Syntheses, characterization and structures of chromium group carbonyl complexes containing a multifunctional Ph2P(o-C6H4)CH=N(CH2) 2(o-C6H4N) ligand

Article abstract of DOI:10.1016/S0022-328X(99)00734-2

Reactions of the phosphine-imine-pyridine-containing ligand Ph₂P(o-C₆H₄)CH=N(CH₂) ₂(o-C₆H₄N) (PNN) with M(CO)₃(NCMe)₃ (M=Cr, Mo, W) produce the tridentate complexes fac-M(CO)₃(η³-PNN). On the other hand, treating W(CO)₄(NCMe)₂ with PNN results in the bidentate complex W(CO)₄(η²-PNN), which converts to fac-W(CO)₃(η³-PNN) upon heating, but no facial→meridional isomerism is evidenced. The new compounds have been characterized by elemental analysis and mass, IR, and NMR spectroscopy. The molecular structures of W(CO)₄(η²-PNN), fac-W(CO)₃(η³-PNN) and fac-Mo(CO)₃(η³-PNN) are determined by an X-ray diffraction study.

Full text of DOI:10.1016/S0022-328X(99)00734-2

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 598 (2000) 353–358
Syntheses, characterization and structures of chromium group
carbonyl complexes containing a multifunctional
Ph2P(o-C6H4)CHꢀN(CH2)2(o-C6H4N) ligand
Ching-Chao Yang a, Wen-Yann Yeh a,*, Gene-Hsiang Lee b, Shie-Ming Peng b
a Department of Chemistry, National Sun Yat-Sen Uni6ersity, Kaohsiung 804, Taiwan
b Department of Chemistry, National Taiwan Uni6ersity, Taipei 106, Taiwan
Received 24 September 1999; received in revised form 15 November 1999; accepted 22 November 1999
Abstract
Reactions of the phosphine–imine–pyridine-containing ligand Ph2P(o-C6H4)CHꢀN(CH2)2(o-C6H4N) (PNN) with
M(CO)3(NCMe)3 (M=Cr, Mo, W) produce the tridentate complexes fac-M(CO)3(h3-PNN). On the other hand, treating
W(CO)4(NCMe)2 with PNN results in the bidentate complex W(CO)4(h2-PNN), which converts to fac-W(CO)3(h3-PNN) upon
heating, but no facial“meridional isomerism is evidenced. The new compounds have been characterized by elemental analysis
and mass, IR, and NMR spectroscopy. The molecular structures of W(CO)4(h2-PNN), fac-W(CO)3(h3-PNN) and fac-
Mo(CO)3(h3-PNN) are determined by an X-ray diffraction study. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Chromium group; Multifunctional ligand
In the present research, we explore the reactions of
PNN with mononuclear chromium group carbonyl
complexes.
1. Introduction
The multifunctional
compound
Ph2P(o-
C6H4)CHꢀN(CH2)2(o-C6H4N) (PNN), which contains
a phosphine, an imine and a pyridyl electron-donating
groups, was prepared by Lavery and Nelson from
2. Results and discussion
co-condensation
of
Ph2P(o-C6H4)C(ꢀO)H
and
2.1. Syntheses
H2N(CH2)2(o-C6H4N) [1]. Due to its flexible structure,
this molecule can act either as a monodentate P,
a bidentate PꢁN or a tridentate PꢁNꢁN ligand, which
is applicable to the design of new catalytic re-
actions [2–5]. For instance, the hemilabile property of
the pyridyl group has made the [(PNN)Pd(allyl)]+
complexes very active in allylic alkylation reactions
[6].
We recently found the reactions of PNN with trios-
mium carbonyl clusters to afford complexes containing
chelate and bridging PNN ligands as well as leading to
CꢁH and CꢁP bond activation of the PNN ligand [7].
Reactions of M(CO)3(NCMe)3 with the PNN
molecule at room temperature result in a facile substi-
tution of the labile acetonitrile ligands to afford fac-
M(CO)3(h3-PNN) in 52, 70 and 72% yields for
M=Cr, Mo and W, respectively (Eq. (1)). On the
other hand, treating W(CO)4(NCMe)2 with PNN pro-
duces the phosphine–imine bidentate complex
W(CO)4(h2-PNN),
which
transforms
to
fac-
W(CO)3(h3-PNN) upon heating (Eq. (2)). The Pd(0),
Pd(II) and Pt(II) complexes containing h1–h3-PNN
ligands were prepared previously by Vrieze and co-
workers [4,8], while the Mo(CO)4 complexes with the
related PꢁN and PꢁNꢁNꢁP ligands were reported by
Rauchfuss [9].
* Corresponding author. Fax: +886-7-5253908.
E-mail address: wenyann@mail.nsysu.edu.tw (W.-Y. Yeh)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00734-2

354
C.-C. Yang et al. / Journal of Organometallic Chemistry 598 (2000) 353–358
PNN) thermally. Previous investigation on the transfor-
mation
of
fac-W(CO)3(h2-dppf)(h1-dppm)
to
mer-W(CO)3(h2-dppm)(h1-dppf) suggested a pathway
through opening of the chelated diphosphine ligand
[13]. Since the flexible PNN ligand reveals little ring
constraint, the inaccessible fac“mer isomerism is prob-
ably due to the electronic effect.
2.2. Characterization of new compounds
(1)
Complexes fac-M(CO)3(h3-PNN) (M=Cr, Mo, W)
form air-stable, dark red crystals. Their FAB mass
spectra exhibit molecular ion peaks at m/z=530, 574
and 662 for 52Cr, 96Mo and 184W, respectively, and
fragments resulting from successive loss of three CO
groups. The IR spectra in the carbonyl-stretching re-
gion for these complexes are similar, suggesting great
resemblance of their structures.
1
The H-NMR spectrum of free PNN in CDCl3 pre-
sents a doublet resonance at 9.01 ppm (JPꢁH=5 Hz) for
the CHꢀN proton and two 2H triplets at 3.93 and 3.04
ppm (JHꢁH=7 Hz) for the (CH2)2 protons, while its
31P{1H}-NMR spectrum shows a singlet at −13.08
ppm for the phosphine group. In the fac-M(CO)3(h3-
PNN) complexes, the phosphine 31P resonances are
shifted downfield to 50.94, 36.13 and 31.73 ppm for
M=Cr, Mo and W, respectively, and the imine CHꢀN
1H resonances are shifted slightly to ca. 9.5 ppm. It has
been noted that, for the metal phosphine complexes of
a similar structure, one generally observes a high-field
shift of the 31P resonance as one descends in a given
group [14]. Furthermore, the (CH2)2 proton resonances
are split into four 1H multiplets in the range 4.30–1.13
ppm to indicate asymmetric coordination of the PNN
ligand, leading to diastereotopic methylene groups.
W(CO)4(h2-PNN) forms orange–red crystals. Its
FAB mass spectrum displays a molecular ion peak at
m/z=690 for 184W, which is 28 more than that of
fac-W(CO)3(h3-PNN), and fragments corresponding to
successive loss of four carbonyls. Apparently, either the
PꢁN or the NꢁN set of PNN ligand is bonded to the W
atom to satisfy the 18-electron rule. On the basis of the
31P-NMR spectrum, which displays a resonance at
24.19 ppm with 183W satellites (1JWꢁP=238 Hz), the
PꢁN coordination mode is preferred. The IR spectra of
W(CO)4(h2-PNN) and fac-W(CO)3(h3-PNN) in the
carbonyl region are shown in Fig. 1; it appears that the
absorptions are shifted to lower energy with increasing
substitution, consistent with the stronger net donor
capability of the PNN ligand compared with CO.
(2)
Attempts to synthesize the tungsten poly(PNN) com-
plexes, such as W(CO)4(PNN)2, W(CO)3(PNN)2 or
W(CO)3(PNN)3, have been unsuccessful. It was found
that treating W(CO)3(NCMe)3 with an excess amount
of PNN, heating or photolysis of W(CO)4(h2-PNN) in
the presence of PNN, or pyrolysis of W(CO)6 and PNN
at high temperature led only to fac-W(CO)3(h3-PNN).
Since both the PꢁN and NꢁN sets of the ligand can
form a stable six-membered chelate ring upon coordina-
tion, it is probable that the chelate effect [10] is govern-
ing the products yielded.
The d6 metal tricarbonyl complexes M(CO)3L3 ex-
hibit facial ( fac) and meridional (mer) isomers. When
L is a good s donor and poor p acceptor relative to
CO, the fac isomer is expected to be more stable
electronically to achieve stronger M–CO back dona-
tion. On the other hand, the mer isomer is less sterically
encumbered and is favored when L contains bulky
groups [11,12]. For example, only fac-W(CO)3(PMe3)3
is existent while both fac-W(CO)3(PPh3)3 and mer-
W(CO)3(PPh3)3 are present [13]. We were unable to
convert fac-W(CO)3(h3-PNN) into mer-W(CO)3(h3-
2.3. Molecular structures
Crystals of W(CO)4(h2-PNN), fac-W(CO)3(h3-PNN)
and fac-Mo(CO)3(h3-PNN) contain an ordered array of
discrete monomeric molecular units, which are mutu-

C.-C. Yang et al. / Journal of Organometallic Chemistry 598 (2000) 353–358
355
Fig. 3. Molecular structure of fac-W(CO)3(h3-PNN). Thermal ellip-
soids are drawn at 30% probability. The hydrogen atoms have been
artificially omitted for clarity.
,
1.955(4) A to C(1). Enhancement of W“CO back-do-
nation for the latter two bondings is consistent with
good s donor and poor p acceptor of the phosphine
(and imine) ligand relative to CO. The PNN ligand
chelates the tungsten atom through the phosphine–
imine groups with the bite angle P(1)ꢁWꢁN(1)=
80.74(2)°. The uncoordinated C(11)ꢁN(1) bond
Fig. 1. IR spectra in the carbonyl region for (a) W(CO)4(h2-PNN)
and (b) fac-W(CO)3(h3-PNN) obtained in CH2Cl2 solvent.
ally separated by normal van der Waals distances.
Their ORTEP diagrams are shown in Figs. 2–4. Selected
bond distances and bond angles for W(CO)4(h2-PNN)
are given in Table 1, and for fac-W(CO)3(h3-PNN) and
fac-Mo(CO)3(h3-PNN) are collected in Table 2.
,
(1.275(5) A) retains a CꢀN double-bond character.
The molecular structures of fac-W(CO)3(h3-PNN)
and fac-Mo(CO)3(h3-PNN) are essentially identical,
where the coordination about the central metal atom is
a distorted octahedron with the PNN ligand capping a
triangular face. Three terminal carbonyl ligands are
linked to W and Mo atoms with the MꢁCO distances in
W(CO)4(h2-PNN) is associated with four terminal
carbonyls with the WꢁCꢁO angles in the range
,
174.7(4)–178.2(4)°. The WꢁCO distances are 2.024(4) A
,
the range 1.927(5)–1.976(6) A and the MꢁCꢁO angles
,
to C(2) and 2.007(4) A to C(4), while those distances
in the range 175.3(6)–178.8(4)°. The P(1)ꢁMꢁN(1),
P(1)ꢁMꢁN(2) and N(1)ꢁMꢁN(2) angles are 79.1(1),
94.2(1) and 82.8(1)° for M=W, and 78.5(1), 94.55(9)
trans to the phosphine and imine groups are slightly but
,
significantly shorter, being 1.982(4) A to C(3) and
Fig. 4. Molecular structure of fac-Mo(CO)3(h3-PNN). Thermal ellip-
soids are drawn at 30% probability. The hydrogen atoms have been
artificially omitted for clarity.
Fig. 2. Molecular structure of W(CO)4(h2-PNN). Thermal ellipsoids
are drawn at 30% probability. The hydrogen atoms have been artifi-
cially omitted for clarity.

356
C.-C. Yang et al. / Journal of Organometallic Chemistry 598 (2000) 353–358
Table 1
respectively. We note that the MoꢁCO bonds are
2
,
Selected bond distances (A) and bond angles (°) for W(CO)4(h -
PNN)
,
slightly shorter (av. 0.008 A) than the WꢁCO bonds,
while the MꢁP(1), MꢁN(1) and MꢁN(2) distances to the
molybdenum atom are longer than those to the tung-
Bond distances
WꢁP(1)
WꢁC(1)
WꢁC(3)
C(1)ꢁO(1)
C(3)ꢁO(3)
P(1)ꢁC(5)
C(10)ꢁC(11)
N(1)ꢁC(12)
,
sten atom by 0.01–0.02 A. Since the atomic sizes of Mo
2.485(1)
1.955(4)
1.982(4)
1.163(4)
1.150(5)
1.826(3)
1.475(5)
1.492(4)
WꢁN(1)
WꢁC(2)
WꢁC(4)
C(2)ꢁO(2)
C(4)ꢁO(4)
C(5)ꢁC(10)
C(11)ꢁN(1)
2.272(3)
2.025(4)
2.007(4)
1.142(5)
1.148(5)
1.401(5)
1.275(5)
and W are comparable, this phenomenon might arise
from electronic effects with different donor ability of
the CO and PNN ligands and/or steric repulsions be-
tween the ligands.
3. Experimental
Bond angles
WꢁC(1)ꢁO(1)
WꢁC(3)ꢁO(3)
P(1)ꢁWꢁN(1)
C(3)ꢁWꢁP(1)
C(11)ꢁN(1)ꢁC(12)
176.9(3)
178.2(4)
80.74(7)
175.6(1)
113.9(3)
WꢁC(2)ꢁO(2)
WꢁC(4)ꢁO(4)
C(1)ꢁWꢁN(1)
C(2)ꢁWꢁC(4)
175.1(4)
174.7(4)
173.2(1)
172.2(2)
3.1. General methods
All manipulations were carried out under an atmo-
sphere of purified dinitrogen with standard Schlenk
techniques [15]. Cr(CO)6, Mo(CO)6 and W(CO)6 from
Strem were used as received. Anhydrous Me3NO was
obtained from Me3NO·2H2O (Aldrich) by sublimation
under vacuum twice. Ph2P(o-C6H4)CHꢀN(CH2)2(o-
C6H4N) was synthesized from condensation of Ph2P(o-
C6H4)C(ꢀO)H and NH2(CH2)2(o-C6H4N) (Aldrich) as
described in the literature [1]. Solvents were dried over
appropriate reagents under dinitrogen and distilled im-
mediately before use [16]. Infrared spectra were
recorded with a 0.1 mm-path CaF2 solution cell on a
Hitachi I-2001 IR spectrometer. 1H- and 31P-NMR
spectra were obtained on a Varian VXR-300 spectrom-
eter at 300 and 121.4 MHz, respectively. Fast-atom-
bombardment (FAB) mass spectra were recorded by
using a VG Blotch-5022 mass spectrometer. Elemental
analyses were performed at the National Science Coun-
cil Regional Instrumentation Center at National
Chung-Hsing University, Taichung, Taiwan.
and 83.1(1)° for M=Mo. The P(1), C(4), C(9), C(10)
and N(1) atoms are planar to within 90.1 A for both
compounds. The C(10)ꢁN(1) double-bond distances are
1.281(7) and 1.276(6) A for the W and Mo complexes,
,
,
Table 2
3
,
Selected bond distances (A) and bond angles (°) for fac-M(CO)3(h -
PNN) (M=W and Mo)
M=W
M=Mo
Bond distances
MꢁP(1)
MꢁN(1)
MꢁN(2)
MꢁC(1)
MꢁC(2)
MꢁC(3)
C(1)ꢁO(1)
C(2)ꢁO(2)
C(3)ꢁO(3)
P(1)ꢁC(4)
C(4)ꢁC(9)
C(9)ꢁC(10)
C(10)ꢁN(1)
N(1)ꢁC(11)
C(11)ꢁC(12)
C(12)ꢁC(13)
C(13)ꢁN(2)
2.484(1)
2.228(4)
2.341(4)
1.976(6)
1.938(5)
1.940(5)
1.144(6)
1.171(6)
1.163(6)
1.837(5)
1.410(7)
1.456(8)
1.281(7)
1.461(7)
1.508(8)
1.492(8)
1.345(6)
2.494(1)
2.243(4)
2.364(4)
1.970(5)
1.931(4)
1.927(5)
1.150(6)
1.166(5)
1.168(5)
1.834(4)
1.403(6)
1.454(7)
1.276(6)
1.475(6)
1.503(7)
1.496(7)
1.351(5)
3.2. Synthesis of fac-Cr(CO)3(p3-PNN)
A 50 ml Schlenk flask was equipped with a magnetic
stir bar and a reflux condenser connected to an oil
bubbler. Cr(CO)6 (101 mg, 0.45 mmol) and acetonitrile
(15 ml) were introduced into the flask under dinitrogen,
and the solution was heated to reflux for 72 h, at which
point the IR spectrum indicated Cr(CO)6 was com-
pletely transformed to Cr(CO)3(NCMe)3. The acetoni-
trile solvent was then removed under vacuum. A
solution of PNN (181 mg, 0.45 mmol) in
dichloromethane (10 ml) was added to the flask by a
syringe and the reaction mixture was stirred at ambient
temperature for 1 h, resulting a solution color change
from bright yellow to deep red. The solution was then
dried under vacuum, and the crude product was crystal-
lized from dichloromethane–hexane to afford dark red
crystals of fac-Cr(CO)3(h3-PNN) (124 mg, 0.23 mmol,
Bond angles
MꢁC(1)ꢁO(1)
MꢁC(2)ꢁO(2)
MꢁC(3)ꢁO(3)
P(1)ꢁMꢁN(1)
P(1)ꢁMꢁN(2)
N(1)ꢁMꢁN(2)
P(1)ꢁMꢁC(1)
C(3)ꢁMꢁN(2)
C(2)ꢁMꢁN(1)
C(10)ꢁN(1)ꢁC(11)
N(1)ꢁC(10)ꢁC(9)
175.3(6)
178.8(4)
177.2(4)
79.1(1)
175.6(5)
178.2(4)
176.2(4)
78.5(1)
94.55(9)
83.1(1)
168.6(2)
177.9(2)
175.9(2)
115.9(4)
126.2(4)
94.2(1)
82.8(1)
168.3(2)
177.8(2)
175.6(2)
115.4(4)
127.1(5)
52%). IR (CH2Cl2, wCO): 1914 s, 1810 s, 1788 s cm−1
.

C.-C. Yang et al. / Journal of Organometallic Chemistry 598 (2000) 353–358
357
1H-NMR (C6D6, 20°C): 9.56 (d, CHꢀN), 8.07–5.90
(m, Ph, Py), 4.30 (m, 1H), 2,95 (m, 1H), 2.10 (m, 1H),
1.13 (m, 1H, CH2) ppm. 31P{1H}-NMR (C6D6, 20°C):
50.94 ppm. MS (FAB) m/z: 530 (M+, 52Cr), 530–28n
(n=1–3).
mmol) in dichloromethane (7 ml) was added to the
flask by a syringe and the reaction mixture was stirred
at ambient temperature for 1 h, resulting a solution
color change from bright yellow to orange red. The
volatile materials were removed under vacuum, and the
residue was crystallized from dichloromethane–hexane
to afford orange red crystals of W(CO)4(h2-PNN) (99
mg, 0.14 mmol, 50%). IR (CH2Cl2, wCO): 2008 s, 1894 s,
3.3. Synthesis of fac-Mo(CO)3(p3-PNN)
1
1856 s cm−1. H-NMR (C6D6, 20°C): 8.52 (d, CHꢀN),
Mo(CO)6 (100 mg, 0.37 mmol) and acetonitrile (15
ml) were refluxed under dinitrogen for 12 h to produce
Mo(CO)3(NCMe)3. The reaction of Mo(CO)3(NCMe)3
and PNN (150 mg, 0.37 mmol) was then carried out
and worked up in a fashion identical with that above.
fac-Mo(CO)3(h3-PNN) (149 mg, 0.26 mmol, 70%) was
obtained as dark red crystals after crystallization from
dichloromethane–hexane. IR (CH2Cl2, wCO): 1920 s,
8.07–6.85 (m, Ph, Py), 4.35 (t, 2H, CH2), 3.11 (t, 2H,
CH2) ppm. 31P{1H}-NMR (C6D6, 20°C): 24.19 (s, with
183W satellites, JWꢁP=238 Hz) ppm. MS (FAB) m/z:
690 (M+, 184W), 690–28n (n=1–4). Anal. Found C,
52.12; H, 3.44; N, 4.00. C30H23N2O4PW; Anal. Calc. C,
52.19; H, 3.35; 4.05%.
3.6. Thermolysis of W(CO)4(p2-PNN)
1
1816 s, 1794 s cm−1. H-NMR (C6D6, 20°C): 9.40 (d,
CHꢀN), 8.05–5.95 (m, Ph, Py), 4.08 (m, 1H), 2,81 (m,
1H), 2.12 (m, 1H), 1.20 (m, 1H, CH2) ppm. 31P{1H}-
NMR (C6D6, 20°C): 36.13 ppm. MS (FAB) m/z: 574
(M+, 96Mo), 574–28n (n=1–3). Anal. Found C, 55.53;
H, 3.65; N, 4.25. C30H25Cl2N2O3PMo (containing a
CH2Cl2 crystal solvent) Anal. Calc. C, 54.64; H, 3.82;
4.24%.
A solution of W(CO)4(h2-PNN) (9 mg) in n-octane
(4 ml) was heated to reflux under dinitrogen for 2 h,
resulting in a solution color change from orange red to
deep red. The octane solvent was removed under vac-
uum, and the residue crystallized from dichloro-
methane–hexane to yield fac-W(CO)3(h3-PNN) (6 mg).
Similar results were obtained by heating W(CO)4(h2-
PNN) in the presence of PNN ligand. There was no
evidence for the formation of W(CO)3(PNN)2 or
W(CO)4(PNN)2.
3.4. Synthesis of fac-W(CO)3(p3-PNN)
W(CO)6 (90 mg, 0.25 mmol) and acetonitrile (20 ml)
were refluxed under dinitrogen for 72 h to produce
W(CO)3(NCMe)3. The reaction of W(CO)3(NCMe)3
and PNN (101 mg, 0.25 mmol) was then carried out
and worked up in a fashion identical with that above.
fac-W(CO)3(h3-PNN) (119 mg, 0.18 mmol, 72%) was
obtained as dark red crystals after crystallization from
dichloromethane–hexane. IR (CH2Cl2, wCO): 1912 s,
3.7. Attempts to isomerize fac-W(CO)3(p3-PNN) to
mer-W(CO)3(p3-PNN) thermally
A solution of fac-W(CO)3(h3-PNN) (5 mg) in toluene
solvent (3 ml) was heated to reflux under dinitrogen for
12 h. The reaction monitored by IR showed no new CO
absorptions to indicate the formation of mer-
W(CO)3(h3-PNN).
1
1808 s, 1786 s cm−1. H-NMR (C6D6, 20°C): 9.45 (d,
CHꢀN), 8.07–5.92 (m, Ph, Py), 4.03 (m, 1H), 3.93 (m,
1H), 2.89 (m, 1H), 1.20 (m, 1H, CH2) ppm. 31P{1H}-
NMR (C6D6, 20°C): 31.73 (s, with 183W satellites,
3.8. Co-pyrolysis of W(CO)6 and PNN in a sealed
tube
J
WꢁP=227 Hz) ppm. MS (FAB) m/z: 662 (M+, 184W),
662–28n (n=1–3). Anal. Found C, 47.96; H, 3.54; N,
3.75. C30H25Cl2N2O3PW (containing a CH2Cl2 crystal
solvent) Anal. Calc. C, 48.19; H, 3.34; 3.74%.
W(CO)6 (23 mg) and PNN (21 mg) were mixed,
ground, and sealed in a Pyrex glass tube under vacuum
(0.01 torr). The tube was placed in a silicon oil bath at
125°C for 1 h, removed from oil bath and cooled to
ambient temperature, and opened in air. The products
were extracted with dichloromethane and crystallized
by adding n-hexane. fac-W(CO)3(h3-PNN) (10%) and
W(CO)4(h2-PNN) (23%) were obtained.
3.5. Synthesis of W(CO)4(p2-PNN)
W(CO)6 (100 mg, 0.28 mmol) and dichloromethane
(5 ml) were placed in a 50 ml Schlenk flask under
dinitrogen. A solution of Me3NO (45 mg, 0.60 mmol)
in acetonitrile (7 ml) was added dropwise into the flask
by a syringe over a period of 20 min. The mixture was
stirred at ambient temperature for 2 h, at which point
the IR spectrum indicated the presence of W(CO)4-
(NCMe)2. The acetonitrile solvent was then removed
under vacuum. A solution of PNN (112 mg, 0.28
3.9. Structural determination for fac-W(CO)3(p3-PNN),
fac-Mo(CO)3(p3-PNN) and W(CO)4(p2-PNN)
Crystals of fac-W(CO)3(h3-PNN) (ca. 0.60×0.50×
0.20 mm3), fac-Mo(CO)3(h3-PNN) (ca. 0.50×0.40×

358
C.-C. Yang et al. / Journal of Organometallic Chemistry 598 (2000) 353–358
Table 3
4. Supplementary materials
Crystal data and refinement details for W(CO)4(h2-PNN), fac-W(CO)3(h3-
PNN) and fac-Mo(CO)3(h3-PNN)
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 136819 for W(CO)4(h2-
PNN), 136817 for fac-W(CO)3(h3-PNN) and 136818
for fac-Mo(CO)3(h3-PNN). Copies of this information
may be obtained free of charge from: The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
ac.uk or www: http://www.ccdc.cam.ac.uk).
W(CO)4-
W(CO)3-
Mo(CO)3-
(h2-PNN)
(h3-PNN)
(h3-PNN)
Formula
C
30H23N2O4PW C29H23N2O3PW C29H23N2O3PMo
Crystal solvent
Formula weight
Temperature (K)
Radiation u (A)
Crystal system
Space group
CH2Cl2
747.24
293(2)
0.71073
Monoclinic
P21/n
CH2Cl2
659.33
293(3)
0.71073
Monoclinic
P21/n
690.32
293(2)
0.71073
Triclinic
,
(
P1
Unit cell dimensions
,
a (A)
8.789(2)
10.533(2)
15.991(3)
80.58(2)
86.52(2)
68.73(2)
1361.0(5)
2
13.400(2)
16.364(2)
13.602(2)
90
102.02(1)
90
2917.3(6)
4
1.701
13.478(3)
16.390(4)
13.611(3)
90
102.34(2)
90
2937(1)
4
1.491
,
b (A)
Acknowledgements
,
c (A)
h (°)
i (°)
k (°)
We are grateful for support of this work by the
National Science Council of Taiwan.
3
,
V (A )
Z
Dcalc. (g cm−3
F(000)
)
1.685
676
4.341
1464
4.232
1336
0.717
References
v (mm−1
)
a
R1/wR2
0.0197/0.0477 0.0290/0.0759 0.0421/0.1079
1.062 1.077 1.053
[1] A. Lavery, S.M. Nelson, J. Chem. Soc. Dalton Trans. (1984)
615.
Goodness-of-
fit on F2
[2] E. Drent, J.A.M. van Broekhoven, M.J. Doyle, J. Organomet.
Chem. 417 (1991) 235.
[3] B.M. Trost, T.R. Verhoeven, J. Am. Chem. Soc. 100 (1978)
3435.
a R1=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ; wR2={ꢀ[w(ꢁFoꢁ −ꢁFcꢁ ) ]/ꢀ wꢁFoꢁ ]}1/2
.
2
2 2
4
0.20 mm3) and W(CO)4(h2-PNN) (ca. 0.60×0.50×
0.50 mm3) were each mounted in a thin-walled glass
capillary and aligned on the Nonius CAD-4 diffrac-
tometer with graphite-monochromated Mo–Ka radia-
[4] G.W. Parshall, S.D. Ittel, Homogeneous Catalysis, Wiley, New
York, 1992.
[5] F. Benvenuti, C. Carlini, M. Marchionna, R. Patrini, A.M.
Raspolli Galletti, G. Sbrana, J. Mol. Catal. A Chem. 140 (1999)
139.
[6] R.E. Ru¨lke, V.E. Kaasjager, P. Wehman, C.J. Elsevier,
P.W.N.M. van Leeuwen, K. Vrieze, J. Fraanje, K. Goubitz, A.L.
Spek, Organometallics 15 (1996) 3022.
[7] W.-Y. Yeh, C.-C. Yang, S.-M. Peng, G.-H. Lee, unpublished
results.
[8] P. Wehman, R.E. Ru¨lke, V.E. Kaasjager, P.C.J. Kamer, H.
Kooijman, A.L. Spek, C.J. Elsevier, K. Vrieze, P.W.N.M. van
Leeuwen, J. Chem. Soc. Chem. Commun. (1995) 331.
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[10] F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, fifth
ed., Wiley, New York, 1988.
,
tion (u=0.71073 A). The data were collected using the
q/2q scan technique with q ranging from 1.94 to 25.00°
for fac-W(CO)3(h3-PNN), 1.93 to 25.00° for fac-
Mo(CO)3(h3-PNN) and 1.29 to 25.00° for W(CO)4(h2-
PNN). All data were corrected for Lorentz and
polarization effects and for the effects of absorption.
The structures were solved by the heavy-atom method
and refined by full-matrix least-square cycles on F2 on
the basis of 4232 observed reflections [I\2|(I)] for
fac-W(CO)3(h3-PNN), 3612 observed reflections for
fac-Mo(CO)3(h3-PNN) and 4438 observed reflections
for W(CO)4(h2-PNN). The non-hydrogen atoms were
refined anisotropically. Hydrogen atoms were included
but not refined. All calculations were performed using
the SHELXTL package. A summary of relevant crystallo-
graphic data is provided in Table 3.
[11] F. Basolo, Polyhedron 9 (1990) 1503.
[12] D.M.P. Mingos, J. Organomet. Chem. 179 (1979) C29.
[13] S.C.N. Hsu, W.-Y. Yeh, J. Chem. Soc. Dalton Trans. (1998)
125.
[14] P.E. Garrou, Chem. Rev. 81 (1981) 229.
[15] D.F. Shriver, M.A. Drezdzon, The Manipulation of Air-Sensi-
tive Compounds, second ed., Wiley, New York, 1986.
[16] D.D. Perrin, W.L. Armarego, D.R. Perrin, Purification of Labo-
ratory Chemicals, Pergamon, Oxford, 1966.
.