Complexes of bidentate phosphane selenide ligands with mesitylenetellurenyl iodide and with tellurium diiodide

Article abstract of DOI:10.1002/ejic.200500843

Bis(diphenylphosphanyl)methane diselenide (dppmSe₂, 1) and bis(diphenylphosphanyl)ethane diselenide (dppeSe₂, 2) reacted with 2 equiv. Br₂ or I₂ to form the insoluble solid products, dppm(SeX₂)_2<

Full text of DOI:10.1002/ejic.200500843

FULL PAPER
DOI: 10.1002/ejic.200500843
Complexes of Bidentate Phosphane Selenide Ligands with Mesitylenetellurenyl
Iodide and with Tellurium Diiodide[
‡]
[a]
[a]
[a]
[b]
Cristian G. Hrib, Peter G. Jones, Wolf-W. du Mont,* Vito Lippolis, and
Francesco A. Devillanova[
b]
Keywords: Phosphane selenides / Tellurium iodides / Heteronuclear NMR / Raman spectroscopy / Soft–soft interactions
Bis(diphenylphosphanyl)methane diselenide (dppmSe
and bis(diphenylphosphanyl)ethane diselenide (dppeSe
reacted with 2 equiv. Br or I to form the insoluble solid
products, dppm(SeX (X = Br, 3; X = I, 4) and dppe(SeX
X = Br, 5; X = I, 6). However, using the iodine-like electro-
phile mesitylenetellurenyl iodide (MesTeI, 7), fairly soluble
complexes, dppmSe [Te(I)Mes] (8) and dppeSe [Te(I)Mes]
9), were obtained. Complexes 8 and 9 contain two T-shaped
10-Te-3) Se–Te(Mes)–I moieties bridged by dppm or dppe;
2
, 1)
tion of 1 with Te and I
was formed. Fortuitously, a crystal of the related compound
dppeSe TeI (11) was also obtained. In 10, a square planar
cis-Se TeI group is part of a six-membered ring, and 11 is a
coordination polymer with trans-Se TeI moieties bridged by
dppe. Averaged P- and Se NMR signals including Se–
2 2 2
, a chelate complex dppmSe TeI (10)
2
, 2)
2
2
2
2
2
)
2
2
)
2
2
2
(
2
2
31
77
77
31
125
2
2
2
2
P couplings, together with broad
Te NMR singlets indi-
(
(
cate phosphane selenide ligand exchange in solution, that is,
the kinetically labile behaviour of complexes 8 and 9.
solid 9 exhibits intermolecular soft–soft interactions between
approximately linear Se–Te–I units. In a side reaction ac-
companying the crystallisation of complex 8, or by the reac-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
Phosphane chalcogenides R RЈP=Y (Y = S, Se) are
2
[
2–5]
known to act as donors towards dihalogen molecules.
Using phosphane selenides, which are stronger donors than
the sulfides, a considerable number of 1:1 adducts
[6–9]
R RЈPSeX have been isolated.
Iodine adducts exhibit
2
2
type A (10-I-2) molecular structures R RЈPSeI (R, RЈ =
2
2
[
7]
[8]
C H , NMe , NEt and R = tBu, RЈ = I) or type C (10-
6
5
2
2
+
– [6,10,11a]
I-2) ionic structures (R PSe) I I ,
whereas bromi-
3
2
3
nation products exhibit type B (10-Se-3) T-shaped PSeBr2
moieties in their structures (R, RЈ = NMe , C H ,
2
6
11
[
9,11a]
iC H ).
With excess iodine, polyiodide salts featuring
3
7
+
[4,10,12]
R PSeI countercations (type D),
could be formed
Scheme 1). Many of these compounds are aggregated by
further soft–soft contacts that lead to ion pairs, chains and
3
(
[
3,4,6,8,9,11b,12]
extended networks.
In particular, type D-like
Scheme 1. Various Lewis-type structures of halogen adducts of
(
iodoseleno)phosphonium cations behave as soft electro- phosphane selenides. These structures must be intended purely as
a formal illustration of the various compounds with no implication
philes by the iodine atom in the β position to the formally
charged phosphorus atom (β-heteroatom Lewis acid-
ity).
as to the real distribution of charges. The same considerations ap-
ply to Scheme 2 and Scheme 3.
[
3,10,12]
1]
[
[
‡] Properties of Chalcogen–Chalcogen Bonds, 24. Part 23: Ref.[
To stimulate the formation of supramolecular networks
using the earlier mentioned types of soft–soft interactions,
we are introducing bifunctional donor-acceptor systems into
our studies. In a previous paper we described the self-as-
a] Institut für Anorganische und Analytische Chemie der Tech-
nischen Universität Braunschweig,
Postfach 3329, 38023 Braunschweig, Germany
Fax: +49-531-3915387
E-mail: w.du-mont@tu-bs.de
[
b] Dipartimento di Chimica Inorganica ed Analitica, Complesso sembly of iodophosphane selenides RRЈP(=Se)I as bifunc-
Universitario di Monserrato,
tional donor-acceptor molecules (selenium donor, iodine
S. S. 554 Bivio per Sestu, 09042 Monserrato (CA), Italia
[
8]
acceptor). The bifunctional selenocarbonyl ligand 1,2-
bis(3-methyl-4-imidazolin-2-selone)ethane was recently
Fax: +39-070-6754456
E-mail: devilla@unica.it
1294
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1294–1302

Complexes of Bidentate Phosphane Selenide Ligands
13]
FULL PAPER
shown to undergo Br [ and IBr[14] oxidative addition at not occur. The P NMR spectrum of this solution shows
31
2
the Se atom of the ϾC=Se group, exhibiting a subtle inter- only one resonance with a 7 Se, P satellite coupling that is
7
31
play of soft–soft and hydrogen-bonding interactions in the smaller than that of the starting material. The 31P NMR
solid.
singlet may be due to a symmetric bonding mode of 1 with
In our present work we evaluate the use of bifunctional iodine, or, alternatively, to a rapid equilibration of coordi-
phosphane selenides, bis(diphenylphosphanyl)methane di- nated and noncoordinated PSe functions (that is, signal av-
selenide (dppmSe , 1) and bis(diphenylphosphanyl)ethane eraging). In the 77Se NMR spectra, titration-like addition
2
77
diselenide (dppeSe , 2), towards halogens (Br , I ) and of I led to stepwise deshielding [1: δ Se = –240 ppm, 1/I
towards the halogen-like electrophile mesitylenetellurenyl (1:1 complex): δ Se = –68 ppm] and line broadening. This
iodide [MesTeI, 7; Mes = 2,4,6-(CH ) C H ] with the in- observation implies signal averaging at all stages of the
2
2
2
2
2
77
[15]
3
3
6
2
tention of creating supramolecular soft–soft networks. Ar- iodine addition. Crystals of the 1:1 product were not ob-
enetellurenyl chlorides and bromides are known to give tained; precipitation by addition of pentane led to the solid
[
16a]
stable 1:1 complexes with triphenylphosphane selenide,
1:2 product 4. Similarly, attempts to prepare 1:1 adducts of
[16a,16b]
tri(morpholine)phosphane selenide
and tris(dimethyl- 1 and 2 with bromine led to formation of insoluble 5 and 6.
amino)phosphane selenide.[
17]
Reactions of dppmSe (1) and dppeSe (2) with MesTeI (7)
2
2
Results and Discussion
With the intention of exerting control over solubility
properties and of introducing the NMR-active 1 Te nu-
cleus as an additional probe for solution studies, we decided
to include tellurenyl iodides in our study. Arenetellurenyl
halides are known to exhibit electrophilic properties
towards soft ligands; typically bromide, iodide and S-donor
ligands lead to T-shaped complexes. A few phosphane sele-
nide–tellurenyl bromide and chloride complexes have been
25
Formation of 1:2 Adducts of dppmSe (1) and dppeSe (2)
2
2
with Br and I
2
2
Addition of 2 equiv. Br or I to solutions of bidentate
2
2
phosphane selenides (dppmSe , 1, and dppeSe , 2) led to
precipitation of solids of the composition dppm(SeX ) (X
2
2
2
2
=
Br, 3; X = I, 4) and dppe(SeX ) (X = Br, 5; X = I, 6)
2 2
[
16,17]
crystallographically studied,
but neither a systematic
(Scheme 2).
structural study nor any heteronuclear NMR spectroscopic
data has yet appeared in the literature. To favour aryl pack-
ing in the solid, we chose the in situ generated mesitylenetel-
[15]
lurenyl iodide [MesTeI, 7; Mes = 2,4,6-(CH ) C H ]
as
3
3
6
2
the iodine-related electrophile for coordination with 1 and
2.
Addition of 1 or 2 to 2 equiv. 7, prepared from Mes Te2
2
with I , led to compounds 8 and 9, which were isolated in
2
moderate yields by crystallisation (Scheme 3). Complexes 8
and 9 were characterised by multinuclear NMR spec-
troscopy in solution, and a single crystal of the dppeSe2
complex 9 was studied by X-ray crystallography.
Attempts to grow single crystals from crude solutions of
8
led to a few single crystals of an unexpected tellurium
diiodide chelate complex 10. Compound 10 was also iso-
lated in small yield from reaction mixtures that were in-
tended to produce a 1:1 complex of 1 with 7. The 31P NMR
spectra of the 1:1 complexes of 1 and 2 with MesTeI show
1
J
77Se,31
coupling constants between those of 1,2 and 8,9
P
Scheme 2. 1:2 Reactions of dppmSe
For an alternative structure of 4, see vibrational spectra.
2
and dppeSe
2
with Br
2
and I
2
.
(Table 1). Compound 10 was also accessible by addition of
elemental tellurium and iodine to dissolved 1 (Scheme 3).
Fortuitously, upon crystallisation of compound 9, a single
Since these materials are insoluble in aprotic-dipolar sol- crystal of the related tellurium diiodide complex 11 of li-
vents and thus cannot be recrystallised, compounds 3–6 gand 2 was also isolated and studied by X-ray crystallogra-
were not obtained as single crystals. In the absence of crys- phy.
tal data, only Raman spectra could be of help in investiga-
Formation of the TeI complexes 10 and 11 from 7 in-
2
ting the structural features of the expected PSeX functions volves breaking the Te–C bond, but the fate of the “lost”
2
of the compounds (see later). Reaction of dppe-diselenide 2 mesityl group remains unclear. Te–C bond cleavage with
with only 1 equiv. I also led to precipitation of the 1:2 mesityl group transfer has previously been observed after a
2
product 6; however, from CH Cl solutions containing 1:1 bromination/bromide abstraction sequence started with
2
2
+
–
+
– [1]
mixtures of dppm-diselenide 1 with iodine, precipitation did Mes Te and led to Mes Te SbF and Mes Te2 SbF6 .
2
3
6
5
Eur. J. Inorg. Chem. 2006, 1294–1302
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1295

C. G. Hrib, P. G. Jones, W.-W. du Mont, V. Lippolis, F. A. Devillanova
FULL PAPER
2 2
Scheme 3. Reactions of dppmSe and dppeSe with MesTeI.
Table 1. 31P-, 77Se- and 125Te NMR spectroscopic data of ligands 1,2, acceptor 7 and complexes 8,9,10 (solvent: CD
Cl
2
2
3
, *CDCl ).
δ = 31P
ppm]
1JP,Se
[Hz]
nJP,Se
[Hz]
δ = 77Se
[ppm]
δ = 125Te
[ppm]
nJP,P
[Hz]
[
dppmSe
dppmSe
dppmSe
2
2
2
(1)[19,20]
25.8
24.1
21.8
36.6
35.8
–
744.5
717.7
682.3
730.0
711.6
–
2.5
–
–
0.7
12.2
–
–240.4
–161
–93*
–353.4
–281
–
–
796
–
17.6
12.4
8.9
64.8
63.7
–
[Te(I)Mes]
2
(8)
TeI
2
(10)
[
19]
dppeSe
dppeSe
2
(2)
–
2
[Te(I)Mes]
2
(9)
798
867
727
614
MesTeI (7)
1
1
:1 complex (1:7)*
:1 complex (2:7)*
24.2
35.6
727.5
720.8
–
–
–170
–
–
–
Thermal decomposition of arenetellurenyl halides can also not allow the resolution of couplings with 31P: the kinetic
involve Te–C bond cleavage (loss of tellurium).[
15]
lability (fast ligand exchange) of complexes 8 and 9 involves
Se–Te bond breaking, whereas P–Se bonds stay intact. In
relation to the signals of noncoordinated monomeric al-
125
NMR Spectroscopic Investigation of Binuclear Complexes 8 kane- and arenetellurenyl halides [(Me Si) CTeI: δ Te =
3
3
[
21]
125
[15]
and 9
1185 ppm,
2,4,6-iPr C H TeI: δ Te = 842 ppm,
3 6 2
125
[15]
2
,4,6-tBu C H TeI: δ Te = 1162 ppm,
2,4,6-Me C H
3 6 2-
3
6
2
The coordination of phosphane selenides with iodine or
the oxidative addition of bromine to phosphane selenides is
accompanied by a decrease in the NMR coupling constant
125
125
TeI: δ Te = 867 ppm], the
Te NMR signals of com-
plexes 8 and 9 are deshielded by about 44–390 ppm. In the
case of 8 and 9 and their mixtures with 1 and 2, the ex-
change is apparently very fast on the NMR time scale.
1
[7–10]
J
31P,77
Se.
The same observation is made when the biden-
tate phosphane selenide 1 reacts with 1 equiv. iodine, and
when 1 or 2 coordinate with 2 equiv. mesitylenetellurenyl
iodide 7. Solutions containing 1 or 2 with fewer than
X-ray Crystallographic Studies
3
1
2
equiv. 7 do not give separate P NMR signals for the
different species in solution, instead averaged signals ap-
pear, which also show averaged Se satellites. The averaged ing bidentate ligand between two Te(I)Mes acceptor moie-
In solid dppeSe [Te(I)Mes] (9), dppeSe acts as a bridg-
2
2
2
7
7
1
magnitudes of J
31P,77
decrease with increasing amounts of ties (Figure 1a). The heavy-atom positions correspond to
Se
7
7
the electrophile 7. The changes in the Se NMR resonances local inversion symmetry (rmsd = 6.6 pm; Figure 1b).
[
18,19]
of 1 and 2
upon coordination with 7 (deshielding coor-
The molecules are packed in a way that allows side-on
3
1
dination shifts) are much larger than those of the P NMR intermolecular soft–soft interactions between approxi-
signals (Table 1). The Se NMR resonances of 8 and 9 ap- mately linear Se–Te–I units, thus linking the molecules in
pear as (pseudo) doublets [X-parts of AAЈX systems]
7
7
[
18–20]
chains parallel to the x axis (Figure 2).
due to J77 31 , but they do not exhibit satellites from coup-
ling with Te. Similarly, the broad Te NMR signals do relevant van der Waals radii. The “T”-type Se–Te(–C)–I
The Te–I contacts are in the range of the sum of the
Se,
25
P
1
125
1296
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1294–1302

Complexes of Bidentate Phosphane Selenide Ligands
FULL PAPER
units deviate slightly from planarity (angles C–Te–Se 90°,
C–Te–I 89°, Se–Te–I 173°; for standard deviations see
Table 2); Se–Te and Te–I distances are in agreement with
[
11]
typical 3c-4e bonding (10-Te-3,
close to 0.5).
both bond orders are
[
15,22,23]
Table 2. Bond lengths, interatomic contact distances [pm] and
(9).[
a]
angles [°] of dppeSe
2
[Te(I)Mes]
2
Te(1)–C(14)
Te(1)–Se(1)
Te(1)–I(1)
Te(1)–Te(1Ј)#1
I(1)–Te(1Ј)#1
Se(1)–P(1)
213.2(4)
C(1)–C(1Ј)
Te(1Ј)–C(14Ј)
Te(1Ј)–I(1Ј)
Te(1Ј)–Se(1Ј)
I(1Ј)–Te(1)#2
Se(1Ј)–P(1Ј)
Se(1Ј)–I(1)#2
151.8(4)
213.8(3)
287.75(4)
289.61(4)
415.83(3)
400.35(4)
215.13(9)
404.32(5)
288.69(3)
288.74(4)
398.87(4)
215.08(9)
414.30(5)
Se(1)–I(1Ј)#1
C(14)–Te(1)–Se(1)
C(14)–Te(1)–I(1)
Se(1)–Te(1)–I(1)
91.5(1)
89.85(9)
172.96(1)
C(1)–P(1)–Se(1)
C(14Ј)–Te(1Ј)–I(1Ј)
113.4(1)
88.95(9)
C(14Ј)–Te(1Ј)–Se(1Ј) 89.96(9)
I(1Ј)–Te(1Ј)–Se(1Ј) 172.55(1)
Te(1Ј)–I(1Ј)–Te(1)#2 72.430(8)
P(1Ј)–Se(1Ј)–Te(1Ј)
P(1Ј)–Se(1Ј)–I(1)#2
C(14)–Te(1)–Te(1Ј)#1 155.37(9)
Se(1)–Te(1)–Te(1Ј)#1
I(1)–Te(1)–Te(1Ј)#1
Te(1)–I(1)–Te(1Ј)#1
P(1)–Se(1)–Te(1)
P(1)–Se(1)–I(1Ј)#1
Te(1)–Se(1)–I(1Ј)#1
C(2)–P(1)–Se(1)
111.30(1)
66.379(8)
72.110(8)
106.32(3)
119.20(2)
67.996(9)
110.2(1)
107.05(3)
119.70(3)
Te(1Ј)–Se(1Ј)–I(1)#2 66.673(9)
C(8Ј)–P(1Ј)–Se(1Ј)
C(2Ј)–P(1Ј)–Se(1Ј)
C(1Ј)–P(1Ј)–Se(1Ј)
113.4(1)
110.0(1)
111.7(1)
C(8)–P(1)–Se(1)
112.7(1)
[
#
a] Symmetry transformations used to generate equivalent atoms:
1: x – 1, y, z; #2: x + 1, y, z.
The Se–Te bonds in complex 9 are longer (Table 3) than
those in chloro- and bromo-phenyl(trimorpholinophos-
[
16a,16b]
phane selenide)tellurium()
(
and bromophenyl[tris-
[
17]
dimethylamino)phosphane selenide]tellurium(),
and
this correlates well with the weaker donor properties of alk-
yl-/arylphosphane selenides compared with aminophos-
[
16a,16b,17,23]
phane selenides.
As expected, SeǞTe donation
Figure 1. (a) Structure of dppeSe [Te(I)Mes] (9); ellipsoid prob- is accompanied by P–Se bond expansion (ligand 2:
2 2
ability level 50%; all hydrogen atoms omitted for clarity; primes
indicate atoms related by pseudosymmetry. (b) Least-squares fit of
the two halves of molecule 9 (only heavy atoms and ipso-C fitted).
[18b]
209.4 pm,
complex 9: 215.1 pm).
Table 3. Important bond lengths (P–Se, Se–Te, Te–X) in solid phos-
phane selenides and phosphane selenidetellurenyl halogenides [pm].
P–Se
Se–Te
Te–X
18a]
dppmSe
2
(1)[
210.3(1)
209.4(2)
215.13(9)
–
–
–
–
dppeSe
dppeSe
2
(2)[
18b]
2
[Te(I)Mes]
2
(9)
287.75(4)
288.74(4)
284.10(5)
283.00(4)
280.37(2)
276.89(9)
278.27(9)
276.3(1)
289.61(4)
288.69(3)
290.67(4)
291.42(4)
294.28(2)
276.1(1)
260.0(2)
274.4(1)
2
15.08(9)
215.33(8)
14.47(8)
dppmSe
2 2
TeI (10)
2
dppeSe TeI
2
2
(11) [
215.80(4)
218.2(2)
217.6(2)
218.3(2)
16b]
Mor
Mor
3
PSeTe(Ph)Br
PSeTe(Ph)Cl[
16b]
3
PSeTe(Ph)Br[
17]
[(CH
3
)
2
N]
3
The chelate complex dppmSe TeI (10) contains a dis-
2
2
Figure 2. Intermolecular interactions in the packing diagram of 9;
selected contact distances [pm]: Se(1)–I(1Ј) 404.32(5), I(1Ј)–Te(1)
torted square planar cis-Se TeI group (12-Te-4) as part of
2
2
a puckered six-membered heterocycle with two different P–
Se–Te angles (95.4 and 102.9°) (Figure 3, Table 4).
3
98.87(4), Te(1)–Te(1Ј) 415.83(3), I(1)–Te(1Ј) 400.35(4), Se(1Ј)–I(1)
14.30(5).
4
Eur. J. Inorg. Chem. 2006, 1294–1302
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1297

C. G. Hrib, P. G. Jones, W.-W. du Mont, V. Lippolis, F. A. Devillanova
FULL PAPER
2 2
Figure 3. Structure of dppmSe TeI (10); ellipsoid probability level
50%; all hydrogen atoms omitted for clarity.
Figure 4. Intermolecular interactions in the packing diagram of 10;
selected contact distances [pm]: Se(1)–Se(1) 345.42(7), Se(2)–I(2)
414.98(6).
Table 4. Bond lengths, interatomic contact distances [pm] and
2 2
angles [°] of dppmSe TeI
(10).[
a]
Te–Se(2)
Te–Se(1)
Te–I(1)
283.00(4)
284.10(5)
290.67(4)
291.42(4)
215.33(8)
345.42(7)
214.47(8)
Se(2)–I(2)#2
P(1)–C(8)
P(1)–C(2)
P(1)–C(1)
P(2)–C(20)
P(2)–C(14)
P(2)–C(1)
414.98(6)
179.7(3)
179.9(3)
182.7(3)
179.7(3)
179.9(3)
182.1(3)
Te–I(2)
Se(1)–P(1)
Se(1)–Se(1)#1
Se(2)–P(2)
Se(2)–Te–Se(1)
Se(2)–Te–I(1)
Se(1)–Te–I(1)
Se(2)–Te–I(2)
Se(1)–Te–I(2)
I(1)–Te–I(2)
86.53(1)
171.38(1)
90.19(1)
88.18(1)
172.01(1)
95.86(1)
95.34(2)
P(2)–Se(2)–I(2)#2 90.09(2)
Te–Se(2)–I(2)#2
C(8)–P(1)–Se(1)
C(2)–P(1)–Se(1)
C(1)–P(1)–Se(1)
147.28(1)
110.9(1)
115.4(1)
112.77(9)
C(20)–P(2)–Se(2) 112.6(1)
C(14)–P(2)–Se(2) 111.68(9)
P(1)–Se(1)–Te
P(1)–Se(1)–Se(1)#1 140.58(2)
C(1)–P(2)–Se(2)
P(2)–C(1)–P(1)
111.93(9)
118.6(2)
Te–Se(1)–Se(1)#1
P(2)–Se(2)–Te
121.91(1)
102.86(2)
[
#
a] Symmetry transformations used to generate equivalent atoms:
1: –x + 1, –y +1, –z; #2: –x + , y – ½, –z + ½.
A similar kind of distortion is documented in the
[
24]
[25]
chelate complexes dppmS TeCl ,
dppmSe HgI ,
2
4
2 2
[
25]
[26]
dppmSe HgBr
and dppmSe ZnBr . The distortion of
2
2
2 2
the tellurium coordination spheres can be explained by the
[18a,27,28]
tendency of the ligands dppmE (E = O, S, Se)
to
2
avoid intramolecular repulsion of the P(=E)Ph groups (1:
2
E = Se). In 10 the torsion angle Se(1)P(1)···P(2)Se(2) is 32°.
The small bite angle Se(1)–Te–Se(2) (86.5°) is associated
with a widening of the opposite angle I(1)–Te–I(2) (95.9°).
Se–Te bond lengths in 10 are shorter than those of 9 be-
cause of the better acceptor properties of TeI compared
2
with MesTeI. Te–I distances [Te–I(1) 290.6 pm, Te–I(2)
2
91.4 pm] are slightly longer than those in 9 but shorter
2
–
than those in the square planar TeI4
anion
Figure 5. (a) Structure of dppeSe
soid probability level 50%; all hydrogen atoms omitted for clarity.
b) Polymeric structure of dppeSe TeI (11). The chain direction is
Te–I distances parallel to the x axis.
2 2
TeI (11); asymmetric unit; ellip-
[
29]
[
298.5(2) pm].
selenourea-Se)tellurium] diiodide
and cis-diiodobis(thiourea-S)tellurium,[
In the case of bis[(µ -iodo)bis(ethylene-
2
[30]
[Te–Se 261.8(1) pm]
(
2
2
31]
1298
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1294–1302

Complexes of Bidentate Phosphane Selenide Ligands
FULL PAPER
are very long [325.1(1) and 316.2(1) pm, respectively]. Com-
Compounds 3 and 5 have similar FT-Raman spectra with
–1
plex 10 also exhibits intermolecular soft–soft interactions two peaks at 144 and 195 cm for 3, and at 157 and
Figure 4).
191 cm–1 for 5, which agree with the presence of asymmetric
The Se(1)–Se(1Ј) interaction is shorter than the sum of Br–Se–Br groups in both compounds.[13,38,39]
the van der Waals radii and the Se(2)–I(1Ј) interaction is at The FT-Raman spectra of the corresponding adducts
the limit of the van der Waals radii. The selenium and with I , 4 and 6, differ from each other; compound 4 has a
(
2
–1
iodine atoms exhibit borderline H···Se(I) intermolecular strong peak at 116 cm accompanied by a weaker peak at
–1
contacts (H···Se 316–334 pm, H···I 296–330 pm).
145 cm , whereas 6 has two well-defined peaks at 145 and
Complex 11 is a helical coordination polymer with cen- 152 cm–1 (see Figure 6).
trosymmetric trans-Se TeI moieties (12-Te-4) bridged by
2
2
centrosymmetric dppe units (Figure 5, Table 5).
2 2
Table 5. Bond lengths [pm] and angles [°] of dppeSe TeI
(11).[a]
Te(1)–Se(1)
Te(1)–I(1)
Se(1)–P(1)
P(1)–C(8)
280.37(2)
294.28(2)
215.80(4)
179.9(2)
P(1)–C(2)
P(1)–C(1)
C(1)–C(1)#2
180.4(2)
182.4(2)
153.0(3)
Se(1)–Te(1)–Se(1)#1
Se(1)–Te(1)–I(1)
Se(1)#1–Te(1)–I(1)
Se(1)–Te(1)–I(1)#1
180.0
I(1)–Te(1)–I(1)#1
P(1)–Se(1)–Te(1)
C(8)–P(1)–Se(1)
C(2)–P(1)–Se(1)
C(1)–P(1)–Se(1)
180.0
86.834(5)
93.167(5)
93.165(5)
102.74(1)
113.29(5)
106.89(5)
112.49(5)
Se(1)#1–Te(1)–I(1)#1 86.833(6)
[
#
a] Symmetry transformations used to generate equivalent atoms:
1: –x + 1, –y, –z; #2: –x, –y, –z.
Figure 6. FT-Raman spectra of 4 (solid line) and 6 (dotted line).
The spectrum of 4 indicates the presence of asymmetric
linear I–Se–I moieties, whereas the spectrum of 6 is more
consistent with a charge-transfer nature, characterised by
The tellurium atom lies on the inversion centre ½, 0, 0
and the midpoint of the C1–C1Ј bond lies on 0, 0, 0. Com-
pared with the distorted chelate complex 10, the coordina-
tion polymer 11 exhibits Se–Te bonds shorter by 3–4 pm
and Te–I bonds longer by 3–4 pm. The coordination envi-
ronment of Te in 11 deviates from square by expansion of
the angle Se(1)–Te–I(1)#1 (93.2°) and compression of the
angle Se(1)–Te–I(1) (86.8°). Among the three compounds
[35]
the presence of linear Se–I–I groups. Strong I -charge-
2
transfer adducts with selenium-donor molecules generally
feature two bands in their FT-Raman spectra near 150 and
–1
1
30 cm which are assigned to the antisymmetric and sym-
metric stretching modes, respectively, of the Se–I–I sys-
9
, 10 and 11, the latter exhibits the shortest coordinative
[34,35,37]
tem.
Se–Te bond (280.3 pm). The Te–I bond lengths are close to
those in trans-diiodobis(tetramethylselenourea-Se)tellurium
(
2
Complexes 8 and 9 have similar FT-Raman spectra with
–1
a strong peak at 126 cm accompanied by a weaker shoul-
31]
trans-Se TeI
moieties)
[295.4(1) pm][
[Te–Se
–1
2
2
der at 142 cm for 8, and, correspondingly, at 129 and
82.1(1) pm], and are also similar to Te–I bonds in related
–1
1
46 cm for 9 (see Figure 7 for the FT-Raman spectrum of
[32]
trans-S TeI moieties (293.3–298.2 pm).
2
2
8).
Vibrational Spectra
FT-Raman spectroscopy is the main method of investiga-
ting the nature of the products obtained by the reactions of
dihalogens/interhalogens with donor molecules containing
1
5- and 16-group elements in the absence of X-ray struc-
[
33–38]
tural data.
Among the compounds reported here, 3–6 are molecular
adducts of dppm and dppe with Br and I , while 8–11 are
obtained by reacting the same ligands with MesTeI. No
crystallographic data are available for 3–6, but structural
information can be obtained by comparing their FT-Raman
2
2
Figure 7. FT-Raman spectra of 8 (dotted line) and 10 (solid line).
On the basis of this similarity, it is possible to infer that
the structural features of 8 are analogous to those of 9;
spectra with those of several structurally characterised I
2
[33–38]
and Br adducts with Se-donor molecules.
In contrast, therefore, for both compounds the two FT-Raman peaks
2
no FT-Raman data are available from the literature for should be tentatively assigned to the symmetric and anti-
compounds similar to 8–11, but the knowledge of the crys- symmetric stretching vibrations of the Se–Te–I system. As
tal structures of 9–11 allows a first tentative correlation be- already mentioned, these assignments cannot be supported
[
40]
tween structural and FT-Raman data for these compounds. by any data from the literature. Significantly, the FT-Ra-
Eur. J. Inorg. Chem. 2006, 1294–1302
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1299

C. G. Hrib, P. G. Jones, W.-W. du Mont, V. Lippolis, F. A. Devillanova
FULL PAPER
man peaks observed for 8 and 9 occur at frequencies close 4: Diselenide 1 (1.08 g, 2.0 mmol) was dissolved in dichlorometh-
ane (20 mL) and a solution of iodine (1.01 g, 4.0 mmol) in dichlo-
romethane (20 mL) was added. The reaction mixture was stirred at
to those normally observed for the peaks typical of strong
charge-transfer adducts featuring linear Se–I–I groups.
room temp. for 3 h, after which the raw product 4 was isolated by
Therefore, the two systems Se–Te–I and Se–I–I appear to
vacuum evaporation of the solvent, and purified by washing with
have a similar vibrational behaviour.
pentane and drying under vacuum evaporation. A red dppm-
The spectrum of 10 shows four peaks at 150 (shoulder),
(
C
2
SeI
2
)
2
complex was obtained. Yield: 1.93 g, 92%; m.p. 138–139 °C.
Se (1049.23): calcd. C 28.60, H 2.11; found C 28.57, H
1
37, 116 and 106 cm–1 in good agreement with its structural
25
H
22
I
4
P
2
2
features (see Figure 7). In fact, by approximating the local
symmetry around the Te atom to the C2v point group, four
Raman-active stretching vibration modes are to be ex-
pected. Therefore, on the basis of the different atomic
–1
.06. FT-Raman: ν˜ = 145 (2), 116 (10) cm .
5: Diselenide 2 (1.11 g, 2.0 mmol) was dissolved in dichlorometh-
ane (20 mL) and a solution of bromine (0.63 g, 4.0 mmol) in
dichloromethane (20 mL) was added. The reaction mixture was
stirred at room temp. for 2 h, after which the raw product 5 was
isolated by vacuum evaporation of the solvent, and purified by
–
1
weight of Se and I, the peaks at 106 and 116 cm should
have a predominant contribution from the symmetric and
antisymmetric stretching modes of the TeI group, respec- washing with pentane and drying under vacuum evaporation. A
2
–
1
tively, while the peaks at 137 and 150 cm should have a yellow dppe(SeBr
predominant contribution from the analogous vibrations of
2
)
2
complex was obtained. Yield: 1.66 g, 95%;
Se (875.95): calcd. C 35.05, H 2.76;
found C 34.98, H 2.98. FT-Raman: ν˜ = 191 (9.5), 157 (10) cm .
m.p. 148–149 °C. C26
H24Br
4
P
2
2
–
1
the TeSe group.
2
The local symmetry around the Te atom in 11 can be 6: Diselenide 2 (1.11 g, 2.0 mmol) was dissolved in dichlorometh-
approximated instead to the D2h point group, and only the ane (20 mL) and a solution of iodine (1.01 g, 4.0 mmol) in dichlo-
A vibrations for the linear I–Te–I and Se–Te–Se groups romethane (20 mL) was added. The reaction mixture was stirred at
g
room temp. for 2.5 h, after which the raw product 6 was isolated
by vacuum evaporation of the solvent, and purified by washing
with pentane and drying under vacuum evaporation. A red dppe-
should be Raman-active. Indeed, the FT-Raman spectrum
–
1
of 11 shows a very strong peak at 110 cm and a much
–
1
weaker peak at around 150 cm . Also in this case, the peak
at lower frequency should have a predominant contribution
from the symmetric stretching vibration of the I–Te–I moi-
ety, whereas that at higher frequency should have a pre-
dominant contribution from the symmetric stretching vi-
bration of the Se–Te–Se moiety. This assignment can be
considered as reasonable since the symmetric I–Te–I and
Se–Te–Se groups are structurally comparable to the sym-
(
C
2
SeI
2
)
2
complex was obtained. Yield: 1.96 g, 92%; m.p. 197–198 °C.
Se (1063.95): calcd. C 29.35, H 2.27; found C 29.29, H
26
H
24
I
4
P
2
2
–1
.23. FT-Raman: ν˜ = 152 (10), 145 (10) cm .
8: Dimesityl ditelluride (0.99 g, 2.0 mmol) was dissolved in dichlo-
romethane (20 mL) and a solution of iodine (0.51 g, 2.0 mmol) in
dichloromethane (10 mL) was added. The reaction mixture was
added to a solution of diselenide 1 (1.08 g, 2 mmol) in dichloro-
methane and was stirred for 24 h at room temp., after which the
raw product 8 was isolated by vacuum evaporation of the solvent,
and purified by washing with pentane, drying under vacuum evapo-
ration and recrystallised by gas diffusion from dichloromethane/
–
–
–
–
metric I3 and IBr , respectively. Indeed, I and IBr ,
2
3
2
when symmetric, are characterised by only one Raman
–
1
[37,38,41]
peak at around 110 and 160 cm , respectively.
Unfortunately, the quality of the FTIR spectra for all the pentane. Yield: 1.93 g, 75%; m.p. 77–78 °C. C43
H
44
I
2
P
2
Se
2
Te
2
3
1
(
(
1289.69): calcd. C 40.05, H 3.44; found C 39.80, H 3.44. P NMR
compounds considered prevents any further discussion.
1
2
CD
2
Cl
2
): δ = 24.1 (s, JP,Se = 717.7 Hz, JP,P = 12.4 Hz, 2 P) ppm.
7
7
1
Se NMR (CD
2
Cl
Cl
2.2 (s, 6 H), 2.5 (s, 12 H), 4.3 (t, JH,P = 13.1 Hz, 2 H), 6.9 (s, 4 H),
2
): δ = –161 (br. d, JSe,P = 750± 50 Hz) ppm.
1
25
1
Te NMR (CD
2
2 2 2
): δ = 796 (br. s) ppm. H NMR (CD Cl ): δ
=
1
3
Experimental Section
2 2
7.3 (m, 8 H), 7.4 (m, 4 H), 7.6 (m, 8 H) ppm. C NMR (CD Cl ): δ
=
4
5
1
21.3 (s, 2 C), 31.2 (s, 4 C), 34.2 (s, 1 C), 117.5 (s, 2 C), 127.5 (s,
C), 127.8 (s, 4 C), 129.2 (t, JC,P = 6.6 Hz, 8 C), 132.8 (t, JC,P
.9 Hz, 8 C), 141.4 (s, 2 C), 147.2 (s, 4 C) ppm. FT-Raman: ν˜ =
NMR spectra were recorded using Bruker spectrometers AC 200,
=
Avance 200, Avance 400 and AMX 300, with 85% H
3 4
PO ,
(
CH Se, (CH Te and SiMe as external or internal standards.
3
)
2
3
)
2
4
–
1
42 (5), 126 (10) cm .
–1
FT-Raman spectra, in the range 500–50 cm , were recorded with
a resolution of 2 cm–1 with a Bruker RFS100 FT-Raman spectrom-
eter, fitted with an In-Ga-As detector (room temp.) operating with
a Nd-YAG laser (excitation wavelength 1064 nm; 50–100 mW),
with a 180° scattering geometry. The values in parentheses next to
the wavenumber values reported for each compound represent the
intensities of the peaks relating to the strongest, taken to be 10.
9
: Dimesityl ditelluride (0.99 g, 2.0 mmol) was dissolved in dichlo-
romethane (20 mL) and a solution of iodine (0.51 g, 2.0 mmol) in
dichloromethane (10 mL) was added. The reaction mixture was
added to a solution of diselenide 2 (1.11 g, 2 mmol) in dichloro-
methane and was stirred for 24 h at room temp., after which the
raw product 9 was isolated by vacuum evaporation of the solvent,
and purified by washing with pentane, drying under vacuum evapo-
ration and recrystallised by gas diffusion from dichloromethane/
3: Diselenide 1 (1.08 g, 2.0 mmol) was dissolved in dichlorometh-
ane (20 mL) and a solution of bromine (0.63 g, 4.0 mmol) in
dichloromethane (20 mL) was added. The reaction mixture was
stirred at room temp. for 2 h, after which the raw product 3 was
isolated by vacuum evaporation of the solvent, and purified by
washing with pentane and drying under vacuum evaporation. An
pentane. Yield: 2.00 g, 77%; m.p. 158–159 °C. C44
(1303.67): calcd. C 40.54, H 3.56; found C 39.00, H 3.57. P NMR
46 2 2 2 2
H I P Se Te
3
1
1
3
4
(CD
2
Cl
2
): δ = 35.8 (s, JP,Se = 711.6 Hz, JP,P = 63.7 Hz, JP,Se
=
=
12.2 Hz, 2 P) ppm. 77Se NMR (CD
Cl
Cl
): δ = 2.4 (s, 6 H), 2.7 (s, 12 H), 2.9 (d,
2.3 Hz, 4 H), 7.03 (s, 4 H), 7.5 (m, 8 H), 7.6 (m, 4 H), 7.8 (m, 8 H)
1
2
2
): δ = –281 (br. d, JSe,P
2
): δ = 798 (br. s) ppm. H
1
25
1
690± 50 Hz) ppm. Te NMR (CD
NMR (CD Cl
2
2
orange dppm(SeBr
m.p. 133–134 °C. C25
found C 34.19, H 2.34. FT-Raman: ν˜ = 195 (10), 144 (10) cm .
2
)
2
complex was obtained. Yield: 1.53 g, 89%;
2
2
H,P
J =
H22Br
4
P
2
Se (861.93): calcd. C 34.84, H 2.57;
2
–
1
13
ppm. C NMR (CD
2
Cl
2
): δ = 21.1 (s, 2 C), 25.3 (s, 2 C), 30.1 (s,
1300
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Inorg. Chem. 2006, 1294–1302

Complexes of Bidentate Phosphane Selenide Ligands
Table 6. Crystallographic data.
FULL PAPER
Compound
Formula
9
10
11
C
44
H
46
I
2
P
2
Se
2
Te
2
C
25
H
22
I
2
P
2
Se
2
Te
28 4 2 2 2
C H28Cl I P Se Te
1107.56
red tablet
M
r
1303.67
red prism
923.69
red prism
Habit
Crystal size [mm]
Crystal system
Space group
Cell constants
a [pm]
b [pm]
c [pm]
0.3×0.2×0.2
monoclinic
0.3×0.2×0.2
monoclinic
0.6×0.5×0.18
monoclinic
P2 /n
1
P2
1
P2
1
/n
1017.60(6)
1917.2(1)
1190.25(8)
102.9(3)
2.2635(2)
2
1.913
4.3
1236
1309.0(2)
979.0(1)
2254.7(3)
103.8(3)
2.8054(7)
4
2.187
5.9
1712
757.13(4)
1313.67(8)
1819.0(1)
101.2(3)
1.7751(2)
2
2.072
5.0
1040
β [°]
V [nm ]
3
Z
D
–
3
x
[Mgm ]
–
1
µ [mm ]
F(000)
T [°C]
–140
60
–140
60
–140
61
2θ
max
Reflections measured
Reflections independent
Transmissions
46435
13698
0.829–0.928
0.023
476
52343
8559
0.555–0.928
0.047
289
37457
5410
0.714–0.928
0.019
178
R
int
Parameters
Restraints
1
0
0
wR (F
R [F, Ͼ4σ(F)]
S
2
, all reflections)
0.063
0.027
0.99
0.092
0.034
1.06
0.042
0.017
1.07
–3
Max. ∆ρ [enm ]
1774
2464
975
2
4
1
(
C), 116.2 (s, 2 C), 127.4 (s, 4 C), 129.3 (t, JC,P = 6.1 Hz, 8 C),
[2] R. A. Zingaro, E. A. Meyers, Inorg. Chem. 1962, 1, 771–774;
D. J. Williams, K. J. Wynne, Inorg. Chem. 1976, 15, 1449–1451.
[3] M. D. Rudd, S. V. Lindemann, S. Husebye, Acta Chem. Scand.
Ser. A 1997, 51, 689–708.
3
29.4 (s, 4 C), 132.0 (t, JC,P = 5.6 Hz, 8 C), 142.1 (s, 2 C), 147.3
–1
s, 4 C) ppm. FT-Raman: ν˜ = 146 (7.6), 129 (10) cm .
0: Diselenide 1 (0.99 g, 2.0 mmol) was dissolved in dichlorometh-
ane (20 mL). Tellurium (0.26 g, 2 mmol) and iodine (0.51 g,
.0 mmol) were added. The reaction mixture was stirred for 4 d at
room temp., after which the raw product 10 was isolated by vacuum
evaporation of the solvent, and purified by washing with pentane,
drying under vacuum evaporation and recrystallised by gas dif-
fusion from dichloromethane/hexane. Yield: 1.61 g, 85%; m.p. 192–
1
[
4] M. Arca, F. A. Devillanova, A. Garau, F. Isaia, V. Lippolis, G.
Verani, F. Demartin, Z. Anorg. Allg. Chem. 1998, 624, 745–
749; W. W. Schweikert, E. A. Meyers, J. Phys. Chem. J. Phys.
Chem. 1968, 72, 1561–1565; D. C. Apperley, N. Bricklebank,
S. L. Burns, D. E. Hibbs, M. B. Hursthouse, K. M. Abdul Ma-
lik, J. Chem. Soc., Dalton Trans. 1998, 1289–1292.
2
[
5] E. Krawczyk, A. Skowronska, Phosphorus Sulfur Silicon 1990,
51, 329.
1
93 °C. C25
22 2 2 2
H I P Se Te (923.69): calcd. C 32.51, H 2.40; found C
[
6] W.-W. du Mont, Main Group Chem. News 1994, 2(3), 18–26;
M. Bätcher, Ph. D. thesis, University of Oldenburg, 1989; J.
Jeske, Ph. D. thesis, Techn. University of Braunschweig, 1997.
7] S. M. Godfrey, S. L. Jackson, C. A. McAuliffe, R. G. Pritchard,
J. Chem. Soc., Dalton Trans. 1997, 4499–4502.
31
1
3
J
2.07, H 2.40. P NMR (CD
2
Cl
P,P = 8.9 Hz) ppm. 77Se NMR (CDCl
53± 50 Hz) ppm. FT-Raman: ν˜ = 150 (3, shoulder), 137 (10), 116
2
): δ = 21.8 (s, JP,Se = 682.3 Hz,
2
): δ = –93 (br. d, 1JSe,P
3
=
6
[
[
[
[
[
–1
(6) and 106 (5) cm .
8] J. Jeske, W.-W. du Mont, P. G. Jones, Chem. Eur. J. 1999, 5,
Structure Determinations: Numerical details are presented in
Table 6. All X-ray data were collected with monochromated Mo-
K radiation (λ = 0.71073 Å) on a Bruker SMART 1000 CCD area
α
detector. Absorption corrections were based on multiple scans. The
structures were solved by direct methods and refined anisotropi-
385–389.
9] S. M. Godfrey, S. L. Jackson, C. A. McAuliffe, R. G. Pritchard,
J. Chem. Soc., Dalton Trans. 1998, 4201–4204.
10] E. Seppälä, F. Ruthe, W.-W. du Mont, P. G. Jones, Chem. Com-
mun. 1999, 1471–1472.
11] a) [10-Se-3] means 10 valence electrons at the central Se atom,
which has 3 substituents: C. W. Perkins, J. C. Martin, A. J. Ard-
uengo III, W. Lau, A. Alegria, J. K. Kochi, J. Am. Chem. Soc.
1980, 102, 7753–7759; b) K.-y. Akiba, Chemistry of Hyperval-
ent Compounds, Wiley-VCH, New York, N. Y., 1999.
2
cally by full-matrix least-squares on F (Program SHELXTL: Prof.
G. M. Sheldrick, Univ. of Göttingen). Hydrogen atoms were in-
cluded using a riding model (except methyl groups which were re-
fined as rigid groups). Structure 9 was refined as a racemic twin.
Structure 11 contains one ordered molecule of dichloromethane
per asymmetric unit. CCDC-289068 (for 9), -289069 (for 10) and
[12] W.-W. du Mont, A. Martens von Salzen, F. Ruthe, E. Seppälä,
G. Mugesh, F. A. Devillanova, V. Lippolis, N. Kuhn, J. Or-
ganomet. Chem. 2001, 623, 14–28; W.-W. du Mont, A. Mar-
tens von Salzen, F. Ruthe, E. Seppälä, G. Mugesh, F. A. Devil-
lanova, V. Lippolis, N. Kuhn, J. Organomet. Chem. 2001, 628,
-
289070 (for 11) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
280.
[
13] F. Bigoli, P. Deplano, F. A. Devillanova, V. Lippolis, M. L.
Mercuri, M. A. Pellinghelli, E. F. Trogu, Eur. J. Inorg. Chem.
1998, 137–141.
[
1] J. Jeske, W.-W. du Mont, F. Ruthe, P. G. Jones, L. M. Mercuri,
P. Deplano, Eur. J. Inorg. Chem. 2000, 1591–1599.
Eur. J. Inorg. Chem. 2006, 1294–1302
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1301

C. G. Hrib, P. G. Jones, W.-W. du Mont, V. Lippolis, F. A. Devillanova
FULL PAPER
[
14] M. C. Aragoni, M. Arca, A. J. Blake, F. A. Devillanova, W.-W.
Apperley, N. Bricklebank, M. B. Hursthouse, M. E. Light, S. J.
Coles, Polyhedron 2001, 20, 1907–1913.
du Mont, A. Garau, F. Isaia, V. Lippolis, G. Verani, C. Wilson,
Angew. Chem. 2001, 113, 4359–4362; Angew. Chem. Int. Ed. [29] S. Pohl, W. Saak, B. Krebs, Z. Naturforsch., Teil B 1985, 40,
2001, 40, 4229–4232.
251–257.
[
15] W.-W. du Mont, H.-U. Meyer, S. Kubiniok, S. Pohl, W. Saak,
Chem. Ber. 1992, 125, 761–766.
[30] O. Foss, R. Hermansen, K. Maroy, T. Moberg, Acta Chem.
Scand. Ser. A 1987, 41, 130–138.
[31] O. Foss, K. Maartmann-Moe, Acta Chem. Scand. Ser. A 1987,
41, 121–129.
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Received: September 21, 2005
Published Online: January 27, 2006
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