Synthesis and characterization of pentamethylcyclopentadienyl-rhodium(III) dialkydithiophosphate complexes: Single-crystal structure of [Cp*RhCl{S2P(OEt)2}]

Article abstract of DOI:10.1016/S0022-328X(99)00127-8

Reactions of [Cp*Rh(μ,-Cl)Cl]₂ with NH₄S₂P(OR)₂ in 1:1 and 1:2 stoichiometry gave complexes of the type [Cp*RhCl{S₂P(OR)₂}] (1) (Cp* = C₅Me₅; R = Et, Prⁿ, Prⁱ) and [Cp*Rh{S₂P(OR)₂}₂] (2) (R = Et). Complex 1 on treatment with AgSO₃CF₃ in acetone followed by addition of a neutral donor ligand (L) gave cationic complexes, [Cp*Rh{S₂P(OR)₂}L][SO₃CF₃] (3) [R = Et; L = PPh₃; P(C₆H₄Me-4)₃ = (Ptol₃), AsPh₃]. All the complexes 1-3 have been characterized by elemental analysis, electronic spectra, IR and NMR (¹H, ³¹P) data. The structure of one of the complexes, [Cp*RhCl{S₂P(OEt)₂}] (1a) has been established unambiguously by single-crystal X-ray analysis. The structure consists of a central rhodium atom coordinated to a η⁵-pentamethylcyclopentadienyl ligand, a chelated dithiophosphate and a chloride ligand.

Full text of DOI:10.1016/S0022-328X(99)00127-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 584 (1999) 159–163
Synthesis and characterization of
pentamethylcyclopentadienyl–rhodium(III) dialkyldithiophosphate
complexes: single-crystal structure of [Cp*RhCl{S2P(OEt)2}]
Vimal K. Jain a,*, Babu Varghese b
a Chemistry Di6ision, Bhabha Atomic Research Centre, Mumbai 400 085, India
b Regional Sophisticated Instrumentation Centre, Indian Institute of Technology, Chennai, India
Received 27 October 1998; received in revised form 2 February 1999
Abstract
Reactions of [Cp*Rh(m-Cl)Cl]2 with NH4S2P(OR)2 in 1:1 and 1:2 stoichiometry gave complexes of the type
[Cp*RhCl{S2P(OR)2}] (1) (Cp*=C5Me5; R=Et, Prn, Pri) and [Cp*Rh{S2P(OR)2}2] (2) (R=Et). Complex 1 on treatment with
AgSO3CF3 in acetone followed by addition of a neutral donor ligand (L) gave cationic complexes, [Cp*Rh{S2P(OR)2}L][SO3CF3]
(3) [R=Et; L=PPh3; P(C6H4Me-4)3=(Ptol3), AsPh3]. All the complexes 1–3 have been characterized by elemental analysis,
electronic spectra, IR and NMR (1H, 31P) data. The structure of one of the complexes, [Cp*RhCl{S2P(OEt)2}] (1a) has been
established unambiguously by single-crystal X-ray analysis. The structure consists of a central rhodium atom coordinated to a
h5-pentamethylcyclopentadienyl ligand, a chelated dithiophosphate and a chloride ligand. © 1999 Elsevier Science S.A. All rights
reserved.
Keywords: Dialkyldithiophosphate; Crystal structure; NMR; Pentamethylcyclopentadienyl–rhodium; Rhodium
2. Results and discussion
1. Introduction
Treatment of [Cp*Rh(m-Cl)Cl]2 with ammonium salts
of dialkyldithiophosphoric acid in 1:1 and 1:2 stoi-
chiometry resulted in almost quantitative formation of
[Cp*RhCl{S2P(OR)2}] (1) and [Cp*Rh{S2P(OR)2}2] (2),
respectively (Scheme 1) as brown-coloured crystalline
solids. The complex 1a can readily be obtained in
quantitative yield by the reaction of 2 with [Cp*Rh(m-
Cl)Cl]2. The complex 1a on treatment with AgSO3CF3
followed by addition of a neutral donor ligand in
acetone afforded [Cp*Rh{S2P(OR)2}L][SO3CF3] (3) as
yellow solids.
During the last three decades or so, considerable
work has been done on classical coordination com-
plexes of platinum group metals with dithioacid ligands
(R2NCS2, ROCS2, RCS2, R2PS2 and (RO)2PS2) [1,2].
However, in recent years a number of organometallic
derivatives of these ligands have been isolated and
characterized by us [3–10] and others [11,12]. Some of
these organometallic derivatives show unusual proper-
ties when compared to their classical coordination
complexes.
Pentamethylcyclopentadienyl–rhodium
complexes
with sulfur ligands are of much current interest [13–16].
However, complexes with dithio ligands are rare
[17,18]. A few Cp*Rh(III) complexes with dithiophos-
phinic acids and dithiocarbamates have been reported
by Robertson and Stephenson [18]. This study deals
with the synthesis and characterization of Cp*Rh(III)
complexes with dithiophosphoric acids.
The electronic spectra of these complexes, except 2,
in benzene displayed three absorptions in the region
282–445 nm. The absorption at ca. 325 nm may be
1
assigned to the A1g“1T2g transition. This band in 1–3
was not much affected by changes in the ligands around
the ‘Cp*Rh’ fragment. However, substituent effects
were reflected in the absorption appearing at longer
wavelength (368–445 nm). This absorption may be
attributed to the first spin-allowed ligand-field band
* Corresponding author.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00127-8

160
V.K. Jain, B. Varghese / Journal of Organometallic Chemistry 584 (1999) 159–163
Fig. 1. Structure of 2.
signals assignable to bidentate and monodentate ligand
moieties. For the monodentate dithio ligand, only one
set of resonances have been observed. The Cp* methyl
protons in 3a and 3b appeared as doublets (4J(P–H) ca.
3.5 Hz) owing to the coupling with the phosphorus of
the PR3 ligand [14,22].
Scheme 1.
(1A1g“1T1g). When chloride in 1 is substituted by a
dithio ligand (e.g. as in 2) or a neutral ligand (e.g. as in
cationic complexes, 3), the absorption maximum was
blue shifted. The electronic spectra of tris–dithio com-
plexes of Rh(III) have been reported earlier [1,19].
The IR spectra were interpreted by comparing the
spectra of these complexes with those of [Cp*RhCl2]2,
free acids and their metal complexes reported from our
laboratory. The bands in the regions 950–1105 and
750–790 cm−1 may be assigned to w(P)–O–C and
wP–O–(C), respectively [20]. The wP–S stretchings
have been assigned in the region 635–660 cm−1. The
P–S and PꢀS stretching frequencies which can give
some information regarding various structural possibili-
ties generally appear in the same region for free acids,
their esters and metal complexes and thus have limited
diagnostic utility [21]. A weak absorption in 1 at 279–
290 cm−1 may be assigned to wRh–Cl [1,18].
The 31P{1H}-NMR spectra of 1 exhibited a doublet
2
with J(103Rh–31P) of ca. 13 Hz due to the dithiophos-
phate ligand. Similarly, the spectra of 3 containing
phosphine ligands displayed two doublets of doublets
due to the coupling with 103Rh and 31P nuclei. They
were attributed to the dithiophosphate and phosphine
ligands. The magnitude of 1J(103Rh–31P) (145 Hz),
3
2J(103Rh–31P) (ca. 11 Hz) and J(31P–31P) (ca. 18 Hz)
couplings are in agreement with the values reported
earlier [14,22]. Substitution of chloride in 1 with neutral
donor ligands resulted in a considerable shielding of the
31P resonance indicating reduced electron density at
rhodium. The 31P-NMR spectrum of 2 displayed a
doublet with 2J(103Rh–31P) 13 Hz at l 93.8 for the
chelating dithio ligand and a singlet at l 112.8 for the
monodentate dithio group (Fig. 1).
1
The H-NMR spectra of 1–3 showed the characteris-
tic resonances and peak multiplicities for the groups
attached to rhodium. The spectra exhibited a sharp
singlet for the Cp* protons. The alkoxy groups of the
dithio ligand in 1 and 3 displayed two separate sets of
resonances indicating non-equivalence of the OR
groups. In 1, the a-protons are not well resolved in
CDCl3 solution, however, in benzene-d6 solution these
signals could be resolved. One set of resonances (the
down field signals) are not much affected on changing
chloride in 1 with a neutral donor ligand in 3. The
ligand dependence of the high-field resonances may be
attributed to the chemical shift anisotropy due to the
aromatic rings of the neutral donor ligands in 3. This
has been demonstrated by the structure of
[Ru{S2P(OEt)2}(h6-p-cymene)(PPh3)][BPh4] in which
one of the OEt group lies down the arene ring and is
parallel to one of the phenyl rings of PPh3, while the
second OEt group remains outside the ring currents
The molecular structure of 1a was unambiguously
determined by X-ray crystallography. An ORTEP draw-
ing of 1a is shown in Fig. 2 with selected bond lengths
and angles in Table 1. The molecular structure consists
1
and hence is slightly affected [8]. The H-NMR spec-
Fig. 2. Molecular structure of [Cp*RhCl{S2P(OEt)2}] (1a) with crys-
trum of 2 showed three sets of dithio ligand proton
tallographic numbering scheme.

V.K. Jain, B. Varghese / Journal of Organometallic Chemistry 584 (1999) 159–163
161
Table 1
non-planar [3] conformation. The four-membered
chelate ring and the Cp* ring are inclined at the angle
of 124.3°.
,
Selected bond lengths (A) and angles (°) for [Cp*RhCl{S2P(OEt)2}]
(1a)
,
Bond length (A)
Rh–C(1)
Rh–C(2)
Rh–C(3)
Rh–C(4)
Rh–C(5)
Rh–Cl
2.125(5)
2.129(5)
2.125 (6) P–S(1)
2.151 (5) P–S(2)
2.153(5)
2.409(2)
Rh–S(1)
Rh–S(2)
2.440(2)
2.4270(13)
1.985(2)
1.985(2)
1.563(4)
1.579(4)
3. Experimental
The ammonium salt of dithiophosphoric acids [25]
and [Cp*Rh(m-Cl)Cl]2 [26] were prepared according to
reported procedures. All the preparations were carried
out under nitrogen atmosphere. The elemental analysis
for C and H were carried out in the Analytical Chem-
istry Division of this research centre. The electronic
spectra of these complexes were recorded in anhydrous
benzene in the region 250–800 nm on a Shimadzu
UV-160 A. The infrared spectra were recorded as Nujol
mulls between CsI plates on a Bomem MB-102 FT-IR
P–O(1)
P–O(2)
Bond angles (°)
C(1)–Rh–C(2)
C(1)–Rh–C(3)
C(1)–Rh–C(4)
C(1)–Rh–C(5)
C(2)–Rh–C(3)
C(2)–Rh–C(4)
C(2)–Rh–C(5)
C(3)–Rh–C(4)
C(3)–Rh–C(5)
C(4)–Rh–C(5)
C(1)–Rh–Cl
C(2)–Rh–Cl
C(3)–Rh–Cl
C(4)–Rh–Cl
C(5)–Rh–Cl
C(1)–Rh–S(1)
C(2)–Rh–S(1)
C(3)–Rh–S(1)
40.1(3)
65.3(3)
63.9(2)
38.3(2)
38.9(3)
63.7(3)
64.0(2)
37.0(3)
62.1(2)
36.4(2)
157.7(2)
126.7(3)
94.2(2)
94.6(2)
125.2(2)
105.5(2)
95.6(2)
122.0(2)
C(4)–Rh–S(1)
C(5)–Rh–S(1)
C(1)–Rh–S(2)
C(2)–Rh–S(2)
C(3)–Rh–S(2)
C(4)–Rh–S(2)
C(5)–Rh–S(2)
Cl–Rh–S(1)
Cl–Rh–S(2)
S(1)–Rh–S(2)
P–S(1)–Rh
158.2(2)
142.2(2)
104.4(2)
142.3(3)
156.1(2)
119.4(2)
96.1(2)
92.68(5)
90.96(5)
80.99(5)
86.46(6)
86.82(6)
94.8(3)
115.4(3)
113.3(2)
114.0(2)
114.1(2)
105.51(8)
1
spectrometer. The H- and 31P{1H}-NMR spectra were
recorded in CDCl3 in 5 mm tubes on a Bruker DPX-
300 NMR spectrometer operating at 300 and 121.42
MHz, respectively. The chemical shifts are relative to
P–S(2)–Rh
O(1)–P–O(2)
O(1)–P–S(1)
O(2)–P–S(1)
O(1)–P–S(2)
O(2)–P–S(2)
S(1)–P–S(2)
1
internal solvent peak (CHCl3, l 7.26 ppm for H) and
external 85% H3PO4 for 31P.
3.1. Preparation of [Cp*RhCl{S2P(OEt)2}] (1a)
To a dichloromethane solution (10 ml) of [Cp*Rh(m-
Cl)Cl]2 (135 mg, 0.22 mmol), solid NH4S2P(OEt)2 (90
mg, 0.44 mmol) was added and the mixture stirred at
room temperature for 3 h. The precipitated ammonium
chloride was filtered off and the filterate was concen-
trated in vacuo to give a brown solid which was recrys-
tallized from dichloromethane–hexane mixture in 81%
(162 mg) yield. M.p. 169–170°C. Found: C, 36.6; H,
5.5. Anal. Calc. C14H25ClO2PS2Rh: C, 36.7; H, 5.5%.
Electronic spectrum: umax 285 (m 4172 M−1 cm−1), 330
(m 2557 M−1 cm−1), 445 nm (m 2682 M−1 cm−1).
1H-NMR (C6D6 l): 1.14, 1.19 (each t, 7 Hz, OCH2Me);
1.44 (s, C5Me5); 4.06, 4.51 (each dq; 10 Hz (d), 7 Hz
(q)). 1H-NMR (CDCl3 l): 1.25, 1.38 (each t, 7 Hz,
OCH2Me); 1.73 (s, C5Me5); 4.13 (m, OCH2). 31P{1H}-
NMR (C6D6 l): 99.4 (d, 2J(103Rh–31P) 12.7 Hz);
31P{1H}-NMR (CDCl3 l): l: 98.2 (d, 2J(103Rh–31P)
12.9 Hz).
of discrete monomeric molecules with distorted octahe-
dral configuration around the rhodium atom having a
pentamethylcyclopentadienyl ring at one face. The ther-
mal ellipsoids of the methyl groups attached to the
cyclopentadienyl ring indicate nearly free liberation of
the cyclopentadienyl ring about the axis normal to its
plane. The Cp*Rh fragment is coordinated with sulfur
atoms of a symmetrically chelated dithiophosphate
group and a chloride ligand. The rhodium atom is
,
situated 1.775 A above the center of the planar Cp*
ring. All h5-Cp*Rh bond distances are ordinary and are
,
approximately equal with an average value of 2.137 A
,
and a range of 2.125(6)–2.153(5) A [23]. One of the
right angles around rhodium, S(1)–Rh–S(2), is consid-
erably reduced (80.99(5)°) owing to the small bite of the
dithio ligand. The two Rh–S bond distances (2.427(1)
Complexes 1b and 1c were prepared similarly and
their pertinent data are given below.
,
,
and 2.440(2) A) [14–16,24] and Rh–Cl (2.409 A)
[15,16] are in good agreement with the values reported
for [Cp*Rh(m-SH)Cl]2 and other related complexes.
3.1.1. [Cp*RhCl{S2P(OPrn)2}] (1b)
,
The P–S bond lengths of 1.985 A are intermediate
between the double (1.94 A) and the single bond values
(2.09 A) indicating partial double bond character as
expected. The four-membered chelate ring RhS2P is
planar (the phosphorus atom shows maximum devia-
Recrystallized from benzene–hexane. M.p. 114°C.
Found: C, 38.5; H, 5.8. Anal. Calc. C16H29ClO2PS2Rh:
C, 39.5; H, 6.0%. Electronic spectrum umax: 285 (m 4320
M−1 cm−1), 330 (m 2668 M−1 cm−1), 444 nm (m 2630
,
,
1
M−1 cm−1). H-NMR (CDCl3 l): 0.88, 0.98 (each t,
,
tion 0.04 A from the plane formed by the Rh, S(1),
7.4 Hz; OCH2CH2Me); 1.65–1.75 (m,OCH2CH2); 1.73
(s,C5Me5); 3.95–4.08 (m, OCH2). 31P{1H}-NMR
S(2), P atoms). In metal complexes, the four-membered
ring has been shown to adopt either a planar [6,8] or a
2
(CDCl3 l): 98.7 (d, J(103Rh–31P) 13.5 Hz).

162
V.K. Jain, B. Varghese / Journal of Organometallic Chemistry 584 (1999) 159–163
3.1.2. [Cp*RhCl{S2P(OPri)2}] (1c)
C5Me5); 2.38 (s, tolMe); 2.77, 4.09 (each dq, 7 Hz (q);
9.3, 8.5 Hz (d); OCH2); 7.22–7.37 (m, C6H4). 31P{1H}-
NMR (CDCl3 l): 35.8 (d,d 1J(103Rh–31P) 145 Hz;
Recrystallized from benzene–hexane. M.p. 161–
162°C. Found: C, 39.3; H, 6.1. Anal. Calc.
C16H29ClO2PS2Rh: C, 39.5; H, 6.0%. Electronic spec-
trum umax: 285 (m 4549 M−1 cm−1), 332 (m 2873 M−1
2
3J(31P–31P) 18.5 Hz; PPh3); 84.9 (d,d, J(103Rh–31P) 11
3
Hz; J(31P–31P) 18.5 Hz, dithio).
cm−1), 445 nm (m 2965 M−1 cm−1). H-NMR (CDCl3
1
l): 1.24, 1.35 (each d, 6.0 Hz, OCHMe2); 1.72 (s,
3.3.2. [Cp*Rh{S2P(OEt)2}(AsPh3)][SO3CF3] (3c)
C5Me5); 4.70, 4.94 (each sextet, 6.0 Hz, OCH). 31P{1H}-
M.p. 162–163°C. Found: C, 44.3; H, 4.4. Anal. Calc.
C33H40AsF3O5PS3Rh: C, 45.1; H, 4.6%. Electronic
spectrum umax: 284 (m 9279 M−1 cm−1), 321 (m 6235
2
NMR (CDCl3 l): 95.8 (d, J(103Rh–31P) 13.0 Hz).
3.2. Preparation of [Cp*Rh{S2P(OEt)2}2] (2)
1
M−1 cm−1), 393 nm (m 4353 M−1 cm−1). H-NMR in
CDCl3 l: 0.88, 1.38 (each t, 7 Hz, OCH2Me); 1.57 (s,
C5Me5); 2.72, 4.10 (dq) 7 Hz (t), 9 Hz (d), OCH2);
7.47–7.52 (br, AsPh3). 31P{1H}-NMR (CDCl3 l): 83.3
This complex was prepared similarly to 1a except
that NH4S2P(OEt)2, was used in four equivalents. The
product was recrystallized from hexane in 86% yield.
M.p. 94°C. Found: C, 35.1; H, 5.8. Anal. Calc.
C18H35O4P2S4Rh: C, 35.5; H, 5.8%. Electronic spectrum
2
(d, J(103Rh–31P) 13 Hz, dithio).
1
umax: 329 (m 5488 M−1 cm−1) 428 (sh) nm. H-NMR
3.4. Reaction between 2 and [Cp*Rh(v-Cl)Cl]2
(CDCl3 l): 1.25, 1.27, 1.36 (each t, 7 Hz, in 1:2:1 ratio,
OCH2Me); 1.75 (s, C5Me5); 4.03–4.14 (m, OCH2).
31P{1H}-NMR (CDCl3 l): 93.8 (d, 2J(103Rh–31P) 13
Hz); 112.8 (s).
To a dichloromethane solution (5 ml) of [Cp*Rh{S2-
P(OEt)2}2] (41 mg, 0.068 mmol), a solution of [Cp*Rh-
(m-Cl)Cl]2 (21 mg, 0.034 mmol) in dichloromethane was
added with stirring, which was continued for 30 min.
The solvent was evaporated in vacuo to give 1a in
quantitative yield as characterized by microanalysis,
1H- and 31P-NMR data.
3.3. Preparation of [Cp*Rh{S2P(OEt)2}-
(PPh3)][SO3CF3] (3a)
To an acetone solution (5 ml) of AgSO3CF3 (40 mg,
0.15 mmol), a solution of [Cp*RhCl{S2P(OEt)2}] (70
mg, 0.15 mmol) in acetone was added with stirring for
15 min, during which time AgCl precipitated out. To
this, solid triphenylphosphine (42 mg, 0.16 mmol) was
added. The colour of the solution changed immediately
to golden-yellow. The stirring continued further at
room temperature for 4 h. The solution was centrifuged
and filtered to remove AgCl. The filtrate was concen-
trated in vacuum to give an orange paste which on
scratching in hexane (2–3 times) gave orange powder
(90 mg, 71%). M.p. 180°C. Found: C, 47.4; H, 4.9.
Anal. Calc. C33H40F3O5P2S3Rh: C, 47.5; H, 4.8%. Elec-
tronic spectrum umax: 282 (m 9942 M−1 cm−1), 328 (m
4. Crystallography
X-ray data on maroon crystals of [Cp*RhCl-
{S2P(OEt)2}] (1a) were collected at 294 K on an Enraf–
Nonius CAD-4 diffractometer using graphite mono-
,
chromated Mo–Ka radiation (u=0.71073 A) employ-
ing the ꢀ−2q scan technique. The unit cell parameters
were determined from 25 reflections measured by ran-
dom search routine and indexed by the method of short
vectors followed by least-squares refinement. The inten-
sity data were corrected for Lorentz-polarization and
absorption effects. The structure was solved using
SHELXS 86 [27] and refined using SHELXL 93 [28] com-
puter programs. The non-hydrogen atoms were refined
anisotropically and are shown in Fig. 2. Crystallo-
graphic data together with data collection details are
given in Table 2. Positional parameters are given in
Table 3. An ORTEP drawing [29] of 1a is shown in Fig.
2.
1
7650 M−1 cm−1), 368 (sh) nm. H-NMR (CDCl3 l):
4
0.92, 1.38 (each t, 7 Hz, OCH2Me); 1.50 (d, J(31P–1H)
3.5 Hz, C5Me5); 2.80, 4.09 (each dq, 7 Hz (q), 9.6, 8.6
Hz (d) OCH2); 7.41–7.53 (br, PPh3). 31P{1H}-NMR
1
3
(CDCl3 l): 37.3 (d,d, J(103Rh–31P) 145 Hz; J(31P–
31P) 18 Hz; PPh3); 84.9 (d,d; 2J(103Rh–31P) 12 Hz;
3J(31P–31P) 18 Hz, dithio).
Complexes 3b and 3c were prepared similarly and the
pertinent data are as follows:
3.3.1. [Cp*Rh{S2P(OEt)2}(Ptol3)][SO3CF3] (3b)
Acknowledgements
M.p. 198–199°C. Found: C, 49.2; H, 5.6. Anal. Calc.
C36H46F3O5P2S3Rh: C, 49.3; H, 5.3%. Electronic spec-
trum: umax 284 (m 11578 M−1 cm−1), 328 (m 7843 M−1
We thank Dr J.P. Mittal, Director, Chemistry
Group, for his support and encouragement of this
work. We are grateful to the Analytical Chemistry
Division, BARC for microanalyses of the complexes.
1
cm−1), 369 (sh) nm. H-NMR (CDCl3 l): 0.91, 1.37
(each t, 7 Hz, OCH2Me); 1.48 (d,4J(31P–1H) 3.5 Hz;

V.K. Jain, B. Varghese / Journal of Organometallic Chemistry 584 (1999) 159–163
163
Table 2
Crystal
[Cp*RhCl{S2P(OEt)2}]
Table 3
data
and
structure
refinement
details
for
Atomic coordinates (×104) and equivalent isotropic displacement
2
3
a
,
parameters (A ×10 ) for [Cp*RhCl{S2P(OEt)2}]
Empirical formula
Formula weight
Temperature
C14H25ClO2PS2Rh
458.8
293(2) K
0.71073
Monoclinic
P21/n
x
y
z
Ueq
40(1)
65(1)
59(1)
52(1)
51(1)
100(2)
69(1)
72(2)
98(3)
84(2)
68(2)
59(1)
178(6)
264(11)
249(10)
160(5)
137(4)
141(4)
88(2)
Rh
Cl
S(1)
S(2)
P
9879(1)
2253(1)
4818(2)
2324(2)
2772(2)
2858(2)
1952(6)
4367(5)
5(6)
503(10)
1600(8)
1746(7)
800(6)
6784(1)
6635(1)
8246(1)
7219(1)
8340(1)
8968(2)
8778(2)
6472(4)
6559(4)
5964(5)
5532(3)
5813(3)
6921(7)
7157(7)
5844(10)
4818(5)
5469(6)
8868(5)
9536(4)
8461(4)
9091(4)
,
Wavelength (A)
10173(1)
10815(1)
8289(1)
9350(1)
8983(4)
9361(3)
9716(6)
10837(6)
10712(6)
9621(6)
9024(5)
9348(13)
11893(10)
11697(11)
9169(12)
7769(6)
8461(10)
8178(6)
9665(7)
10056(7)
Crystal system
Space group
Unit cell dimensions
,
a (A)
12.731(2)
9.171(3)
17.437(8)
108.87(2)
1926.5(12)
4
1.582
1.325
936
0.1×0.1×0.08 mm
2.39–24.97
05h515; 05k510;
−205l519
3547
3385 [Rint=0.0262]
c scan
0.97 and 0.72
O(1)
O(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
Dcalc. (Mg m−3
)
Absorption coefficient (mm−1
F(000)
)
−1164(8)
−73(17)
2408(15)
2759(10)
636(11)
729(10)
114(8)
Crystal size
Theta range of data collection (°)
Index ranges
Reflections collected
Independent reflections
Absorption correction
Max and min transmission
Refinement method
5701(7)
6764(8)
89(2)
96(2)
Full-matrix least-squares
.
on
a Ueq is defined as one third of the trace of the orthogonalized Uij
tensor.
F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I\2|(I)]
R indices (all data)
3383/0/191
1.079
R1=0.0381, wR2=0.0925
R1=0.0506; wR2=0.1060
0.684 and −0.565
Apreda, C. Foces-Foces, F.H. Cano, J. Chem. Soc. Dalton Trans.
(1989) 1987.
[15] Z. Tang, Y. Nomura, Y. Ishii, Y. Mizobe, M. Hidai, Organometal-
lics 16 (1997) 151.
[16] Z. Tang, Y. Nomura, Y. Ishii, Y. Mizobe, M. Hidai, Inorg. Chim.
Acta 267 (1998) 73.
Largest difference peak and hole
−3
,
(eA
)
[17] P.R. Sharp, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry-II, vol. 8, Pergamon
Press, Oxford, 1995, p. 115.
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(1976) C46. (b) D.R. Robertson, T.A. Stephenson, J. Chem. Soc.
Dalton (1978) 486.
[19] C.K. Jorgensen, J. Inorg. Nucl. Chem. 24 (1962) 1571.
[20] D.E.C. Corbridge, Top. Phosphorus Chem. 6 (1961) 235.
[21] (a) D.M. Adams, J.B. Cornell, J. Chem. Soc. A (1968) 1299. (b)
R.A. Chittenden, L.C. Thomas, Spectrochim. Acta 20 (1964) 1679.
[22] W.D. Jones, U.L. Kuykendall, Inorg. Chem. 30 (1991) 2615.
[23] H.K. Das, W.G. Klemperer, V.W. Day, Inorg. Chem. 28 (1989)
1423.
[24] J.J. Bonnet, P. Kalck, R. Poiblanc, Inorg. Chem. 16 (1977) 1514.
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1235.
[26] C. White, A. Yates, P.M. Maitlis, Inorg. Synth. 29 (1992) 228.
[27] G.M. Sheldrick, SHELXS 86, Program for Crystal Structure Deter-
mination, Univesity of Go¨ttingen, Go¨ttingen, Germany, 1986.
[28] G.M. Sheldrick, SHELXL 93, Program for Crystal Structure
Refinement, University of Go¨ttingen, Go¨ttingen, Germany, 1993.
[29] C.K. Johnson, ORTEP II, a FORTRAN Thermal Ellipsoid Plot
Program for Crystal Structure Illustrations: Report ORNL-5138,
Oak Ridge National Laboratory, Oak Ridge TN, 1976.
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