ni(III) $ Ni(II) couple (Fig. 1). The assignment of oc-
tahedral geometries to [Ni(II) 2](PF6)2 (12) follows from
its paramagnetism, leff ¼ 3:06 BM, which indicates
S ¼ 1 and this was further confirmed by single-crystal X-
ray study (vide infra). Thus, from the elemental analysis
data, IR, UV/visible, 125Te NMR, FAB mass spectrum,
magnetic susceptibility the formation of [Ni(II) 2](PF6)2
is suggested.
2.3. Crystal structure of 8
The protonated salt (8) crystallizes from a solution
consisting of water and methanol (1:1) with solvent of
crystallization (H2O) which is hydrogen bonded to the
macrocycle. The thermal ellipsoid plot [13] with 50%
probability together with the atomic labeling scheme is
shown in Fig. 2. Selected bond lengths and angles are
collected in the Table 1. The crystal structure confirmed
the reduction of CH@N bonds and the formation of
macrocyclic polyamine as well as protonation at nitro-
gen centres. The asymmetric unit contains half the
macrocycle similar to its parent Schiff base (2) [6a]. In 8
none of the bromide counter ions are situated inside the
macrocyclic cavity, but one lies above the macrocycle
and forms intermolecular hydrogen bonding with the
amine and water hydrogens [14]. These distances
2.2.3. Reactions with Ni(II) ion
Reaction of NiCl2 ꢁ 6H2O with one mole of 2 in re-
fluxing methanol followed by the addition of excess of
PFꢀ6 afforded air stable red Ni(II) paramagnetic complex
(12) (Scheme 2). Complex 12 is insoluble in chlorocar-
bons and hydrocarbons. However, it dissolves in coor-
dinating solvents such as MeCN, DMF and DMSO.
However, it results in rapid decomposition via dis-
placement of the azatelluromacrocycle 2 in DMSO. This
was confirmed by 1H NMR spectroscopic studies on the
compound in DMSO-d6. A similar observation has been
observed by Reid and co-workers [4m] for the seven-
coordinate Mo(II) and W(II) species derived from the
selenoether ligands 1,5,9,13-tetraselenacyclohexadecane
([16]aneSe4) and 1,6-diselena-3,4-benzocyclononane.
The infrared spectroscopic measurements showed the
presence of the PFꢀ6 anion. The mC@N absorption
stretching frequency for 12 was found at 1644 cmꢀ1. The
electronic spectrum of the complex was recorded at
room temperature in CH3CN in the range 190–900 nm.
The solution phase electronic spectra (>200 nm) of the
ligand 2 consists of two intense bands centered at 291.6,
368.0 nm which can be assigned to the intraligand p–pꢃ
transitions. For the complex 12 intense peak is found at
294.8 nm which may be attributed to the charge-transfer
transitions. The bands observed at 367, 488 and 809.5
nm are due to p–pꢃ and d–d transitions, respectively.
The diffuse reflectance spectrum of the complex showed
peaks at 370, 534 and 802 nm, thus confirming the
presence of same species in solution and solid state.
In the FAB Ms the peaks at m=z 927 and 784 for the
complex 12 were for [12–PF6] and [12–2PF6], respec-
tively. The cyclic voltammogram of 12 showed the oxi-
dation and reduction peaks at 0.8 and 0.9 V,
respectively, at scan rate 100 mV/s. It reveals a well-
ꢀ
ꢀ
ꢀ
ꢀ
Br(1)ꢁ ꢁ ꢁH(1B) 2.369 A, Br(1)ꢁ ꢁ ꢁH(2B) 2.431 A,
Br(2)ꢁ ꢁ ꢁH(1W1) 2.860 A, Br(2) H(1A)ꢁ ꢁ ꢁ2.498 A,
ꢀ
ꢀ
N(2)ꢁ ꢁ ꢁH(2A) 0.900 A and N(2)ꢁ ꢁ ꢁH(2B) 0.900 A indi-
cate presence of strong hydrogen bonds. The macrocycle
is highly puckered. All four nitrogens are not planar and
ꢀ
the mean plane deviation from the plane is 0.7766 A.
The intramolecular distance between symmetry related
ꢀ
nitrogen atom is 5.473 A while intramolecular Teꢁ ꢁ ꢁTe
ꢀ
distance is 7.108 A. The intramolecular Teꢁ ꢁ ꢁTe distance
ꢀ
is greater than the corresponding distance (4.979 A) in
the Schiff base 2.
The Te(1)–C(11) distance of [2.121(5) A] and Te(1)–
ꢀ
C(21) distance of [2.131(4) A] compares well with the
ꢀ
ꢀ
mean value of Te–C (aromatic) of 2.166 A given by
Fig. 1. Cyclic voltammogram of 12.

1456
S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
Fig. 2. An ORTEP diagram of 8.
Table 1
ꢀ
Significant bond lengths (A) and angles (°) for 8
Te–C(11)
2.121(5)
0.67(3)
Te–C(21)
2.131(4)
0.64(5)
O(1WA)–O(1WB)
N(1)–C(17)
N(2)–C(28)
O(2W)–O(2W)#1
N(1)–C(18)
N(2)–C(27)
1.509(5)
1.490(5)
96.34(17)
110.7(3)
122.0(3)
111.0(4)
121.2(3)
111.8(4)
1.510(6)
1.503(5)
114.0(3)
118.9(4)
111.5(4)
119.3(3)
111.9(3)
C(11)–Te–C(21)
C(28)–N(2)–C(27)
C(16)–C(11)–Te
C(28)#1–C(18)–N(1)
C(26)–C(21)–Te
N(2)–C(28)–C(18)#1
C(17)–N(1)–C(18)
C(12)–C(11)–Te
C(16)–C(17)–N(1)
C(22)–C(21)–Te
N(2)–C(27)–C(26)
ꢀ
Allen et al. [15] and with 2.125(16) A observed for Te–C
in 2-bromotelluro-N-(p-tolyl)benzylamine [16]. The an-
gle C(11)–Te–C(21) is 96.34° and geometry around tel-
lurium can be considered as V-shaped.
of Te atoms. In contrast, in square planar Pd complexes
having two trans Pd–Te bonds [18–20], the Pd–Te bond
ꢀ
lengths are in the range from 2.589 to 2.606 A (average
ꢀ
2.597 A), thus indicating a strong donor and trans in-
fluences of Te donor.
2.4. Crystal structure of 10
The geometry around Pd is trapezoid planar with
mean Te, N bite angle of 93.7° and smaller bite angles of
N–Te (82.8(2)°) and Te–Te 89.68(2)°. The smaller
Te(1A) and Te(1B) bite angles force the telluriums to be
The molecular structure of 10 is shown in Fig. 3
and selected bond lengths and bond angles are given in
Table 2. In complex 10, the Pd2þ cation is interestingly
coordinated to only two nitrogen atoms of same di-
aminomethane unit and two tellurium atoms. The
adaptability of 2 to form cis-square planar complex with
Te2N2 donor sets forces a twofold symmetry. The av-
ꢀ
at a strong interacting distance of 3.591 A which is 4.971
ꢀ
A in the free ligand [6a]. The mean Te–C bond distance
ꢀ
(2.14 A) is close to the sum of the PaulingÕs single bond
2
ꢀ
covalent radii for tellurium (1.37 A) and the sp hy-
ꢀ
bridized carbon (0.74 A). Both the telluriums have
ꢀ
erage Pd–N distance of 2.098 A is slightly higher than
identical pyramidal geometry. The angles around Te
[C(1D)–Te(1B)–C(1B)] and [C(1C)–Te(1A)–(1A)] aver-
age 94.3° and are close to the corresponding angle in the
free ligand [6a]. Interestingly the tellurium atoms in
addition to acting as donor atoms to Pd, also act as
acceptors to N and Te. The mean Teꢁ ꢁ ꢁN intramolecular
distances [Te(B)ꢁ ꢁ ꢁN(1D)] and [Te(1A)ꢁ ꢁ ꢁN(1C)] are
ꢀ
the sum of Pauling’s single bond covalent radii (2.01 A)
ꢀ
while the mean Pd–Te distance (2.5463 A) is signifi-
ꢀ
cantly shorter than the sum of the covalent radii (2.68 A)
of Te and Pd. This shortening in Pd–Te bond distance
may be due to the soft–soft interaction. The Pd–Te
distances are, however, comparable to the Pd(1)–Te(1)
2.540(2) A and Pd(3)–Te(5) 2.554(2) A, respectively, in
[{Pd(OC6H4)(TeMe)TeI}4][17] which has cis-disposition
ꢀ
ꢀ
ꢀ
ꢀ
2.738 A well within the van der WaalÕs distance of 3.7 A
and the Te–C–C–C–N moieties are planar.

S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
1457
Fig. 3. An ORTEP diagram of complex 10 cation.
Table 2
Significant bond lengths (A) and angles (°) for 10
ꢀ
Te(1A)–C(1C)
Te(1A)–Pd
2.129(7)
Te(1A)–C(1A)
Te(1B)–C(1B)
2.150(7)
2.138(7)
2.5483(7)
2.099(6)
1.479(9)
1.475(9)
1.458(10)
1.457(9)
99.0(2)
2.5443(7)
2.145(7)
2.097(6)
1.284(9)
1.275(9)
1.254(10)
1.266(10)
94.9(3)
Te(1B)–C(1D)
Pd–N(1A)
Te(1B)–Pd
Pd–N(1B)
N(1A)–C(7A)
N(1B)–C(7B)
N(1A)–C(8A)
N(1B)–C(8B)
N(1C)–C(7C)
N(1D)–C(7D)
N(1C)–C(8C)
N(1D)–C(8D)
C(1C)–Te(1A)–C(1A)
C(1A)–Te(1A)–Pd
C(1B)–Te(1B)–Pd
N(1A)–Pd–N(1B)
N(1B)–Pd–Te(1A)
N(1B)–Pd–Te(1B)
C(7A)–N(1A)–Pd
C(7B)–N(1B)–C(8B)
C(8B)–N(1B)–Pd
C(7D)–N(1D)–C(8D)
C(2A)–C(1A)–Te(1A)
N(1A)–C(8A)–C(8B)
C(6B)–C(1B)–Te(1B)
N(1B)–C(8B)–C(8A)
C(6C)–C(1C)–Te(1A)
C(2D)–C(1D)–Te(1B)
N(1D)–C(7D)–C(6D)
C(7A)–N(1A)–C(8A)
C(1C)–Te(1A)–Pd
C(1B)–Te(1B)–C(1D)
C(1D)–Te(1B)–Pd
N(1A)–Pd–Te(1A)
N(1A)–Pd–Te(1B)
Te(1A)–Pd–Te(1B)
C(8A)–N(1A)–Pd
C(7B)–N(1B)–Pd
C(7C)–N(1C)–C(8C)
C(6A)–C(1A)–Te(1A)
N(1A)–C(7A)–C(6A)
C(2B)–C(1B)–Te(1B)
N(1B)–C(7B)–C(6B)
C(2C)–C(1C)–Te(1A)
N(1C)–C(7C)–C(6C)
C(6D)–C(1D)–Te(1B)
N(1D)–C(8D)–C(8C)
N(1C)–C(8C)–C(8D)
99.8(2)
99.5(2)
93.7(2)
99.5(2)
94.4(2)
82.8(2)
176.9(2)
93.1(2)
175.9(2)
89.68(2)
107.5(4)
137.1(5)
119.9(7)
128.7(5)
129.2(7)
111.8(5)
129.8(7)
121.2(5)
120.8(7)
118.8(5)
108.9(7)
109.7(7)
136.9(5)
116.4(6)
106.4(4)
119.0(6)
111.0(5)
108.0(6)
129.0(5)
107.6(6)
118.9(5)
121.3(5)
120.2(7)
115.4(6)
2.5. Crystal structure of 11
Fig. 4. The crystal structure shows a trapezoid planar
geometry around Pt(II) cation which is coordinated by
two nitrogen atoms of the same diaminomethane unit, a
tellurium and a carbon atom. The average Pt–N dis-
tance is in excellent agreement with the sum of covalent
Complex 11 also crystallizes in monoclinic system
with space group P21=n. The selected bond length and
angles are given in Table 3 and the molecule is shown in

1458
S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
Table 3
ꢀ
Significant bond lengths (A) and angles (°) for 11
Pt–N(1A)
Pt–N(1B)
1.994(7)
Pt–C(1A)
Pt–Te
2.028(8)
2.5180(6)
2.149(8)
1.472(11)
1.445(13)
80.3(4)
2.087(7)
2.149(7)
1.273(12)
1.259(13)
1.186(10)
82.4(3)
Te–C(1C)
N(1B)–C(7B)
Te–C(1B)
N(1B)–C(8B)
N(1A)–C(8A)
N(1A)–C(7A)
O–C(7C)
N(1A)–Pt–C(1A)
C(1A)–Pt–N(1B)
C(1A)–Pt–Te
N(1A)–Pt–N(1B)
N(1A)–Pt–Te
N(1B)–Pt–Te
162.4(3)
100.7(2)
90.5(3)
177.0(2)
96.8(2)
97.1(2)
C(1C)–Te–C(1B)
C(1B)–Te–Pt
C(1C)–Te–Pt
100.0(2)
134.4(6)
126.6(8)
115.0(6)
112.5(7)
118.2(5)
110.2(8)
108.6(8)
132.6(7)
C(7B)–N(1B)–C(8B)
C(8B)–N(1B)–Pt
C(7A)–N(1A)–Pt
N(1B)–C(7B)–C(6B)
C(6B)–C(1B)–Te
C(6C)–C(1C)–Te
N(1A)–C(7A)–C(6A)
O–C(7C)–C(6C)
C(6A)–C(1A)–Pt
117.1(8)
108.4(6)
118.4(7)
130.0(8)
127.7(6)
121.8(5)
114.9(8)
126.1(8)
111.3(7)
C(7B)–N(1B)–Pt
C(7A)–N(1A)–C(8A)
C(8A)–N(1A)–Pt
C(2B)–C(1B)–Te
C(2C)–C(1C)–Te
N(1B)–C(8B)–C(8A)
N(1A)–C(8A)–C(8B)
C(2A)–C(1A)–Pt
Fig. 4. An ORTEP diagram of complex 11 cation.
ꢀ
ꢀ
radii of Pt and N. The Pt–Te distance of 2.5180(6) A
observed in complex is considerably shorter than the
ꢀ
sum of covalent radii (2.68 A), however, it is comparable
molecular distance of 2.76 A observed in bis(2-for-
myl)ditelluride [22]. Further, the cations are linked into
ꢀ
weak dimers by weak Teꢁ ꢁ ꢁPt contacts (3.483 A) (Fig. 5)
ꢀ
with the Pt–Te distance of 2.512(1) A observed in
giving dimeric complex. Interestingly, such dimers have
been proposed as possible intermediates in reaction [23].
Complex 11, is the first example of a structurally char-
acterised complex having both intra and intermolecular
Pt–Te bonding.
[Pt{NC5H4–2–(CH2)–Te– C6H4–4–OMe)}Cl2] [21]. The
transmetallation of Te with Pt leads to unsymmetrical
chelate rings. The Teꢁ ꢁ ꢁN chelate ring in this case is six
membered with a large bite angle of 96.8(2)° whereas the
opposite CN bite angle is 80.3°. This leads to a highly
distorted square planar geometry.
2.6. Crystal structure of 12
ꢀ
The intramolecular Teꢁ ꢁ ꢁO distance of 3.004 A im-
plies a weak coordination of oxygen to tellurium as it is
significantly shorter than the van der WaalÕs radii of 3.6
Crystals of complex 12 were obtained by vapour
diffusion of diethyl ether into a solution of the complex
in CH3CN. The ORTEP diagram of 12 is given in Fig. 6.
ꢀ
A. However, this is much larger than the mean intra-

S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
1459
bond distance is significantly longer than the Ni–Te
5
ꢀ
distance 2.485(1) A in [(g -Cp)Ni(PEt3)TeMes] [24].
Here again adaptability of 2 leads to a cis-disposition of
Te donors.
3. Experimental
The complex precursors, i.e., Pd(C6H5CN)2Cl2 [25]
and Pt(COD)Cl2 [26] were prepared by following the
reported procedures. Bis(o-formylphenyl) telluride was
prepared as described in the literature [7]. 1,2-Diami-
noethane (EN), 1,2-diaminopropane (1-MeEN), 1,3-
diaminopropane (PN), 1,6-diaminohexane (HN), tri-
ethylenetetraamine (TRIEN) and diethylenetriamine
(DIEN) were distilled before use. FAB MS analyses
were recorded on a JEOL SX 102/DA-6000 mass spec-
trometer/data system using Xenon (6 kV) as the FAB
gas. The accelerating voltage was 10 kV and the spectra
were recorded at room temperature. In case of isotopic
pattern, the value given is for the most intense peak. EI
mass spectra were obtained on a Jeol D-300(EI/CI)
spectrometer and are reported as m=z (ion percent rel-
ative intensity). The melting points are uncorrected and
were determined on a Veego melting point apparatus
using a capillary tube. Elemental analyses were per-
formed on a Carlo Erba elemental analyser model 1106.
Electronic absorption spectra were obtained in CHCl3/
CH3CN at 25 °C in a 1 cm quartz cuvette on a ther-
mostat Shimadzu UV-2100 apparatus. The IR spectra
were recorded on a Perkin–Elmer 681 spectrometer. The
solid samples were examined as KBr pellets. FAR IR
spectra of polyethylene pellet were recorded on Bruker
Fig. 5. Packing diagram of 11.
Complex 12 crystallizes in the triclinic system (space
group P1) with Z ¼ 2. Though the R value is not satis-
factory, it confirms the proposed structure beyond
doubt.
ꢀ
The Ni–Te mean bond distance 2.66 A as expected is
longer than the sum of the single bond covalent radii of
ꢀ
Ni(II) in octahedral environment (0.83 A) and Te (1.37)
ꢀ
A. This is due to ‘‘hard’’ N and ‘‘soft’’ Te bonding. This
Fig. 6. An ORTEP diagram of complex 12 cation.

1460
S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
IFS 66V FT-IR spectrometer. Nuclear magnetic reso-
nance spectra, 1H (299.94 MHz), 13C (75.42 MHz),
125Te (94.75 MHz) were recorded on a Varian VXR
300S spectrometer. Chemical shifts are cited with respect
to SiMe4 as internal standard (1H and 13C) and TeMe2
as external standard (125Te). Magnetic susceptibility of
the complexes has been studied at room temperature.
Complex Hg[Co(SCN)4] was used as the standard. Cy-
clic voltammetry (CV) experiments were performed on a
Scanning Potentiostat EG and G PARC Model 362
instrument which consists of one-compartment cell with
platinum working and counter electrodes and a stan-
dard Ag/AgCl reference electrode. Tetrabutylammo-
nium tetrafluoroborate (Aldrich) was used as the
supporting electrolyte. All solutions were purged with
nitrogen before the CV data were recorded. Measure-
ments were conducted in 0.1 mol dmꢀ3 NBu4BF4 in
acetonitrile with sample concentration 0.05 mM with the
scan rates of 100 mV/s. Under these conditions
[Fe(C5H5)2]/[Fe(C5H5)2]þ has E1=2 0.46 mV.
3.1.3. Synthesis of bis(diphenyltelluride)BISHN Schiff
base (5)
Yield: 0.15 g, 61%; m.p. 120 °C. Anal. Calc. for
C40H44N4Te2: C, 57.47; H, 5.30; N, 6.70. Found: C,
57.43; H, 5.57; N, 6.62%. MS (FAB): m=z 838 (Mþ for
128Te), 648, 627, 419, 329, 314, 214, 1H NMR (CDCl3): d
8.60 (s, 4H, azomethine-H), 7.76–7.72 (m, 4H, aromatic
H) 7.50–7.48 (d, J ¼ 6 Hz, 4H, aromatic H) 7.33–7.27
(m, 4H, aromatic H) 7.17–7.09 (m, 4H, aromatic H),
3.64–3.56 (m, 8H, NCH2) 1.66–1.64 (m, 8H, NCH2–
CH2) 1.35 (bs, 8H NCH2–CH2–CH2); 13C NMR
(CDCl3): d 125.85, 138.14, 130.67, 127.39, 129.76,
138.14 (aromatic C), 165.5 (azomethine-C), 60.09
(NCH2), 31.11 (NCH2CH2), 27.12; 125Te NMR
(CDCl3): d-242.9. IR (KBr) mmax/cmꢀ1: 1624 (C@N
stretching).
3.1.4. Synthesis of bis(diphenyltelluride)BISTRIEN
Schiff base (6)
Yield: 0.085 g, 32%; m.p. 180 °C. Anal. Calc. for
C40H48N8Te2: C, 53.62; H, 5.40; N, 12.50. Found: C,
53.86; H, 4.88; N, 11.76%. MS (FAB): m=z 732, 582,
502, 462, 369. IR (KBr) mmax/cmꢀ1: 1640 (CH@N
stretching).
3.1. Synthesis of macrocyclic Schiff bases: general proce-
dure
A solution of bis(o-formylphenyl) telluride (1) (0.2 g,
0.59 mmol) in acetonitrile (100 ml) was added to a
stirred solution of a; x-diamine (0.5 mmol) in CH3CN
(100 ml) over a period of 1 h. The mixture was stirred
for 5 h and the precipitated pale yellow powder was
filtered off, washed with acetonitrile and recrystallized
from CHCl3/CH3CN (1:1).
3.1.5. Synthesis of bis(diphenyltelluride)BISDIEN Schiff
base (7)
Yield: 0.15 g, 60%; m.p. 213–215 °C (d). Anal. Calc.
for C36H38N6Te2: C, 53.39; H, 4.73; N, 10.38. Found: C,
53.46; H, 4.93; N, 10.59%. FAB mass spectrum m=z 828
(Mþ + H2O), 810 (Mþ for 128Te), 613, 460, 307, 289, 154;
1H NMR (CDCl3): d 8.67 (s, 4H, azomethine-H), 8.65–
7.00 (m, 16H, aromatic H), 3.82 (m, 8H, NCH2–C) 3.06
(t, J ¼ 6 Hz, 8H NCH2–CH2–NH); 125Te NMR
(CDCl3): d )745.5. IR (KBr) mmax/cmꢀ1: 1636 (CH@N).
3.1.1. Synthesis of bis(diphenyltelluride)BIS-1-MeEN
Schiff base (3)
Yield: 0.157 g, 71%; m.p. 230–232 °C (d). Anal. Calc.
for C34H32N4Te20.5H2O: C, 53.67; H, 4.37; N, 7.36.
Found: C, 53.4; H, 4.2; N, 7.06%. MS (EI): m=z 751 (Mþ
for 128Te), 609, 376, 288, 248, 232. 125Te NMR (CDCl3):
3.2. Synthetic procedures for the transition metal com-
plexes
3.2.1. Synthesis of [Pd(II) 2]Cl2 (9)
d )745 (major), )721, )731, )750. IR (KBr) mmax/cmꢀ1
1631.4 (C@N stretching).
:
To a chloroform (10 ml) solution of 2 (0.1 gm, 0.138
mmol), Pd(C6H5CN)2Cl2 (0.053 g, 0.138 mmol) in di-
chloromethane (10 ml) was added dropwise. On stirring
for 2 h, the yellow precipitate initially formed redis-
solved and a clear red solution was obtained. The sol-
vent was evaporated and the residue was dissolved in
methanol (5 ml). From this solution yellow crystals of
[Pd(II) 2]Cl2 were obtained by vapour diffusion of di-
ethyl ether. Yield: 0.11 g, 88.3%; m.p. 180 °C (d). Anal.
Calc. for C32H28N4Te2ꢀPdCl2 ꢁ 2H2O: C, 41.01; H, 3.44;
N, 5.98. Found: C, 40.75; H, 3.78; N, 6.48%. FAB mass
3.1.2. Synthesis of bis(diphenyltelluride)BISPN Schiff
base (4)
Yield: 0.136 g, 61%; m.p. 255–256 °C (d). Anal. Calc.
for C34H32N4Te21.5H2O: C, 52.43; H, 4.53; N, 7.19.
Found: C, 52.42; H, 4.18; N, 7.12%. MS (FAB): m=z 769
1
(Mþ + H2O), 753 (Mþ), H NMR (CDCl3): d 8.60 (s,
4H, azomethine-H), 7.71–7.68 (m, 4H, aromatic H)
7.46–7.43 (m, 4H, aromatic H) 7.37–7.31 (m, 4H, aro-
matic H) 7.18–7.12 (m, 4H, aromatic H), 4.78 (bs, 8H,
H2O) 3.75 (t, J ¼ 6 Hz, 8H, NCH2–CH2), 2.08 (quintet,
1
spectrum m=z 867 (Mþ–Cl), 830 (Mþ–2Cl); H NMR
(CD3OD): d 9.02 (s, 2H, azomethine-H), 8.91 (s, 2H,
azomethine-H), 7.98–7.92 (m, 4H, aromatic H), 7.77–
7.70 (m, 4H, aromatic-H), 7.67–7.54 (m, 4H, aromatic
H), 7.33–7.28 (m, 2H, aromatic H), 7.07 (d, 2H, J ¼ 7:9
J ¼ 6 Hz, 4H, CH2–CH2–CH2); 125Te(CDCl3):
d
)410.4. IR (KBr) mmax/cmꢀ1: 1700, 1680 (C@N stretch-
ing).

S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
1461
Hz, aromatic H), 4.53–4.45 (m, 2H, CH2), 4.31–4.11 (m,
4H, CH2), 4.06–3.98 (m, 2H, CH2); 13C NMR (DMSO-
d6): d 175.0, 168.1 (coordinated and uncoordinated
azomethine C), 143.7, 143, 141.7, 140.6, 138.3,
138.0,136.8, 135.6, 126.0, 124.5 (aromatic C), 68.8,
63.0(CH2); 125Te NMR (DMSO-d6): d 722; IR (KBr)
m
342 bw, 281 bw, 249, 236 (polyethylene). Conductance
(KM): 142.68 Xꢀ1 cm2 molꢀ1: (methanol).
291, 152, 120; IR (KBr): 1697 m(C@O), 1646 m(C@N)
cmꢀ1
.
3.2.4. Synthesis of [Ni(II) 2](PF6)2 (12)
The ligand 2 (0.1 g, 0.14 mmol) was added to 20 ml of
methanol under nitrogen. This was brought to reflux
and then NiCl2 ꢁ 6H2O (0.033 g, 0.14 mmol) was added.
The suspension changed to clear red solution within 5
min. It was allowed to reflux for additional 15 min. The
solution was filtered and to the filtrate an excess of
NH4PF6 was added. Immediately a red precipitate was
obtained which was filtered and washed with methanol.
Crystals were grown from this sample by diffusing di-
ethyl ether into the nitromethane solution. Yield: 0.135
g, (90%); m.p. 238–240 °C (d). Anal. Calc. for
C32H28N4Te2NiP2F12: C, 35.84; H, 2.63; N, 5.22.
Found: C, 35.69; H, 2.56; N, 4.86%. MS (FAB): 927
(Mþ–PF6), 784 (Mþ–2PF6), 490, 391, 309, 292, 273, 178,
152, 120; UV/Vis (MeCN, k, nm (2, Mꢀ1 cmꢀ1)): 294.8
(15,890), 367 (4630), 488 (630), 809.5 (84). leff : 3.06
BM.; IR (KBr): 1644 m(C@N) 838 m(P–F), 557 d(F–P–F)
max/ cmꢀ1: 1638.8 (C@N stretching), 439.1 bw, 391 bw,
3.2.2. Synthesis of [Pd(II) 2](PF6)2[6b] (10)
To a chloroform (10 mL) solution of 2 (0.1 g, 0.14
mmol), Pd(C6H5CN)2Cl2 (0.053 g, 0.14 mmol) in di-
chloromethane (10 mL) was added dropwise. On stirring
for 2 h the yellow precipitate formed initially redissolved
and a clear red solution resulted. The solvent was
evaporated and the residue was dissolved in methanol (5
mL). To this an excess of NH4PF6 was added. The
precipitated yellow product was filtered off, washed with
methanol and recrystallized from CH3CN by vapour
diffusion of diethyl ether. Yield: 0.13g, (87%); m.p: 202–
204 °C (d). Anal. Calc. for C32H28N4Te2PdP2F12: C,
34.29; H, 5.00; N, 2.5. Found: C, 34.42; H, 5.13; N,
2.45%. MS (FAB): m=z 977 (Mþ–PF6), 832 (Mþ–2PF6),
483, 331, 291, 178, 152, 120; 1H NMR (CD3CN): d 8.99
(s, 2H, azomethine-H), 8.82 (s, 2H, azomethine-H), 7.97
(d, 2H, aromatic-H), 7.91 (d, 2H, aromatic-H), 7.81 (m,
4H, aromatic-H), 7.66 (m, 4H, aromatic-H), 7.37 (t, 2H,
aromatic-H), 7.14 (d, 2H, aromatic-H), 4.51 (d, 2H,
CH2), 4.23 (d, 2H, CH2),4.12 (d, 2H, CH2) 3.92 (d, 2H,
CH2); 13C NMR (CD3CN): d 170.81, 163.76 (coordi-
nated and uncoordinated azomethine C), 139.32, 138.73,
136.90, 136.30, 134.16, 133.93, 132.81, 131.73 (aromatic
carbon), 63.75, 58.11 (CH2); 125Te NMR (CD3CN): d
740. IR (KBr): 1639.8 (C@N stretching), 834.8 (PFꢀ6 )
cmꢀ1
cmꢀ1
.
3.3. Crystal-structure determination of compounds 8, 10,
11, and 12
3.3.1. Data collection, structure solution and refinement
The diffraction measurements were carried out on a
Siemens R3m/V diffractometer using graphite-mono-
ꢀ
chromated Mo Ka radiation ( ¼ 0.71073 A). The struc-
ture solutions and refinement were routine [27–29].
Some details of data collection and refinement are given
in Tables 4 and 5. The high R value of complex 12 re-
Table 4
Crystal data and structure refinement for 8 and 10
3.2.3. Synthesis of 11
8
10
To the ligand 2 (0.1 g, 0.14 mmol) in dichloromethane
(15 mL) was added Pt(COD)Cl2 (0.051 g, 0.14 mmol) in
dichloromethane (2 mL). The reaction was stirred for 16
h, during that time it turned to reddish brown in colour.
The solvent was evaporated and the residue was dis-
solved in methanol by warming. Excess methanol was
evaporated to get 15 ml of the reaction mixture. To this
an excess of ammonium hexaflurophosphate was added.
A reddish brown precipitate that separated out imme-
diately was recrystallized from acetonitrile by vapour
diffusion of diethyl ether. Yield: 0.060 g., (46%); m.p.
260–262 °C (d). Anal. Calc. for C23H19N2TePtOPF6: C,
34.20; H, 2.35; N, 3.47. Found: C, 34.24; H, 2.43; N,
3.45%. 1H NMR (acetone-d6): d 10.24 (d, 1H, aldehydic
H), 9.17 (s, 1H, azomethine H), 8.73 (t, 1H, azomethine
H), 8.47–7.1 (m, 12H, aromatic H), 4.59–4.03 (m, 4H,
@NCH2CH2N@); 125Te NMR (CD3CN): d 708.39 and
684.12; MS (FAB): m=z 663 (Mþ–PF6), 558, 429, 309,
Empirical formula
Fw
Crystal system
C32H46Br4N4O3Te2 C32H28F12N4P2PdTe2
1109.57
Monoclinic
P2=n
1120.12
Monoclinic
P211=n
Space group
ꢀ
a (A)
10.890(5)
7.414(4)
24.334(13)
96.43
8.2250(10)
21.280(4)
21.150(4)
94.190(10)
3691.9(11)
4
ꢀ
b (A)
ꢀ
c (A)
b (°)
V (A )
3
ꢀ
1952.3(17)
2
293(2)
Z
Temperature (K)
293(2)
2.230
Absolute coefficients
)
5.623
(mmꢀ1
Observed reflections
6957
8467
½I > 2rꢄ
a
Final RðF Þ ½I > 2rꢄ
0.0449
0.1040
0.0512
0.1162
wRðF 2Þ indices
½I > 2rꢄ
P
P
P
a Definition: RðF0Þ ¼ kF0j ꢀ Fcjj= jF0j and wRðF02Þ ¼ f ½wðF02
P
2
2 1=2
ꢀFc2Þ ꢄ= ½wðFc2Þ g
.

1462
S.C. Menon et al. / Journal of Organometallic Chemistry 689 (2004) 1452–1463
Table 5
Crystal data and structure refinement for 11 and 12
in Nuclear Sciences (BRNS), Department of Atomic
Energy, Bombay for funding this work. Additional help
from the Regional Sophisticated Instrumentation center
(RSIC), Indian Institute of Technology (IIT), Bombay
for 300 MHz NMR spectroscopy, RSIC, CDRI Luc-
know for mass recording facility and Tata Institute of
Fundamental Research (TIFR), Bombay for 500 MHz
NMR spectroscopy is gratefully acknowledged. R.J.B.
acknowledge the DOD-ONR program for funds to up-
grade the diffractometer.
Compound
11
12
Empirical formula
C23H19F6N2OP- C32H28F12N4Ni-
PtTe
P2Te2
Fw
Crystal system
807.06
Monoclinic
P21=n
12.3253(14)
14.6557(14)
13.4054(11)
90
1072.43
Triclinic
P1
Space group
ꢀ
a (A)
10.800(8)
13.468(9)
13.918(11)
89.67(6)
101.53(7)
81.49(3)
1961(3)
2
ꢀ
b (A)
ꢀ
c (A)
a (°)
b (°)
c (°)
97.000(7)
90
References
3
ꢀ
V (A )
2403.4(4)
4
2.230
Z
D(calcd) (Mg/m3)
Temperature (K)
1.817
293(2)
[1] (a) M. Vetrichelvan, Y.-H. Lai, K.F. Mok, J. Chem. Soc. (2003)
295;
293(2)
0.71073
7.161
(b) B.J. Love, J.M. Vere, M.W. Glenny, A.J. Blake, M.
Schroeder, Chem. Commun. (2001) 2678;
(c) R.D. Adams, Acc. Chem. Res. 33 (2002) 171;
ꢀ
k (A)
0.71073
2.121
6592
Absolute coefficents (mmꢀ1
)
Observed reflections ½I > 2rꢄ 5108
a
€
(d) P. Comba, A. Kuhner, Eur. J. Inorg. Chem. (1999) 509;
(e) P. Comba, A. Kuhner, A. Peters, J. Chem. Soc., Dalton Trans.
Final RðF Þ ½I > 2rꢄ
0.0422
0.1071
0.1240
0.3268
6538/40/526
1.099
wRðF 2Þ indices ½I > 2rꢄ
€
(1999) 509;
Data/restrains/parameters
Goodness-of-fit on F 2
5107/106/409
1.029
€
€
(f) P. Comba, J. Ensling, P. Gutlich, A. Kuhner, A. Peters, H.
Pritzkow, Inorg. Chem. 38 (1999) 3316, and references
therein;
P
P
P
a Definition: RðF0Þ ¼ kF0j ꢀ Fcjj= jF0j and wRðF02Þ ¼ f ½w
P
2
2
1=2
ðF02 ꢀ Fc2Þ ꢄ= ½wðFc2Þ g
.
€
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