Synthesis, Characterization and Structural Studies on the First Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone (dpkdnph), fac-[Re(CO)3(dpkdnph)Cl]

Article abstract of DOI:10.1002/1099-0682(20022)2002:2<481::AID-EJIC481>3.0.CO;2-0

When di(2-pyridyl) ketone 2,4-dinitrophenylhydrazone (dpkdnph) was allowed to react with [Re(CO)5Cl] in refluxing toluene fac-[Re(CO)3(dpkdnph)Cl] was formed in good yield. Spectroscopic measurements on fac-[Re(CO)3(dpkdnph)Cl] revealed strong solvent dep

Full text of DOI:10.1002/1099-0682(20022)2002:2<481::AID-EJIC481>3.0.CO;2-0

FULL PAPER
Synthesis, Characterization and Structural Studies on the First Rhenium
Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone (dpkdnph),
fac-[Re(CO)3(dpkdnph)Cl]
Mohammed Bakir[a]
Keywords: Rhenium / Carbonyl ligands / Hydrazones
When di(2-pyridyl) ketone 2,4-dinitrophenylhydrazone
(dpkdnph) was allowed to react with [Re(CO)5Cl] in re- acetonitrile solution of fac-[Re(CO)3(dpkdnph)Cl] show well
fluxing toluene fac-[Re(CO)3(dpkdnph)Cl] was formed in separated linear CH3CN and pseudo-octahedral fac-
good yield. Spectroscopic measurements on fac-[Re(CO)3- [Re(CO)3(dpkdnph)Cl], with the major distortion about rhe-
(dpkdnph)Cl] revealed strong solvent dependence as mani- nium being due to the bidentate binding of dpkdnph to form
fested by the high sensitivity of its electronic absorption a six-membered Re−N−C−C−C−N metallacyclic ring in a boat
crystal of fac-[Re(CO)3(dpkdnph)Cl]·CH3CN grown from an
spectra to solvent variation. Electrochemical measurements
on fac-[Re(CO)3(dpkdnph)Cl] in DMF show electrochemical
conformation. The molecular packing shows a web of fac-
[Re(CO)3(dpkdnph)Cl]·CH3CN units interlocked via a net-
properties with quasi-reversible reductions following an irre- work of intra- and intermolecular non-covalent interactions
versible one-electron transfer. Structural studies on a brown that include donor/acceptor and hydrogen bonds.
Introduction
2,4-dinitrophenylhydrazones have been reported, to the best
of my knowledge there has been no report on the isolation
of dpkdnph.[1]
Hydrazones and their compounds have been extensively
studied for their rich physicochemical properties, reactivity
patterns and applications in many important chemical pro-
cesses that include non-linear optics, medicine, molecular
sensing and separations.[1Ϫ16] The synthesis and character-
ization of rhenium carbonyl compounds of di(2-pyridyl) ke-
tone (dpk), di(2-pyridyl)amine (dpa), di(2-pyridyl) ketone
oxime (dpk·oxime), and di(2-pyridyl) ketone p-nitrophenyl
hydrazone (dpknph) were described by us previously.[17Ϫ20]
Electrochemical measurements on fac-[Re(CO)3(dpk)Cl]
and fac-[Re(CO)3(dpk.oxime)Cl] revealed strong solvent de-
pendence and the possible use of fac-[Re(CO)3(dpk)Cl] as
an electrochemical sensor for electrophiles that include
metal ions.[17Ϫ19] Optical and thermodynamic measure-
ments in polar solvents on dpknph and fac-[Re(CO)3-
(dpknph)Cl] show the presence of two charge-transfer
bands for the free ligand and its metal compound; the elec-
tronic/charge transfer in fac-[Re(CO)3(dpknph)Cl] is faster
than that in dpknph, and therefore fac-[Re(CO)3-
(dpknph)Cl] can be used as a spectrophotometric sensor for
metal ions.[20,21] These results prompted us to explore how
a variation in the ligand backbone affects the electrochem-
ical and optical properties of the complex, and here I report
the synthesis, characterization and solid-state structure of
the first metal compound of di(2-pyridyl) ketone 2,4-di-
nitrophenyl hydrazone (dpkdnph). Although a variety of
Results and Discussion
The reaction between [Re(CO)5Cl] and dpkdnph in tolu-
ene under reflux gave fac-[Re(CO)3(dpkdnph)Cl] in good
yield. This reaction is similar to those reported for the syn-
thesis of fac-[Re(CO)3(L-L)Cl] (L-L ϭ dpk, dpk.oxime,
dpknph) from [Re(CO)5Cl] and L-L in refluxing
toluene.[17Ϫ20] The formulation of the isolated rhenium-car-
bonyl as fac-[Re(CO)3(dpkdnph)Cl] is based on the results
of a number of spectroscopic measurements and a compar-
ison of these results with those reported for fac-[Re(CO)3-
(L-L)Cl].[17Ϫ20] In the IR spectrum of fac-[Re(CO)3-
(dpkdnph)Cl] three strong bands appeared in the ν(CϭO)
stretching region similar to those observed for fac-[Re-
(CO)3(dpknph)Cl] and other tricarbonylhalorhenium(I)
compounds with polypyridyl-like ligands, thus confirming
the assigned fac geometry.[17Ϫ20] The ν(CϭN) absorption of
the hydrazone moiety and the combined ν(CϭC) and ν(Cϭ
N) of the pyridine vibrations are normal and in the same
region as in fac-[Re(CO)3(dpknph)Cl].[20] A single absorp-
tion band was observed for the ν(NH) stretching mode sig-
nalling a free NϪH in the solid state.[22] The 1H NMR spec-
trum of fac-[Re(CO)3(dpkdnph)Cl] (see Exp. Sect.) is solv-
ent dependent, indicating a solvent-solute interaction. No
evidence of paramagnetic line broadening or unusual shifts
of resonances appeared in the spectra of this compound,
thus confirming its diamagnetic character.
[a]
Department of Chemistry, The University of the West Indies-
Mona Campus,
Kingston 7, Jamaica, W. I.
Eur. J. Inorg. Chem. 2002, 481Ϫ486
WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
1434Ϫ1948/02/0202Ϫ0481 $ 17.50ϩ.50/0
481

M. Bakir
FULL PAPER
Figure 1. Electronic absorption spectrum of fac-[Re(CO)3-
(dpkdnph)Cl] in: (a) CH2Cl2 (3.00 ϫ 10Ϫ5 ); (b) CH3CN (3.00 ϫ
10Ϫ5 ); (c) DMF (1.00 ϫ 10Ϫ5 )
The electronic absorption spectra of fac-[Re(CO)3-
(dpkdnph)Cl] show spectral features similar to those re-
ported for fac-[Re(CO)3(dpknph)Cl], although subtle differ-
ences are apparent.[20,21] The charge-transfer bands in fac-
[Re(CO)3(dpkdnph)Cl] shift to high-energy relative to fac-
[Re(CO)3(dpknph)Cl] due to a decrease in the electron-
withdrawing ability of dpkdnph compared to dpknph. In
non-polar solvents such as CH2Cl2 a highly intense high-
energy charge-transfer band appeared (Figure1a), in polar
solvents such as CH3CN two charge-transfer bands ap-
peared (Figure 1b), and in highly polar solvents such as
DMF a low-energy charge-transfer band appeared (Fig-
ure 1c). The intensity and location of these bands are solv-
ent dependent. The gradual addition of a physical or chem-
Figure 2. Electronic absorption spectrum of fac-[Re(CO)3-
(dpkdnph)Cl] in DMF (1.00 ϫ 10Ϫ5 ) (a) in the absence of sun-
light, (b) after 3 h of sunlight exposure and (c) after 6 h of
sunlight exposure
The electrochemical properties of fac-[Re(CO)3-
ical stimulus to a solution of fac-[Re(CO)3(dpkdnph)Cl] (dpkdnph)Cl] in non-aqueous media were investigated us-
causes an interconversion between the low- and high-energy ing voltammetric techniques. Cyclic voltammograms of fac-
intra-ligand charge-transfer bands of fac-[Re(CO)3- Re(CO)3(dpkdnph) in DMF are shown in Figure 3. In these
(dpkdnph)Cl]. For example, when a DMF solution of fac- voltammograms rich redox processes appeared. The first re-
[Re(CO)3(dpkdnph)Cl] was exposed to sunlight, the intens- duction wave at Ep,c ϭ Ϫ0.76 V is one-electron and irrevers-
ity of the low-energy charge-transfer band decreased and ible. Scan rate variations on this wave from 100Ϫ2000 mV/s
the intensity of the high-energy band increased (Figure 2). revealed no sign of reversibility pointing to structural/
The spectrophotometric response of fac-[Re(CO)3- chemical modification following the first electronic transfer.
(dpkdnph)Cl] towards physical and chemical stimuli is sim- Two quasi-reversible reduction waves appeared at Ep
ϭ
ilar to that reported for fac-[Re(CO)3(dpknph)Cl] and stud- Ϫ1.24 V (Ep,c ϭ Ϫ1.29 and Ep,a ϭ Ϫ1.18 V) and Ϫ1.62 V
ies are in progress to explore the thermodynamics and kin- (Ep,c ϭ Ϫ1.75 and Ep,a ϭ Ϫ1.48 V) pointing to the stability
etics of the interconversion between the high- and low-en- of the electrochemically generated species following the se-
ergy forms of fac-[Re(CO)3(dpkdnph)Cl] and its use as a cond and third electron transfer. The quasi-reversible reduc-
spectrophotometric sensor.
tion wave at Ϫ1.62 V is assigned to the ReI/0 couple as it
482
Eur. J. Inorg. Chem. 2002, 481Ϫ486

A Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone
FULL PAPER
falls in the potential range observed for such a couple in a is planar with all nitrogen and carbon atoms sp2 hybridized.
variety of rhenium compounds of polypyridyl-like ligands The bond lengths and angles (Table 1) of the coordinated
of the type fac-[Re(CO)3(L-L)Cl], where L-L ϭ dpk, atoms are normal and similar to those reported for a variety
dpk.oxime, dpknph and others.[17Ϫ20] The irreversible ox- of rhenium compounds of the type fac-[Re(CO)3(N-N)X],
idation wave at Ep,a ϭ ϩ1.74 V carries a peak current larger where N-N ϭ α-diimine ligand and X ϭ anion.[24Ϫ26]
than that observed for the first irreversible reduction wave
and points to its multi-electron character. The peak poten-
tial of this wave and its multi-electron character is similar
to that reported for fac-[Re(CO)3(dpk.oxime)Cl] and sug-
gests
a
metal-mediated oxidation of coordinated
dpkdnph.[19] Electrochemically generated product waves ap-
peared at Ep,a ϭ Ϫ1.62, ϩ0.15, ϩ0.55 and ϩ0.98 V
pointing to structural modifications following electron
transfer(s). Their appearance, coupled with the reversibility
of the reduction waves, points to the formation of electro-
chemically generated transient intermediates sensitive to
their surroundings that can be used to explore the electro-
chemical behaviour of various substrates toward fac-[Re-
(CO)3(dpkdnph)Cl] in a procedure similar to that reported
for fac-[Re(CO)3(dpk)Cl].[17,18]
Figure 4. ORTEP drawings of the structure of fac-
[Re(CO)3(dpknph)Cl]·CH3CN; thermal ellipsoids are drawn at the
30% probability level
˚
Table 1. Bond lengths [A] and angles [°] for fac-
[Re(CO)3(dpkdnph)Cl]·CH3CN
Re(1)ϪC(3)
Re(1)ϪC(1)
Re(1)ϪC(2)
Re(1)ϪN(2)
Re(1)ϪN(1)
Re(1)ϪCl(1)
C(2)ϪO(2)
C(3)ϪO(3)
C(1)ϪO(1)
C(4)ϪN(3)
C(4)ϪC(25)
N(3)ϪN(4)
N(4)ϪC(31)
N(5)ϪO(5)
N(5)ϪO(4)
N(6)ϪO(6)
N(6)ϪO(7)
1.900(4)
1.909(4)
1.924(4)
2.187(3)
2.210(3)
2.4732(11)
1.138(5)
1.151(5)
1.142(5)
1.298(5)
1.488(5)
1.351(4)
1.368(4)
1.213(4)
1.228(4)
1.203(6)
1.240(6)
C(3)ϪRe(1)ϪC(1)
C(1)ϪRe(1)ϪC(2)
C(3)ϪRe(1)ϪN(2)
C(1)ϪRe(1)ϪN(2)
C(2)ϪRe(1)ϪN(2)
C(1)ϪRe(1)ϪN(1)
N(2)ϪRe(1)ϪN(1)
N(1)ϪRe(1)ϪCl(1)
O(2)ϪC(2)ϪRe(1)
O(3)ϪC(3)ϪRe(1)
O(1)ϪC(1)ϪRe(1)
N(3)ϪC(4)ϪC(15)
N(3)ϪC(4)ϪC(25)
C(4)ϪN(3)ϪN(4)
O(5)ϪN(5)ϪO(4)
O(6)ϪN(6)ϪO(7)
N(7)ϪC(5)ϪC(6)
89.73(18)
90.61(17)
94.66(14)
91.94(15)
175.43(15)
174.87(15)
83.10(11)
85.09(8)
179.0(4)
178.4(4)
176.4(4)
114.8(3)
124.9(3)
118.6(3)
123.1(3)
124.9(4)
177.2(10)
Figure 3. Cyclic voltammograms of fac-[Re(CO)3(dpkdnph)Cl] in
DMF solutions 0.1  in [N(nBu)4](PF6)) at a glassy carbon
working electrode at a scan rate of 400 mVsϪ1 vs. SCE
Single crystals of fac-[Re(CO)3(dpkdnph)Cl]·CH3CN
were grown from an acetonitrile solution of fac-[Re(CO)3-
(dpkdnph)Cl] and the structure was determined using X-
ray crystallography. An ORTEP drawing of fac-
[Re(CO)3(dpkdnph)Cl]·CH3CN (Figure 4) shows well sep-
arated linear CH3CN and pseudo-octahedral fac-[Re-
(CO)3(dpkdnph)Cl]. The distortion from an octahedral
geometry about rhenium is due to the N,N-bidentate bind-
ing of dpkdnph and the formation of a six-membered
metallacyclic ring (Re1ϪN1ϪC15ϪC00ϪC25ϪN5) in a
The packing of molecules (Figure 5) shows anti-parallel
boat conformation with the pyridine rings in a butterfly (Λ) fac-[Re(CO)3(dpkdnph)Cl]·CH3CN units interlocked via a
formation. The NϪN bite angle [N(1)ϪRe1ϪN(2)] of network of non-covalent interactions that include hydrogen
83.03(11)° is of the same order as the 84.6° bite angles ob- bonding of the type X···HϪC, where X ϭ O, N or Cl and
served for the dpkO,OH in [ReOCl2(dpkO,OH)],[23] and is oxygen-nitrogen charge-transfer between the ortho-nitro
larger than the 74.3° reported for bipy in fac-[Re(CO)3- groups of adjacent molecules. Selected views of the non-
(bipy)(OPOF2)].[24] These results reveal that the six-mem- covalent interactions are shown in Figure 6 and their bond
bered metallacyclic ring in rhenium compounds with angles and distances are listed in Table 2. The amide (NH)
polypyridyl-like ligands is less constrained than the five- proton of the hydrazone backbone forms an intramolecular
membered metallacyclic ring in rhenium compounds with classical hydrogen bond of the type NϪH···O with the oxy-
α-diimine ligands. The 2,4-dinitrophenylhydrazone moiety gen atom (O4) of the ortho-nitro group. The acetonitrile
Eur. J. Inorg. Chem. 2002, 481Ϫ486
483

M. Bakir
FULL PAPER
around the oxygen atom participating in the non-covalent
C(24)ϪH(24)···O(6) interaction.
Figure 5. Packing of the molecules of fac-[Re(CO)3-
(dpkdnph)Cl]·CH3CN in the unit cell; non-covalent bonds are in-
dicated by dashed lines
˚
Table 2. Bond lengths [A] and angles [°] of the non-covalent inter-
actions
in
the
packed
structure
of
fac-[Re(CO)3-
(dpkdnph)Cl]·CH3CN
Bond[a]
Distance
Angle
O(4)···H(4)ϪN(4)
2.647
2.450
2.609
2.790
2.853
2.954
126.7
166.3
136.1
146.7
120.1
99.4, 80.6
O(6)···H(24)ϪC(24)(1)
N(7)···H(23)ϪC(23)(2)
Cl(1)···H(32)ϪC(32)(3)
Cl(1)···H(33)ϪC(33)(4)
N(5)ϪO(4)···N(5)ϪO(4)(5)
[a]
Symmetry transformations used to generate equivalent atoms:
(1): 1/2 Ϫ x, 1/2 ϩ y, 3/2 Ϫ z; (2): Ϫ1/2 ϩ x, 1/2 Ϫ y, 1/2 ϩ z; (3):
Ϫ1/2 ϩ x, 1/2 Ϫ y, Ϫ1/2 ϩ z; (4): 3/2 Ϫ x, 1/2 ϩ y, 3/2 Ϫ z; (5):
1 Ϫ x, Ϫy, 2 Ϫ z).
Owing to their convenient synthesis, rich physicochemical
properties and potential use as molecular sensors, work is
in progress to explore the electro-optical properties, solid
state structures and solution conformations of a variety of
di(2-pyridyl) ketone derivatives and their rhenium com-
pounds.
Figure 6. Selected views of the non-covalent bonding in the packed
structure of fac-[Re(CO)3(dpknph)Cl]·CH3CN; non-covalent bonds
are indicated by dashed lines
molecule binds to the adjacent proton (Figure 6b), whereas
the p-nitro group binds to an adjacent fac-[Re(CO)3-
(dpkdnph)Cl] unit and the axial chloride doubly
bridges
two
adjacent
phenyl
rings
in
a
[C(32)ϪH(32)···Cl(1)···H(33)ϪC(33)] bonding form (Fig-
ure 6c). The bond lengths and angles of the non-covalent
interactions are of the same order as those reported for a
variety of compounds containing such bonds.[27Ϫ29] The
difference in the oxygenϪnitrogen bond length (Table 1) of
Experimental Section
Reagents and Reaction Procedures: Solvents were reagent grade and
thoroughly deoxygenated prior to use. All other reagents were ob-
tained from commercial sources and used without further purifica-
the para-nitro group hints to an increase in electron density tion. All reactions were performed under a nitrogen atmosphere.
484 Eur. J. Inorg. Chem. 2002, 481Ϫ486

A Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone
Physical Measurements: Electronic absorption spectra were re-
cerning data collection.[30Ϫ32] The location of the rhenium atom
FULL PAPER
corded on a PerkinϪElmer Lambda 19 UV/Vis/NIR spectrometer. was determined from a Patterson map, and the remaining non-
Solution 1H NMR spectra were recorded on a Bruker ACE 200-
MHz Fourier transform spectrometer and referenced to the resid-
hydrogen atoms were located in subsequent difference Fourier
maps. All non-hydrogen atoms were refined with anisotropic ther-
ual protons in the deuterated solvent. Infrared spectra were re- mal parameters. In the final least-squares cycle, 344 parameters
corded as KBr pellets on a PerkinϪElmer Spectrum 1000 FT-IR
Spectrometer. Photochemical measurements were conducted on de-
oxygenated solutions before and after exposure to sunlight. Elec-
trochemical measurements were performed with the use of a Prin-
ceton Applied Research (PAR) Model 173 potentiostat/galvanostat
and Model 276 interface in conjunction with a 286 PC. Data were
acquired with the EG&G PARC Headstart program and manip-
ulated using Microsoft Excel Program. Measurements were per-
formed in solutions that were 0.1  in [N(nBu)4](PF6).The Ep,a, Ep,c
and Ep ϭ (Ep,a ϩ Ep,c)/2 values were referenced to the potassium
chloride saturated calomel electrode, SCE, at room temperature
and are uncorrected for junction potentials. The number of elec-
trons in the redox waves was determined using the oxidative peak
were fitted to 4095 observations, for a data to parameters ratio of
11.90:1. The least-squares residuals and other relevant parameters
are given in Table 3.
Table 3. Crystal data and structure refinement for fac-
[Re(CO)3(dpkdnph)Cl]·CH3CN
Empirical formula
Formula mass
Temperature
C22H15ClN7O7Re
711.06
298(2) K
˚
Wavelength
0.71073 A
Crystal system
Space group
Unit cell dimensions
Monoclinic
P21/n
a ϭ 12.1221(19) A, α ϭ 90°
b ϭ 14.226(2) A, β ϭ 98.691(13)°
ϩ
current of the reversible one electron FeCp2/FeCp2 couple as an
˚
internal standard. Electrochemical cells were of conventional de-
sign based on scintillation vials or H-cells. A glassy-carbon disc was
used as the working electrode and Pt-wire as a counter electrode.
˚
˚
c ϭ 14.6170(19) A, γ ϭ 90°
3
˚
V
Z
2491.7(7) A
4
Analytical Procedures: Microanalyses were performed by MEDAC
Ltd., Department of Chemistry, Brunel University, Uxbridge,
United Kingdom.
Density (calculated)
Absorption coefficient
F(000)
1.895 mg/m3
5.042 mmϪ1
1376
Theta range for data collection 2.01 to 25.00 °
Preparation of dpkdnph: A mixture of dpk (200 mg, 1.09 mmol),
2,4-dinitrophenylhydrazine (220 mg, 1.12 mmol), ethanol (100 mL)
and conc. HCL (0.25 mL) was refluxed for 5 h. The resulting reac-
tion mixture was allowed to stand at room temperature for 3 h. A
yellow solid was filtered off, washed with diethyl ether, hexane and
dried; yield 350 mg, 0.96 mmol (88%). C17H12N6O4 (364.3): calcd.
C 56.04, H 3.33, N 23.06; found C 55.86, H 3.32, N 22.98. IR (KBr
disk): ν(NϪH) 3320 cmϪ1. The low solubility of dpkdnph in polar
and non-polar solvents prevented any solution measurements on
this compound.
Reflections collected/unique
Completeness to theta: 25.00
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
8326/4095 [R(int) ϭ 0.0417]
93.2%
Empirical
0.3158 and 0.2749
Full-matrix least-squares on F2
4095/0/344
R1 ϭ 0.0227, wR2 ϭ 0.0547
R1 ϭ 0.0294, wR2 ϭ 0.0568
0.646 and Ϫ0.695 e·AϪ3
Largest diff. peak and hole
Preparation of fac-[Re(dpkdnph)(CO)3Cl]: A mixture of [Re(CO)5-
Cl] (200 mg, 0.55 mmol), dpkdnph (250 mg, 0.67 mmol) and tolu- Acknowledgments
ene (50 mL) was refluxed for 20 h. The resulting mixture was al-
I acknowledge funding from the following: The University of the
West Indies (UWI), Inter-America Development Bank (IDB) for
funds to establish the X-ray laboratory at UWI-Mona.
lowed to cool to room temperature and reduced in volume to ഠ
25 mL. A yellow solid was filtered off, washed with hexane and
diethyl ether, and dried; yield 300 mg, 0.45 mmol (82%).
C20H12ClN6O7Re (670.0): calcd. C, 35.87, H 1.80, N 12.54; found
C 35.91, H 1.91, N 12.48. IR (KBr disk): ν(CϭO) 2020, 1900, 1890
cmϪ1, ν(NO2) 1340, ν(NϪH) 3273. 1H NMR ([D6]DMSO): δ ϭ
11.80 (s, 1 H, NH), 9.15 (d, 1 H, dnph), 8.95 (d, 1 H, dnph), 8.85
(s, 1H dnph), 8.50Ϫ8.00 (closely spaced overlapped triplets and
doublets, 6 H, dpk), 7.8 (overlapped triplets, 2 H, dpk). In CDCl3:
δ ϭ 11.98 (s, 1 H, NH), 9.40 (d, 1 H, dnph), 9.16 (s, 1 H, dnph),
9.14 (d, 1 H, dnph), 8.45 (d, 1 H, dpk), 8.25Ϫ8.10 {overlapped
triplet (8.16) and doublet (8.15), 2 H, dpk}, 8.04 (t, 1 H, dpk), 7.85
(d, 2 H, dpk), 7.65 (t, 1 H, dpk), and 7.55 (t, 1 H, dpk). UV/Vis
{CH2Cl2, nm(ε)}: 396 sh (28,700); 358 (37,600), 268 (39,400).
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X-ray Crystallography: When fac-[Re(CO)3(dpkdnph)Cl] was al-
lowed to stand in acetonitrile solution for several days brown cubic
crystals of fac-[Re(CO)3(dpkdnph)Cl]·CH3CN were obtained. A
single crystal was selected and mounted on a glass fibre with epoxy
cement. A Bruker diffractometer equipped with a Mo-Kα radiation
source and a graphite monochromator was used for data collection,
and the SHELXTL software package version 5.1 was used for
structure solution. Cell parameters and other crystallographic in-
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