Edge-Shared [M2Cl10]2- complexes of reaction between oxophilic group 4 metal and phosphorus ylides1

Article abstract of DOI:10.1134/S0036023612070170

The reactions between oxophilic group 4 metal chlorides, α-keto ylides in THF, led to the forma-tion of titanium, zirconium and hafnium edge-shared [M₂Cl₁₀]^2- complexes (1a-3f). We describe that the reaction between MCl

Full text of DOI:10.1134/S0036023612070170

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 7, pp. 1005–1013. © Pleiades Publishing, Ltd., 2012.
PHYSICAL METHODS
OF INVESTIGATION
EdgeꢀShared [M2Cl10]2– Complexes of Reaction between Oxophilic
Group 4 Metal and Phosphorus Ylides1
S. J. Sabouncheia, M. Ahmadia, P. Shahriaria, F. HoseiniꢀFashamia, and S. Samieeb
aFaculty of Chemistry, University of BuꢀAli Sina, Hamedan, 65174 Iran
b Department of Chemistry, Faculty of Science, Shahid Chamran University, Ahvaz, Iran
eꢀmail: Jsabounchei@yahoo.co.uk
Received February 17, 2010
Abstract—The reactions between oxophilic group 4 metal chlorides, ꢀketo ylides in THF, led to the formaꢀ
α
tion of titanium, zirconium and hafnium edgeꢀshared [M2Cl10]2– complexes (1a–3f). We describe that the
reaction between MCl4 (M = Ti, Zr and Hf) with phosphorus ylides produce edgeꢀshared [M2X10]2– comꢀ
plexes instead of Oꢀcoordination previously reported complexes. Adding dimethyl sulfoxide (DMSO) to
these complexes in room temperature crystalline solid [M(DMSO)8]
⋅
4Cl
⋅
m
H2O DMSO] (M = Ti (1g),
⋅
Zr (2g) and Hf (3g); m = 0–3) together with phosphonium salts in mother liquid were formed. The comꢀ
pounds were characterized by elemental analysis, IR and 1H, 13C and 31P NMR spectroscopy.
DOI: 10.1134/S0036023612070170
1
The utility of metalated phosphorus ylides in synꢀ have initiated an investigation of the chemistry of
thetic chemistry has been well documented [1, 2].
Phosphorus ylides are remarkable ligands which have
attracted much attention in synthetic, catalytic and
theoretical fields of transition metal chemistry [3].
TiCl4, ZrCl4 and HfCl4 with phosphorus ylides as a
ligand. As part of these studies, we report the preparaꢀ
tion and characterization complexes of the type
(Ar3PCH2COR)2[M2Cl10] (R = OCH2C6H5, C4H3S,
C6H4NO2 and C6H4Cl, Ar = Ph; R = C6H4NO2,
C6H4Cl, Ar = PhMe). But the most interesting point
of our study is the coordination center of DMSO in
solution. The reaction of DMSO with metals plays an
important role in biological and catalytic processes,
and also in the chemistry of complex compounds [13].
The nature of dimethyl sulfoxide as a monodentate
ligand is explored in this set of experiments [14, 15]. In
each particular case, the problem for study is the
determination of the coordination center of DMSO
(Sꢀ or Oꢀcoordination respectively). Dimethyl sulfoxꢀ
ide is a polar aprotic solvent, thus allowing studies of
its coordination properties. It is an ambidentate
ligand, usually coordinating via the oxygen atom [16],
but to a number of soft electronꢀpair acceptors, it is
also coordinating via the sulfur atom [17]. The domiꢀ
nating coordination figures of zirconium(IV) and
hafnium(lV) complexes are the square antiprism [18],
very often distorted octahedron and distorted sevenꢀ
coordinated complexes are fairly common [19, 20].
The complexes of ꢀketoꢀstabilized phosphorus ylides
α
with late transitionꢀmetal ions are thoroughly investiꢀ
gated [4, 27]; there are a few examples of such comꢀ
plexes with early transition metals [7, 8].
We attend to the oxophilic group 4 metals, Ti, Zr
and Hf that can be classified as a hard metal. The
extent of the interaction between the metal centers is
clearly dependent on the electronic properties of the
constituent metals but the nature of the bridging
ligand framework can also play a significant role.
Among the species displaying metal–metal interacꢀ
tions, the dinuclear compounds represented by the
faceꢀshared [M2X9]2– and edgeꢀshared [M2X10]2–
(dimer) species are particularly noteworthy as they are
formed by many transition metals [7]. The decahaꢀ
lodimetallate [M2Cl10]2– anions of zirconium(IV) and
hafnium(IV) within the second and third row of the
transition d elements have been prepared as their
triphenylmethyl derivatives [Ph3C]2[M2Cl10] and the
structural data of the hafnium derivative have been
reported. The structure of the hafnium dinuclear
anion is similar to that of the corresponding titanium
We prepared crystalline solid [M(DMSO)8]
⋅
4Cl
⋅
derivative, with P
Cl+4 as counterion [11a]. The bondꢀ
ing parameters of the [Hf2Cl10]2– anion and also the
crystal structure of [Me2SCH2Cl]2[Zr2Cl10], have been
reported [11b, 12]. In view of these observations we
m
H2O DMSO (1g–3g = 0–3) together with phosꢀ
⋅
; m
phonium salt of the type Ar3PCH2COR (R =
OCH2C6H5, C4H3S, C6H4NO2 and C6H4Cl, Ar = Ph;
R = C6H4NO2, C6H4Cl, Ar = PhMe) in mother liquid
were formed.
1
The article is published in the original.
1005

1006
SABOUNCHEI et al.
EXPERIMENTAL
ments were made by the KBr disk method. Melting
points were measured on a SMP3 apparatus. Solutionꢀ
state 1H, 31P and 13C NMR spectra at ambient temperꢀ
ature were obtained in DMSOꢀd6 or CDCl3 using a
FTꢀNMR Bruker 300 (300 MHz) and FTꢀNMR
JEOL FX 90 Q (90 MHz) spectrometers. Chemical
shifts (ppm) are reported according to internal TMS
and external 85% phosphoric acid.
General
All reactions were carried out under a nitrogen
atmosphere. THF and diethyl ether were distilled from
sodium benzophenone just before use. All other solꢀ
vents were reagent grade and used without further
purifications. All glassware was dried for 2 h (150 C)
prior to use. Metal halide salts were purchased and
used as received from Aldrich Chemical Co. The
°
phosphorous ylides Ph3P=CHCOOCH2C6H5 (
Ph3P=CHCOC4H3S (
2)4b, Ph3P=CHCOC6H4NO2
3)5, Ph3P=CHCOC6H4Cl (
CHCOC6H4NO2 and
Y5 4b
CHCOC6H4Cl (Y6 4b
the published procedures.
Y
1)4a,
Preparation of Phosphorus Ylides
Y
(
Y
Y
4)6, (
p
ꢀtolyl)3P=
(pꢀtolyl)3P=
α
ꢀBromo ketone (1 mmol) was dissolved in 20 mL
of acetone and then a solution of triphenylphosphine
PPh3) or paratolylphosphine (P( ꢀtolyl)3) (1 mmol)
(
)
(
p
)
were synthesized according to
in the same solvent (5 mL) was added dropwise to the
above solution. The resulting solution was stirred for
13 h. The solid product (phosphonium salt), was filꢀ
tered off, washed with diethyl ether and dried under
Instrumentation
Elemental analysis for C, H and N were performed reduced pressure. Addition of the phosphonium salt
using a PerkinꢀElmer 2400 series analyzer. IR spectra (1 mmol) to an aqueous solution of NaOH (0.5 M) led
were recorded on a Shimadzu 435ꢀUꢀ04 spectrophoꢀ to the elimination of HBr and gave the free ligand
tometer in the region 350ꢀ4000 cm–1 and the measureꢀ (Scheme 1).
m
o
S
5
H2
p
i
2
R =
,
,
,
,
,
Cl
O
C
O2N
Cl
O2N
3
4
M = Ti, Zr and Hf
Ar = Ph (phenyl); PhMe (paratolyl)
i
=
ipso
;
o
=
ortho
;
m
=
meta
;
p
=
para
O
O
C
C
Br
Acetone NaOH
r.t. (13 h) 40°C, (24 h)
+ PAr3
R
C
R
CH PAr3
H2
dry THF
r.t. (3 h)
MCl
4
+
O
2–
O
C
Cl
Cl
Cl
H3C
CH3
Cl
Cl
Cl
Cl
PAr3
,
2
R
C
M
M
55°C
Cl
Cl
H
H
Cl
S
S
O
O
S
S
O
O
O
PAr3
C
+ HCl
+
M
R
C
O
O
S
S
H
O
O
S
S
Scheme 1.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

EDGEꢀSHARED [M2Cl10]2– COMPLEXES
1007
Preparation of Complexes
Complexes of Titanium
(DMSO)
δ
: 21.50 (s). 13C NMR (DMSO)
δ
: 36.20 (d,
J
= 61.4 Hz, CH2); 140.26 (s, COPh(i)); 135.11 (s,
COPh(o)); 129.47 (s, COPh(m)); 119.59 (d, = 88.6 Hz,
PPh3(i)); 134.17 (d, = 10.3 Hz, PPh3(o)); 130.42 (
= 12.68 Hz, PPh3(m)); 131.64 (s, PPh3(p)); 192.27
J
Synthesis of bis[benzoylacetatetriphenylphosphoꢀ
nium]diꢀ ꢀchloroꢀbis[tetrachlorotitanate(IV)] (1a).
J
d,
µ
J
General procedure. A 100ꢀmL Schlenk tube was
charged with (0.53 mL, 0.53 mmol of TiCl4 (1 M soluꢀ
tion in CH2Cl2) and 20 mL of THF. To this yellow
solution was added Y1 (0.20 g, 0.53 mmol) in 15 mL of
THF and stirred for 20 min. The pale yellow solution
was concentrated to 2 mL, and diethyl ether (15 mL)
added to precipitate the moistureꢀsensitive white
(s, CO). Anal. calcd. for C52H42Cl12O2P2Ti2: C 48.72,
H 3.30. Found C 48.56, H 3.25.
Data for bis[(pꢀnitrophenylmethyIene)triparaꢀ
tolylphosphonium]diꢀ ꢀchloroꢀbis[tetrachlorotitanꢀ
µ
ate(IV) (1e). Orange solid. Ylied (0.3 g, 92%); mp
124 (decomp); IR(KBr) : 1686 (C = O), 995
(P–C) cm–1; 1H NMR (DMSO)
: 2.5 (s, 9H, CH3),
6.4 (d, = 9.82 Hz, 2H, CH), 7.33–8.36 (m, 16H,
Ph); 31P NMR (DMSO) : 20.41 (s); 13C NMR
(DMSO) : 21.6 (s, 3C, CH3), 37.3 (d, = 65.2 Hz,
°
C
ν
δ
complex. Ylied (0.21 g, 70%); mp 69–70
°
C
; IR (KBr)
: 1731 (C=O), 921 (P–C), cm–1; 1H NMR (DMSO)
: 5.5 (d, = 13.35 Hz, 2H, CH), 5.0 (s, 2H, CH2),
.01–7.95 (m, 20H, Fh); 31P NMR (DMSO)
: 20.77
J
ν
δ
δ
J
δ
J
7
δ
CH2), 145.7 (s, 1C, COPh(i)), 140.2 (s, 2C,
COPh(o)), 124.2 (s, 2C, COPh(m)), 151.0 (s, 1C,
(s), 26.37 (s, triphenylphosphoxide); 13C NMR
(DMSO) : 31.0 (d, J = 56.0 Hz, CH2), 67.9 (s, 1C,
δ
COPh(p)), 116.3 (d,
134.0 (d, = 12.21 Hz, 6C, P(
= 11.4 Hz, 6C, P( ꢀtolyl)3(m)), 131.0 (s, 3C, P(pꢀ
J
= 90.8 Hz, 3C, P(
pꢀtolyl)3(i)),
CH2), 126.4 (s, 1C, COPh(i)), 131.4 (s, 2C,
COPh(o)), 129.3 (s, 2C, COPh(m)), 131.8 (s, 1C,
J
pꢀtolyl)3(o)), 130.9 (d,
J
p
COPh(p)), 118.3 (d,
J
= 88.5 Hz, 3C, PPh3(i)), 133.8
= 12.70 Hz,
tolyl)3(p)), 192.6 (s, CO). Anal. calcd. for
C58H46Cl10N2O6P2Ti2: C 50.51, H 3.36, N 2.03; Found
C 50.41; H 3.32, N 2.19.
(d, = 10.58 Hz, 6C, PPh3(o)), 130.3 (d,
J
J
6C, PPh3(m)), 135.2 (s, 3C, PPh3(p)), 164.8 (s, CO).
Anal. calcd. for C54H48Cl10O4P2Ti2: C 50.94, H 3.80;
Found C 50.90, H 3.32.
Data for bis[(pꢀchlorophenylmethyIene)triparaꢀ
tolylphosphonium]diꢀ ꢀchloroꢀbis[tetrachlorotitanꢀ
µ
Data for bis[(4ꢀthionylmethyl)triphenylphosphoꢀ
ate(IV)] (1f). Cream solid. Yield (0.22 g, 77%);
m.p. 112–114 ; IR(KBr) : 1674 (C=O), 1589, 991
(P–C) cm–1; 1H NMR (DMSO)
: 2.4 (s, 9H, CH3),
6.2 (d, = 13.0 Hz, 2H, CH), 7.29–8.25 (m, 16H,
Ph); 31P NMR (DMSO) : 20.7 (s); 13C NMR
(DMSO) : 21.7 (s, 3C, CH3), 36.2 (d, = 61.4 Hz,
nium]diꢀ ꢀchloroꢀbis[tetrachlorotitanate(IV)] (1b).
µ
°
C
ν
Pale brown solid. Ylied (0.21 g, 70%); mp 225–228 C
°
δ
(decomp); IR (KBr)
δ
δ
: 1654 (C=O) 938(P–C) cm–1;
J
1H NMR (DMSO)
: 6.34 (d, J = 13.3 Hz, 2H, CH2);
δ
7
.32–8.37 (m, 18H, arom.). 31P NMR (DMSO):
δ
J
13
21.51 (s). C NMR (DMSO)
CH2); 137.52 (s, C(2)); 134.51 (s, C(3)); 137.52 (s,
C(4)); 141.75 = 6.6, C(5)); 119.05 (d, = 88.2 Hz,
3C, PPh3(i)); 133.66 (d, = 10.2 Hz, 6C, PPh3(o));
129.82 (d, = 13.0 Hz, 6C, PPh3(m)); 129.09 s, 3C,
PPh3(P)); 184.73(d, = 4.5, CO). Anal. calcd. for
δ
: 35.39 (d, J = 58.7,
CH2), 140.1 (s, 1C, COPh(i)), 145.7 (br, 4C,
COPh(o) and COPh(p)), 129.4 (s, 1C, COPh(m)),
(
d
,
J
J
116.5 (d,
10.9 Hz, 6C, P(
6C, P( ꢀtolyl)3(m)), 131.6 (s, 3C, P(
J
= 91.6 Hz, 3C, P(
p
ꢀtolyl)3(i)), 134.0 (d,
= 13.2 Hz,
ꢀtolyl)3(p)),
J =
J
pꢀtolyl)3(o)), 130.9 (d,
J
p
J
(
p
J
192.1 (s, CO). Anal. calcd. for C58H54Cl12O2P2Ti2: C
50.99, H 3.98; Found C 50.54, H 3.81.
C48H40Cl10O2P2S2Ti2: C 47.06, H, 3.29; Found C
47.22, H 3.20.
Data for bis[(pꢀnitrophenylmethylene)tripheꢀ
Complexes of Zirconium
nylphosphonium]diꢀ ꢀchloroꢀbis[tetrachlorotitanꢀ
µ
ate(IV)] (1c). Orange solid. 0.27 g (94%). mp 153–
155 decomp. IR (KBr) : 1685 (C=O), 995 (P–
C) cm–1. 1H NMR (DMSO)
: 6.43 (d, =13.7, 2H,
CH2); 7.76–8.34 (m, 19H, arom.). 31P NMR
(DMSO) : 36.65 (d,
: 21.32 (s). 13C NMR (DMSO)
= 58.5 Hz, CH2); 140.07 (s, COPh(i)); 135.24 (s,
COPh(o)); 124.35 (s, COPh(m)); 151.15 (s,
COPh(p)); 119.39 (d, = 89.8 Hz, PPh3(i)); 134.21
(d, = 8.7, PPh3(o)); 130.49 (d, = 11.5, PPh3(m));
131.19 ( , PPh3(p)); 192.39 (s, CO). Anal. calcd. for
Synthesis of bis[benzoylacetatetriphenylphosphoꢀ
°
C
ν
nium]diꢀ ꢀchloroꢀbis[tetrachlorozirconate(IV)] (2a).
µ
δ
(
J
General procedure. A 100ꢀmL Schlenk tube was
charged with (0.12 g, 0.53 mmol) of ZrCl4 and 20 mL
of THF. To this colorless solution was added Y1 (0.20 g,
0.53 mmol) in 8 mL of THF. The solution, which
remained colorless, was stirred for 2 h. The colorless
solution was concentrated to 2 mL, and diethyl ether
(15 mL) added to precipitate the moistureꢀsensitive
δ
δ
J
J
J
(
J
s
pale yellow complex. Ylied (0.19 g, 58%); mp 82–
1
C52H42Cl10N2O6P2Ti2: C 47.93, H 3.25, N 2.15; Found
C 47.16, H 3.21, N 2.11.
84
°
C
; IR(KBr)
ν
: 1732 (C=O), 996 (P–C) cm–1; H
NMR (DMSO)
δ
: 5.5 (d, J = 13.75 Hz, 2H, CH), 5.1
31
Data for bis[(pꢀchlorophenylmethylene)tripheꢀ (s, 2H, CH2), 6.97–8.12 (m, 20H, Ph); P NMR
nylphosphonium]diꢀ ꢀchloroꢀbis[tetrachlorotitanꢀ (DMSO) : 20.85 (s), 26.35 (s, triphenylphosphoxiꢀ
ate(IV)] (1d). Cream solid. 0.14 g (72%). mp 98– de); 13C NMR (DMSO)
: 29.7 (d, = 55.1 Hz, CH2),
100 . IR (KBr)
: 1674 (C=O), 990 (P–C) cm–1. 67.6 (s, 1C, CH2), 126.3 (s, 1C, COPh(i)), 131.2 (s,
µ
δ
δ
J
°
C
ν
1H NMR (DMSO)
: 6.47 (d, J = 13.62 Hz, 2H, 2C, COPh(o)), 129.0 (s, 2C, COPh(m)), 131.6 (s, 1C,
δ
CH2); 7.21–8.33 (m, 19H, arom.). 31P NMR COPh(p)), 118.1 (d,
J = 88.9 Hz, 3C, PPh3(i)), 133.6
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

1008
SABOUNCHEI et al.
(d,
J
= 10.80 Hz, 6C, PPh3(o)), 130.0 (d,
J
= 12.83
Data for bis[(pꢀchlorophenylmethylene)triparaꢀ
ꢀchloroꢀbis[tetrachlorozirconꢀ
Hz, 6C, PPh3(m)), 134.9 (s, 3C, PPh3(p)), 164.6 (s, tolylphosphonium]diꢀ
µ
CO). Anal. calcd. for C54H48Cl10O4P2Zr2: C 47.69, H ate(IV)] (2g). White solid. Yield (0.12 g, 79%); mp
3.56; Found C 47.50, H 3.50.
118–120
1H NMR (DMSO)
13.0 Hz, 2H, CH), 7.23–8.30 (m, 16H, Ph);
31P NMR (DMSO) : 20.7 (s); 13C NMR (DMSO)
21.7 (s, 3C, CH3), 36.0 (d, = 62.9 Hz, CH2), 140.2
(s, 1C, COPh(i)), 145.8 (br, 4C, COPh(o) and
COPh(p)), 129.5 (s, 1C, COPh(m)), 116.5 (d,
91.7 Hz, 3C, P( ꢀtolyl)3(i)), 134.0 (d, = 10.9 Hz, 6C,
P( ꢀtolyl)3(o)), 130.9 (d, = 13.2 Hz, 6C, P(
tolyl)3(m)), 131.5 (s, 3C, P( ꢀtolyl)3(p)), 192.1 (s,
°C
; IR (KBr)
ν
: 1674 (C=O), 990 (P–C) cm–1;
: 2.5 (s, 9H, CH3), 6.2 (d,
δ
J =
Data for bis[(4ꢀthionylmethyl)triphenylphosphoꢀ
nium]diꢀ ꢀchloroꢀbis[tetrachlorozirconate(IV)] (2b)).
µ
δ
δ
:
Pale yellow solid. Ylield (0.19 g, 58%); mp 286–288 C
°
decomp. IR (KBr)
: 1654 (C=O), 937 (P–C) cm–1.
ν
J
1H NMR (DMSO)
δ
: 6.35 (d, J = 12.5 Hz, 2H, CH2);
31
J
=
7
.33–8.35 (m, 18H, arom.). P NMR (DMSO)
21.49 (s). 13C NMR (DMSO)
: 35.60 (d, = 51.4 Hz,
CH2); 138.00 (s, C(2)); 134.95 (s, C(3)); 137.54 (s,
C(4)); 142.13 (d, = 7.6 Hz, C(5)); 119.37 (d,
88.7 Hz, PPh3(i)); 133.98 (d, = 10.6 Hz, PPh3(o));
130.19 (d, = 12.6 Hz, PPh3(m)); 129.09 ( , PPh3(p));
185.14 (d, = 5.8, CO). Anal. calcd. for
δ:
p
J
δ
J
p
J
pꢀ
p
J
J =
CO). Anal. calcd. for C58H54Cl12O2P2Zr2: C 47.95, H
3.75; Found C 47.80, H 3.69.
J
J
s
J
C48H40Cl10O2P2S2Zr2: C 43.95, H 3.07; Found C 44.15,
H 3.22.
Complexes of Hafnium
Data for bis[(pꢀnitrophenylmethylene)triphenylphosꢀ
Data for bis[benzoylacetatetriphenylphosphoꢀ
phonium]diꢀ ꢀchloroꢀbis[tetrachlorozirconate(IV)] (2c).
µ
nium]diꢀ ꢀchloroꢀbis[tetrachlorohafnate(IV)] (3a).
µ
Orange solid. 0.11 g (35%). mp 140–143
°
C
decomp.
: 1686 (C=O), 994 (P–C) cm–1. 1H NMR
: 6.56 d, = 11.6, 2H, CH2); 7.75–8.38
: 21.02 ( ).
= 55.7, CH2); 140.06
, COPh(o)); 124.36 (
, COPh(p)); 119.38 ( = 88.1,
(d, = 8.5, PPh3(o)); 130.47 (d,
= 10.1, PPh3(m)); 131.17 ( , PPh3(p)); 192.44 (s,
Pale brown solid. Ylied (0.20 g, 61%); mp 90–92
IR(KBr) : 1732 (C=O), 1625, 1601, 1587, 1486,
1438, 1379, 1263, 1127, 1072, 968 (P–C), 906, 805,
746, 728, 695 cm–1; 1H NMR (DMSO)
: 5.6 (d,
14.51 Hz, 2H, CH), 5.1 (s, 2H, CH2), 6.93–7.92 (m,
°
C;
IR (KBr)
(DMSO)
ν
ν
δ
(
J
31
(m
, 19H, arom.). P NMR (DMSO)
13C NMR (DMSO)
: 36.6 (d,
(s, COPh(i)); 135.23 (
COPh(m)); 151.18 (
PPh3(i)); 134.20
δ
s
δ
J =
δ
(
J
s
s,
31
20H, Ph); P NMR (DMSO)
δ
: 20.83 (s), 26.20 (s,
s
d, J
triphenylphosphoxide); 13C NMR (DMSO)
δ
: 67.6 (s,
(
J
(
1C, CH2), 128.4 (s, 1C, COPh(i)), 131.2 (s, 2C,
COPh(o)), 129.0 (s, 2C, COPh(m)), 131.7 (s, 1C,
J
s
CO). Anal. calcd. for C52H42Cl10N2O6P2Zr2: C 44.94,
H 3.05, N, 2.02; Found C 44.71, H, 3.13, N 2.08.
Data for bis[(pꢀchlorophenylmethylene)tripheꢀ
COPh(p)), 118.2 (d,
J
= 88.9 Hz, 3C, PPh3(i)), 133.7
= 12.84 Hz,
(d, = 10.56 Hz, 6C, PPh3(o)), 130.0 (d,
J
J
6C, PPh3(m)), 135.0 (s, 3C, PPh3(p)), 164.6 (s, CO).
Anal. calcd. for C54H48Cl10O4P2Hf2: C 42.27, H 3.15;
Found C 42.18, H 3.10.
nylphosphonium]diꢀ
ate(IV)] (2d). White solid. 0.24 g (77%). mp 103–
105 . IR (KBr)
: 1674 (C=O), 989 (P–C) cm–1. 1H
NMR (DMSO) : 6.41 (d, = 13.8 Hz, 2H, CH2);
.21–8.26 (m, 19H, arom.). P NMR (DMSO)
µ
ꢀchloroꢀbis[tetrachlorozirconꢀ
°
C
ν
Data for cis[(4ꢀthionylmethyl)triphenylphosphoꢀ
δ
J
31
nium]diꢀ
µ
ꢀchloroꢀbis[tetrachlorohafnateIV)]
(3b).
7
δ:
13
Pale brown solid. 0.22 g (59%). mp 297–299 C
°
21.52 (s). C NMR (DMSO)
CH2); 140.27 (s, COPh(i)); 135.11 (s, COPh(o));
129.46 (s, COPh(m)); 119.64 ( = 88.9 Hz,
PPh3(i)); 134.20 (d, = 10.5 Hz, PPh3(o)); 130.42 (d,
= 12.7 Hz, PPh3(m)); 131.66 ( , PPh3(p)); 192.30 (s,
δ
: 36.29 (d, J = 61.8,
decomp. IR (KBr)
ν
: 1655 (C=O), 939 (P–C) cm–1.
: 6.15 (d, = 13.8 Hz, 2H, CH2);
1H NMR (DMSO)
δ
J
d, J
31
7.08–8.15 (
m
, 18H, arom.). P NMR (DMSO) :
δ
J
13
21.38 (s). C NMR (DMSO)
134.71 (s, C(3)); 137.32 (s, C(4)); 141.82 (d,
C(5)); 118.96 (d, = 88.6 Hz, PPh3(i)); 133.68 (d,
10.5 Hz, PPh3(o)); 129.96 (d, = 12.9 Hz, PPh3(m));
δ: 137.73 (s, C(2));
J
s
J
= 7.5 Hz,
CO). Anal. calcd. for C52H42Cl12O2P2Zr2: C 45.63, H
3.09; Found C 45.37, H 3.20.
J
J =
J
Data for bis[(pꢀnitrophenylmethylene)triparaꢀ
129.23 (s, PPh3(p)); 184.50 (s, CO). Anal. calcd. for
C48H40Cl10Hf2O2P2S2: C 38.79, H 2.71; Found
C 38.65, H 2.84.
tolylphosphonium]diꢀ ꢀchloroꢀbis[tetrachlorozirconꢀ
µ
ate(IV)] (2f). Orange solid. Ylied (0.15 g, 49%); mp
160 (decomp); IR(KBr) : 1688 (C=O), 994 (P–
C) cm–1; 1H NMR (DMSO)
: 2.4 (s, 9H, CH3), 6.3
(d,
31P NMR (DMSO)
21.7 (s, 3C, CH3), 35.8 (d,
(s, 1C, COPh(i)), 140.2 (s, 2C, COPh(o)), 124.2 (s, (DMSO)
2C, COPh(m)), 151.1 (s, 1C, COPh(p)), 116.3 (
8.35 (m, 19H, arom.). 31P NMR (DMSO)
90.9 Hz, 3C, P( ꢀtolyl)3(i)), 134.0 (d, : 36.71 (d, = 62.0 Hz, CH2);
= 10.5 Hz, 13C NMR (DMSO)
6C, P( ꢀtolyl)3(o)), 135.8 (d, = 12.5 Hz, 6C, P( 140.08 (s, COPh(i)); 135.25 (s, COPh(o)); 124.34 (s,
tolyl)3(m)), 131.0 (s, 3C, P( ꢀtolyl)3(p)), 192.7 (s, COPh(m)); 151.10 (s, COPh(p)); 119.40 (d, = 89.3 Hz,
CO). Anal. calcd. for C58H46Cl10N2O6P2Zr2: C 47.52, PPh3(i)); 134.22 (d, = 9.1 Hz, PPh3(o)); 130.50 (d,
H 3.16, N 1.91; Found C 46.93, H 3.02, N 2.02. = 12.1 Hz, PPh3(m)); 131.12 (s, PPh3(p)); 192.36 (s,
°
C
ν
δ
Data for bis[(pꢀnitrophenvlmethylene)triphenylphosꢀ
J
= 13.9 Hz, 2H, CH), 7.61–8.36 (m, 16H, Ph); phonium]diꢀ
: 20.42 (s); 13C NMR (DMSO)
= 60.5 Hz, CH2), 145.8 IR (KBr)
µ
ꢀchloroꢀbis[tetrachlorohafnate(IV)] (3c).
δ
δ:
Orange solid. 0.12 g (45%). mp 136–138
: 1683 (C=O), 994 (P–C) cm–1. 1H NMR
: 6.56 (d, = 13.7 Hz, 2H, CH2); 7.77–
: 21.26 (s).
°
C decomp.
J
ν
δ
J
d,
J
=
δ
p
J
δ
J
p
J
p
pꢀ
J
J
J
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

EDGEꢀSHARED [M2Cl10]2– COMPLEXES
1009
Cl(2)
Cl(4)
O(10)
C(72)
C(71)
Cl(3)
C(11)
S(7)
C(12)
C(41)
S(1)
O(1)
O(7)
Hf(1)
S(2)
S(4)
O(4)
C(81)
C(61)
S(6)
C(42)
O(8)
O(5)
C(51)
S(5)
O(6)
S(8)
Cl(1)
C(82
O(2)
O(3)
C(22)
C(62)
C(21)
O(9)
C(52)
S(3)
C(32)
C(31)
S(9)
C(92)
O(11)
C(91)
Fig. 1. The molecular structure of 3g
.
C(7)
C(10)
C(14)
C(8)
Su
C(6)
C(1)
C(12)
O(4)
C(1)
O(2)
O(5)
O(6)
C(3)
C(2)
C(3)
C(15)
C(4)
Zn(1)
C(8)
C(5)
O(7)
C(9)
O(3)
O(1)
Cl(3)
C(9)
O(9)
S(1)
O(8)
C(16)
C(19)
O(3)
O(4)
O(5)
O(6)
C(17)
O(2)
O(1)
Fig. 2. The molecular structure of 2g
.
CO). Anal. calcd. for C52H42Cl10Hf2N2O6P2: C 39.92, 1673 (C=O), 990 (P–C) cm–1. 1H NMR (DMSO)
:
δ
H 2.71, N 1.79; Found C 39.42, H 2.62, N 1.92.
6.42 (
arom.). P NMR (DMSO)
(DMSO) : 36.20 (d, = 60.4 Hz, CH2); 140.28 (
COPh(i)); 135.12 (s, COPh(o)); 129.48 (s,
d, J = 13.6 Hz, 2H, CH2); 7.38–8.41 (m, 19H,
31
13
δ: 21.53 (s). C NMR
Data for bis[(pꢀchlorophenylmethylene)triphenylphosꢀ
δ
J
s,
phonium]diꢀ
µ
ꢀchloroꢀbis[tetrachlorohafnate(IV)] (3d).
White solid. 0.26 g (75%). mp 107–109
°C. IR (KBr) :
ν
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

1010
SABOUNCHEI et al.
( P+–C–) of phosphoranes and their
Table 1.
metal complexes
ν
(CO) and
ν
21.6 (s, 3C, CH3), 36.5 (d,
(s, 1C, COPh(i)), 145.9 (s, 2C, COPh(o)), 124.3 (s,
2C, COPh(m)), 151.1 (s, 1C, COPh(p)), 116.2 (d,
91.6 Hz, 3C, P( ꢀtolyl)3(i)), 134.0 (d, = 10.8 Hz, 6C,
P( ꢀtolyl)3(o)), 131.0(d, = 13.2 Hz, 6C, P(
tolyl)3(m)), 131.1 (s, 3C, P( ꢀtolyl)3(p)), 192.3 (s,
CO). Anal. calcd. for C58H46Cl10N2O6P2Hf2: C 42.47,
H 2.83, N 1.71; Found C 42.32, H 2.80, N 1.65.
Data for bis[(pꢀchlorophenylmethylene)triparatolylphosꢀ
J = 61.4 Hz, CH2), 140.1
J
=
Complexes
νP+–C– (cm–1
)
ν
C=O (cm–1
)
Ref.
p
J
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ylides
p
J
pꢀ
p
APPYa
BPPYb
Y1
Y2
Y3
Y4
Y5
Y6
1530
1525
1610
1527
1529
1579
1600
1581
1731
1732
1732
1654
1654
1655
1685
1686
1683
1674
1674
1673
1686
1688
1690
1674
1674
1675
–
24
25
4a
4b
5
–
887
879
884
882
886
882
923
996
968
938
937
939
995
994
994
990
989
990
995
994
992
991
990
991
phonium]diꢀ
µ
ꢀchloroꢀbis[tetrachlorohafnate(IV)]
(3f).
White solid. Yield (0.27, 80%); mp 125–127
°
C;
1
IR(KBr)
(DMSO)
ν
: 1675 (C=O), 991 (P–C) cm–1; H NMR
: 2.4 (s, 9H, CH3), 6.3 (d, = 13.5 Hz, 2H,
δ
J
CH), 7.11–8.24 (m, 16H, Ph); 31P NMR (DMSO)
:
δ
6
20.6 (s); 13C NMR (DMSO)
(d, = 60.6 Hz, CH2), 140.1 (s, 1C, COPh(i)), 145.8
(br, 4C, COPh(o) and COPh(p)), 129.3 (s, 1C,
COPh(m)), 116.5 (d, = 91.6 Hz, 3C, P( ꢀtolyl)3(i)),
134.0 (d, = 11.0 Hz, 6C, P( ꢀtolyl)3(o)), 131.0 (d,
= 13.3 Hz, 6C, P( ꢀtolyl)3(m)), 131.6 (s, 3C, P(
δ
: 21.6 (s, 3C, CH3), 36.0
4b
4b
J
J
p
la
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
This work
J
p
2a
J
p
pꢀ
3a
tolyl)3(p)), 192.2 (s, CO). Anal. calcd. for
C58H54Cl12O2P2Hf2: C 42.81, H 3.34; Found C 42.73,
H 3.51.
1b
2b
3b
Preparation of Octakis(dimethyl sulfoxide)titanium(IV) (1g)
1c
General
procedure.
With
0.1
g
of
2c
(RCOCH2PAr3)2[Ti2Cl10] (R = OCH2C6H5, C4H3S,
C6H4NO2 and C6H4Cl; Ar = Ph and (R = C6H4NO2
and C6H4Cl; Ar = PhMe) was added DMSO in room
temperature. The solution, which remained colorless,
so 5 day crystalline solid was formed. The colorless
solution contain two product, one of the product
3c
1d
2d
3d
1e
[
Ti(DMSO)8] in crystalline solid and another product,
phosphonium salt in mother liquid, mp 140–142 C,
IR(KBr) : 1020 (S=O, symmetric stretch), 950
°
ν
2e
(S=O, asymmetric stretch), 488 (Ti–O, symmetric
stretch), 448 (Ti–O, asymmetric stretch) cm–1. Anal.
calcd. for C16H48O8S8Ti: C 28.56, H 7.19; Found C
28.02, H 6.88.
3e
1f
2f
Data for octakis(dimethyl sulfoxide)zirconium(IV)
(2g). mp 153–155
°
C
, IR(KBr) : 1030 (S=O, symꢀ
ν
3f
metric stretch), 953 (S=O, asymmetric stretch), 484
(Ti–O, symmetric stretch), 436 (Ti–O, asymmetric
stretch) cm–1. Anal. calcd. for C16H48O8S8Zr: C 26.83,
H 6.75; Found C 26.51, H 6.63.
a
acetylmethylmetriphenylphosphorane.
benzoylmethylenephenylphosphorane.
b
Data for octakis(dimethyl sulfoxide)hafnium(IV)
COPh(m)); 119.59 (d,
= 10.7 Hz, PPh3(o)); 130.43 (d,
PPh3(m)); 131.63 ( , PPh3(p)); 192.24 (s, CO). Anal.
calcd. for C52H42Cl12Hf2O2P2: C 40.47, H 2.74; Found
C 40.35, H 2.50.
J
= 89.0 Hz, PPh3(i)); 134.18
(3g). mp 168–170
C, IRνmax/cm–1 1024 (S=O, symꢀ
°
(d,
J
J
= 12.9 Hz,
metric stretch), 952 (S=O, asymmetric Mstretch),
483 (Ti–O, symmetric stretch), 441 (Ti–O, asymmetꢀ
ric stretch). Anal. calcd. for C16H48HfO8S8: C 23.92, H
6.02; Found C 23.12, H 5.78.
s
Data for bis[(pꢀnitrophenylmethylene)triparatolylphosꢀ
phonium]diꢀ ꢀchloroꢀbis[tetrachlorohafnate(IV)] (3e).
µ
RESULTS AND DISCUSSION
Orange solid. Ylied (0.12 g, 45%); mp 153 C
°
(decomp); IR(KBr)
ν
: 1690 (C=O), 992 (P–C) cm–1;
: 2.4 (s, 9H, CH3), 6.2 (d,
The reaction between the group 4 metal halide salts
α
1H NMR (DMSO)
δ
J
=
and the
ꢀketo ylides Y1, Y2, Y3, Y4, Y5 and Y6 in THF
12.7 Hz, 2H, CH), 7.56–8.41 (m, 16H, Ph); led to the formation of complexes of the type
31P NMR (DMSO) : 20.38 (s); 13C NMR (DMSO)
δ
δ:
(
Ar3PCH2COR)2[M2Cl10] la–3f). The anionic
(
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

EDGEꢀSHARED [M2Cl10]2– COMPLEXES
1011
No
No
1a
1b
1c
1d
1e
1f
2a
2b
2c
R
OCH2C6H5 C4H3S C6H4NO2 C6H4Cl C6H4NO2 C6H4Cl OCH2C6H5 C4H3S C6H4NO2
R'
M
H
Ti
H
Ti
H
Ti
H
Ti
Me
Ti
Me
Ti
H
H
H
Zr
Zr
Zr
2d
2e
2f
3a
3b
3c
3d
3e
3f
R
C6H4Cl C6H4NO2 C6H4Cl OCH2C6H5 C4H3S C6H4NO2 C6H4Cl C6H4NO2 C6H4Cl
R'
M
H
Me
Zr
Me
Zr
H
H
H
H
Me
Hf
Me
Hf
Zr
Hf
Hf
Hf
Hf
R'
Cl
Cl
O
H
Cl
Cl
Cl
Cl
Cl
Cl
R'
P
M
M
C
R
Cl
Cl
H
R'
2
Fig. 3. Suggested structure of 1a–3f
.
[M2Cl10]2– and the cationic (RCOCH2PAr3)+ units are built up of discrete octakis(dimethyl sulfoxide)zircoꢀ
held together by electrostatic forces. The M1 and M2
atoms in the [M2Cl10]2– dimer environment are sixꢀ
coordinate with a distorted octahedral configuration.
The reaction of APPY and BPPY with MCl4 (M = Ti,
Zr and Hf) produced Oꢀcoordination complexes [7].
nium(IV) and hafnium(IV) complexes, chloride ions
and with an additional dimethyl sulfoxide molecule and
two or three water molecules in the lattice. This work
also showed that the zirconium(IV) ions are surꢀ
rounded by eight oxygen atoms from the dimethyl sulꢀ
foxide molecules in a fairly regular square antiprism
In this work, the reaction of MCl4 with ꢀketo phosꢀ
α
phorus ylides edgeꢀshared [M2Cl10]2– complexes are
formed. The decahalogenodimetalate(IV) dianions as
their phosphorus ylides are well soluble in DMSO.
After five day in room temperature crystalline solid
1g–3g together with phosphonium salts in mother liqꢀ
uid were formed.
(Fig. 2). The
ν
(CO) and
(P+–C–) in 1a–3f are comꢀ
ν
pared, in Table 1.
As mentioned earlier, in each particular case, the
problem for study is the determination of the coordiꢀ
nation center of DMSO (the S or O atoms; Sꢀ or Oꢀ
coordination respectively). This problem is traditionꢀ
ally solved from the displacement of the band due to
the stretching vibration νSO, lying in the near infrared
range. Among other possible methods of determining
the coordination centers of DMSO, this method
Proton decoupled 31PꢀNMR spectra in room temꢀ
perature showed only one sharp singlet around 21 ppm
for 1a–3f. As we described earlier the reaction between
MCl4 (M = Ti, Zr and Hf) with phosphorus ylides proꢀ
duce edgeꢀshared [M2X10]2– complexes instead of Oꢀ
coordination that previously reported [7]. The 31P
chemical shift values for these complexes appear to be
downfield by about δ ≈ 6–7 ppm with respect to the
parent ylides. Gutmann and coꢀworkers [26] suggest
the existence of the [Zr2X10]2– anion in the reaction
between ZrCl4 and Ph3CCi in acetonitrile solution.
These complexes are soluble in DMSO and crystalline
solid of 1g–3g were formed gradually in room temperaꢀ
ture. The structure of this crystal indicated that DMSO
coordinated from oxygen into metal center. This is simꢀ
ilar to the structures of the octakis(dimethyl sulfoxꢀ
ide)zirconium (IV) chloride dimethyl sulfoxide trihyꢀ
drate [18] and octakis(dimethyl sulfoxide)hafnium(IV)
chloride dimethyl sulfoxide dihydrate [17] (Fig. 1) were
Table 2. M–O and S=O symmetric and asymmetric stretching
vibration frequencies in 1g–3g
S=O
Complexes symmetric asymmetꢀ symmetꢀ asymmetꢀ
stretch ric stretch ric stretch ric stretch
S=O
M–O
M–O
DMSO
1054
1020
1030
1024
954
950
953
952
–
–
Ti(DMSO)8
Zr(DMSO)8
Hf(DMSO)8
488
484
483
448
436
441
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

1012
SABOUNCHEI et al.
JP–CH of the complexes 1a–3f with ylides
The 13C NMR spectra of 1a–3f in room temperaꢀ
Table 3. Compared
ture are the up field shift of the signals due to ylidic
carbon. High solubility of ylides in CDCl3 allowed us
to record the spectrum in this solvent but for the comꢀ
plexes we had to use DMSOꢀd6 and presence of a sepꢀ
tet pick due to solvent at 39.5 ppm in the CH resoꢀ
nance region caused that some of these signals were
not seen. The 13CꢀNMR spectrum revealed resoꢀ
nances only in the range of 127–130 ppm, associated
with the phenyl groups. Table 3 contains the coupling
constant of 1a–3f compared with parent ylides. This
indicates interaction between [M2Cl10] with counteꢀ
rion showed in Scheme 1.
1JP–C
(CH2)
2JP–H
(CH2)
Parameters
Complexes/Ligands
Y1
la
124.89
56.00
55.10
–
–
13.35
13.75
14.51
23.12
13.26
13.35
13.81
22.85
13.70
11.58
13.73
23.75
13.62
13.81
13.62
22.67
9.82
2a
3a
Y2
1b
2b
3b
Y3
lc
112.73
58.75
51.45
–
ACKNOWLEDGMENTS
110.20
57.15
55.77
62.04
110.30
61.44
61.82
60.42
113.47
65.20
60.05
61.40
112.00
61.40
62.90
60.60
We are highly grateful to the university of BuꢀAliꢀ
Sina for a grant and Mr. Zebarjadian for recording the
NMR spectra.
2c
3c
Y4
1d
2d
3d
Y5
le
Supplementary Information
Supplementary data contains three figures, the
molecular structure of octakis(dimethyl sulfoxꢀ
ide)hafnium(IV) chloride dimethyl sulfoxide dihyꢀ
drate (Fig. 1) the molecular structure of octakis(dimeꢀ
thyl sulfoxide)zirconium(IV) chloride dimethyl sulꢀ
foxide (Fig. 2).
2e
3e
Y6
1f
13.90
12.70
23.12
13.00
13.00
14.50
REFERENCES
1. H. J. Cristau, Chem. Rev. 94, 1299 (1994).
2. O. I. Kolodiazhnyl, Tetrahedron 52, 1855 (1996).
3. A. W. Johnson, Ylides and Imines of Phosphorus (Wiley,
2f
3f
New York, 1993).
4. (a) S. J. Sabounchei, A. R. Dadrass, F. Akhlaghi, et al.,
Polyhedron 27, 1963 (2008); (b) S. J. Sabounchei,
occupies essentially a monopoly position. It is not
applicable, however, in those cases where the range in
which νSO appears is overlapped by the bands due to
other vibrations [13]. Attempts to improve the situation
by means of an analysis of the spectra in the range in
which the metalꢀDMSO stretching vibrations appear
H. Nemattalab, V. Jodaian, J. Chin. Chem. Soc. 55
,
197 (2008); (c) S. J. Sabounchei, A. R. Dadrass,
M. Jafarzadeh, and H. R. Khavasi, J. Organomet.
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H. Nemattalab, S. Salehzadeh, et al., Inorg. Chim.
Acta 362, 105, (2009); (e) S. J. Sabounchei, H. Nematꢀ
(tentatively, νM–S = 500–260, νM–O = 530–380 cm–1
)
talab, and H. R. Khavasi, J. Organomet. Chem. 692
,
[13, 21, 22], have generally had little success, because
of the indefinite nature of the assignments and the
overlap of the corresponding spectral intervals. Preꢀ
liminary results from normal coordinate analysis show
that there are major contributions from S–O stretchꢀ
ing in the IR bands at 927 and 897 cm–1 [23]. The MO
and SO stretching vibration frequencies 1g–3g are
listed in Table 2.
5440, (2007); (f) S. J. Sabounchei, V. Jodaian, and
H. R. Khavasi Polyhedron 26, 2845, (2007); (g)
S. J. Sabounchei, A. R. Dadrass, and S. Samiee, Phosꢀ
phorus, Sulfur, Silicon 181, 1, (2006); (h) S. J. Sabꢀ
ounchei, H. Nemattalab, F. Akhlaghi, and H. R. Khavasi,
Polyhedron 27, 3275 (2008)
5. M. Kobayashi, F. Sanda, and T. Endo, Macromolecules
32, 4751 (1999).
6. H. J. Bestmann and B. Arnason, Chem. Ber. 95, 1513
The 1H NMR spectrum of 1a–3f in room temperꢀ
ature showed resonances associated with the aromatic
phenyl groups around 7–8 ppm and resonances correꢀ
sponding to the methinic protons around 6–7 ppm as
a doublet. The suggested structure for these complexes
(Fig. 3) shows that involving a phosphonium cation
(1962).
7. J. A. Albanese, D. L. Staley, A. L. Rheingold, and
J. L. Burmeister, Inorg. Chem. 29, 2209 (1990).
8. E. DiezꢀBarra, J. FernandezꢀBaeza, M. M. Kubicki,
et al., J. Organomet. Chem. 542, 291 (1997); A. Antiꢀ
nolo, F. CarrilloꢀHermosilla, E. DiezꢀBarra, et al.
J. Organomet. Chem. 570, 97 (1998).
and a ꢀdichloro M2Cl10 dianion.
μ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 7 2012

EDGEꢀSHARED [M2Cl10]2– COMPLEXES
1013
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