Synthesis, crystal structures and spectroscopic properties of cationic carbyne complexes of molybdenum and tungsten supported by tripodal nitrogen, phosphorus and sulphur donor ligands

Article abstract of DOI:10.1016/S0022-328X(98)00564-6

Reaction of the tridentate ligands HCpy₃ or Ppy₃ (py = 2-pyridyl) with Cl(CO)₂py₂M=CPh (M = Mo, W) in THF at elevated temperature followed by metathesis with NaBPh₄ in CH₃CN affords [(n

Full text of DOI:10.1016/S0022-328X(98)00564-6

Journal of Organometallic Chemistry 563 (1998) 191–200
Synthesis, crystal structures and spectroscopic properties of cationic
carbyne complexes of molybdenum and tungsten supported by tripodal
nitrogen, phosphorus and sulphur donor ligands
Fu-Wa Lee, Michael Chi-Wang Chan, Kung-Kai Cheung, Chi-Ming Che *
Department of Chemistry, The Uni6ersity of Hong Kong, Pokfulam Road, Hong Kong
Received 25 February 1998
Abstract
Reaction of the tridentate ligands HCpy3 or Ppy3 (py=2-pyridyl) with Cl(CO)2py2MꢀCPh (M=Mo, W) in THF at elevated
temperature followed by metathesis with NaBPh4 in CH3CN affords [(p3-Xpy3)(CO)2MꢀCPh]+ (M=W, X=P (2), HC (3);
M=Mo, X=P (4)) in high yield. Interaction between 1,1,1-tris(diphenylphosphinomethyl)ethane (CH3C(CH2PPh2)3) or 1,4,7-
trithiacyclononane (TTCN) and Cl(CO)2py2WꢀCPh in the presence of AgPF6 in refluxing CH3CN gives
[{CH3C(CH2PPh2)3}(CO)2WꢀCPh]PF6 (5) and [(TTCN)(CO)2WꢀCPh]PF6 (6), respectively. These complexes exhibit intense
absorption bands at 320–340 nm and weak absorptions in the 400–500 nm region, while excitation at 330 nm in dichloromethane
give intense orange to red emission. The structure of the product (1) from reaction of Ppy3 with Cl(CO)2py2WꢀCPh was
established by X-ray crystallography and shows that only two of the pyridine rings in Ppy3 are bound to the metal center. The
crystal structures of 2·EtOH and 3·EtOH show that the W–N distance trans to the carbyne moiety is significantly longer than
those which are cis, and this is attributed to the strong trans influence of CPh compared to CO. © 1998 Elsevier Science S.A. All
rights reserved.
Keywords: Carbyne complexes; Crystal structures; Molybdenum; Photoluminescence; Tripodal ligands; Tungsten.
1. Introduction
facial ligands with various donor atoms, namely nitro-
gen, phosphorus and sulphur, on the reactivity of the
carbyne moiety and complex as a whole, cationic
phenylcarbyne derivatives of the type [(p3-
L’)M(CO)2(ꢀCPh)]+ (M=Mo, W; p3-L’=tris(2-
pyridyl)methane (HCpy3), tris(2-pyridyl)phosphine
(Ppy3), 1,1,1-tris(diphenylphosphinomethylethane
(CH3C(CH2PPh2)3) and 1,4,7-trithiacyclononane (TT-
CN) were prepared. Characterization of these com-
plexes by X-ray crystallography was undertaken to
allow for structural comparisons. It is noteworthy that
the strength of the donor atom trans to the carbyne
moiety in related tungsten–carbyne complexes can af-
fect the strength [5] and hence the reactivity [6] of the
WꢀC bond.
The chemistry of cationic carbyne complexes of
group 6 metals [1] is less developed than their neutral
counterparts [2,3], while the incorporation of neutral
tridentate ligands into these systems is rare. We recently
reported on the cationic carbyne complexes of group 6
metals bearing facial nitrogen donor ligands and these
illustrated the strong |-donating strengths of 1,4,7-
trimethyl-1,4,7-triazacyclononane (Me3TACN) and
1,4,7-triazacyclononane (TACN) [4].
In an attempt to study the effects of different neutral
* Corresponding author. Tel.: +852 28592154; fax: +852
28571586; e-mail: cmche@hkucc.hku.hk
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00564-6

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F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
2. Results and discussion
Reactions of the tridentate ligands HCpy3 and Ppy3
with Cl(CO)2py2MꢀCPh (M=Mo, W) in THF at ele-
vated temperature yielded yellow solids which are solu-
ble in acetonitrile but insoluble in dichloromethane.
The structure of the product using Ppy3 in the case of
tungsten was established by X-ray crystallography as
[Cl(p2-Ppy3)(CO)2WꢀCPh] (1), where one pyridine ring
does not coordinate to the tungsten atom. We envis-
aged that metathesis of the chloride group with a
non-coordinating anion would result in tridentate coor-
dination of the facial ligand. Hence, addition of sodium
tetraphenylborate to the yellow solids in warm acetoni-
trile afforded the corresponding cationic complexes
[(p3-Xpy3)(CO)2MꢀCPh]+ (M=W, X=P (2), HC (3);
M=Mo, X=P (4)) (Scheme 1). It is notable that for
the triamine ligand Me3TACN, the macrocyclic effect is
manifested in the unassisted displacement of the chlo-
ride ligand from the metal center [4].
Scheme 2.
On the contrary, the reaction of [Ru(DMF)6](OTs)2
[9] with 2 equivalents of Ppy3 affords [(p3-Ppy3)2Ru]2+
with only N donors. Therefore, it is apparent that Ppy3
can replace ‘soft’ donors such as triphenylphosphine to
give complexes containing P donors but displaces ‘hard’
ligands to afford species with N donors only. The latter
situation is observed in this work where Ppy3 coordi-
nates solely via nitrogen atoms in complexes 1, 2 and 4.
Refluxing CH3C(CH2PPh2)3 or TTCN with
Cl(CO)2py2WꢀCPh in CH3CN showed no observable
change. However, with the addition of one equivalent
of silver hexafluorophosphate, the cationic complexes
The coordination mode of Ppy3 in molybdenum and
tungsten carbyne derivatives merits further discussion.
Although
2,2%-bipyridine
(bpy)
and
1,2-bis-
(diphenylphosphino)ethane (dppe) respectively, react
with Cl(CO)2py2WꢀCPh to form Cl(L–L)(CO)2WꢀCPh
[7] (L–L=bpy, dppe), complexes of the types A and B
(Scheme 2) with mixed N/P coordination have not been
reported. Wilkinson and co-workers [8] reported that
reaction of RuCl2(PPh3)3 and RhCl(PPh3)3 with excess
Ppy3 gave the products C and D, respectively, (Scheme
2) with both P and N as donor atoms.
[{CH3C(CH2PPh2)3}(CO)2WꢀCPh]+
(5)
and
[(TTCN)(CO)2WꢀCPh]+ (6) respectively, were ob-
tained in high yields. The TTCN derivative is relatively
unstable: decomposition occurs in aerobic CH3CN after
3 days with the appearance of free TTCN ligand. The
unstable nature of 6 may be accredited to the low
coordinating strength of TTCN. In summary,
Cl(CO)2py2MꢀCPh (M=Mo, W) are good precursors
for the preparation of cationic carbyne complexes con-
taining neutral facial ligands such as Ppy3, HCpy3,
CH3C(CH2PPh2)3 and TTCN.
Selected NMR and IR spectral data of complexes
1–6 and related carbyne complexes are summarized in
1
Table 1. The H- and 13C{1H}-NMR data suggest that
in solution complexes 1–6 contain a mirror plane along
the metal–carbyne bond which bisects the tridentate
ligand and the terminal carbonyl groups. The 13C
chemical shifts of the carbyne carbon atoms are within
the range expected for Group 6 complexes [3]. A com-
parison of the 13C{1H}-NMR spectral data should re-
veal the influence of the metal atoms and the facial
ligands upon the MꢀC and metal-bound CꢀO moieties.
The 13C l(C
6
Ph) values of Cl(CO)2py2WꢀCPh, Cl(p2-
Scheme 1.
Ppy3)(CO)2WꢀCPh (1) and Cl(CO)2(bpy)WꢀCPh are

F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
193
Table 1
Selected IR and 13C{1H}-NMR data for related Group 6 carbyne complexes
Complex
w(CO)a (cm−1
)
l(C
6
Ph)c (ppm)
l(CO)c (ppm)
References
[Cl(p2-Ppy3)(CO)2WꢀCPh], 1
[(p3-Ppy3)(CO)2WꢀCPh]BPh4, 2
[(p3-HCpy3)(CO)2WꢀCPh]BPh4, 3
[(p3-Ppy3)(CO)2MoꢀCPh]BPh4, 4
[{p3-CH3C(CH2PPh2)3}(CO)2WꢀCPh]PF6, 5
[(TTCN)(CO)2WꢀCPh]PF6, 6
[(Me3TACN)(CO)2MoꢀCPh]BPh4
[(TACN)(CO)2MoꢀCPh]BPh4
[(Me3TACN)(CO)2WꢀCPh]BPh4
[Cl(CO)2py2WꢀCPh]
1980s, 1885s
1984s, 1899s
1988s, 1894s
1998s, 1918s
1999s, 1934s
2007s, 1925s
1980s, 1906s
1997s, 1914s
1975s, 1879s
1985s, 1897sb
1986s, 1899sb
266.3
286.3
288.1
297.2
294.8
293.1
298.0d
294.3d
288.0d
262.7e
265.8e
223.2
221.1
222.0
223.1
211.6
214.0
225.2d
225.8d
224.6d
220.4e
222.2e
[4]
[4]
[4]
[7]
[7]
[Cl(CO)2(bpy)WꢀCPh]
a KBr unless specified otherwise.
b In CH2Cl2.
c In CD3CN unless specified otherwise.
d In d6-acetone.
e In CDCl3.
Table 2
Absorption and emission data
b
Compounds
UV–visa nm (log mmax
)
Emission umax
,
nm (~, vs)
Quantum yield bem×10−5
[Cl(p2-Ppy3)(CO)2WꢀCPh], 1
[(p3-Ppy3)(CO)2WꢀCPh]BPh4, 2
315 (4.19)
342 (4.01)
420 (3.74)
339 (4.11)
488sh (2.95)
350 (3.69)
496 (3.26)
336 (3.87)
488 (3.17)
336 (2.53)b
472 (2.94)
633 (0.25)
626 (0.21)
614 (0.11)
669 (0.009)
23
33
20
11
[(p3-HCpy3)(CO)2WꢀCPh]BPh4, 3
[(p3-Ppy3)(CO)2MoꢀCPh]BPh4, 4
[{p3-CH3C(CH2PPh2)3}(CO)2WꢀCPh]PF6, 5
[(TTCN)(CO)2WꢀCPh]PF6, 6
a In CH3CN unless otherwise stated.
b In CH2Cl2.
comparable since the electronic effect of the py2, p2-
Ppy3 and bpy ligands on the WꢀC moiety should be
similar. However, replacement of the chloride in 1 by a
pyridyl group leads to a downfield shift for the carbyne
carbon in 2 (286.3 cf. 266.3 ppm for 1). Corresponding
The UV-visible absorption and emission data for the
carbyne complexes are summarized in Table 2. Com-
plexes 2–6 exhibit intense absorption bands at 320–340
nm and weak absorptions in the 400–500 nm region.
The large extinction coefficients observed for the high
energy bands suggest that they originate from charge
transfer transitions which are presumably MLCT [10].
With reference to previous studies [10–12], the low
energy absorptions at u\400 nm with low mmax are
assigned to dxy“dy* transition (where dy* is comprised
of dxz, dyz and y* of the phenylcarbyne moiety). Excita-
tion of the complexes 2–5 at 330 nm in
dichloromethane give intense orange to red emissions.
The large difference between the energies of the emis-
sion and lowest allowed absorption plus the relatively
long emission lifetimes suggest that the transitions in-
volved are spin-forbidden processes [12]. The emissive
w(CO), l(C6 Ph) and l(CO) values were found for 2 and
3; HCpy3 and Ppy3 are both |-donors and y-acceptors
and evidently exhibit similar chelating properties.
Changing from tungsten in 2 to molybdenum in 4
causes downfield 13C l(C
6 Ph) and l(CO) shifts plus
higher IR w(CO) values. This can be rationalized by the
higher electron density of the third row transition metal
which leads to greater metal–carbonyl y-back bonding.
Complexes 5 and 6 bearing P and S donor atoms
respectively, display more downfield l(C6 Ph) signals and
higher w(CO) values than derivatives with nitrogen-
donor ligands. Hence CH3C(CH2PPh2)3 and TTCN
appear to be weaker |-donors and/or better y-accep-
tors than HCpy3 and Ppy3.
3
state is likely to be [(dxy)1(dy*)1].
Complexes 1, 2, 3 and 5 have been characterized by
X-ray diffraction methods in order to probe the antici-

194
F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
Fig. 1. Perspective view of [Cl(p2-Ppy3)(CO)2WꢀCPh] (40% probability ellipsoids).
Fig. 2. Perspective view of [(p3-Ppy3)(CO)2WꢀCPh]+ (40% probability ellipsoids).
pated changes in structural parameters imposed by
different donor atoms and ligands. The perspective
views of the cations in 1, 2, 3 and 5 with atomic
numbering schemes are shown in Figs. 1–4 while crys-
tal data and selected bond lengths and angles are listed
in Tables 3–7, respectively. The W(1)–C(3) distances
and W(1)–C(3)–C(4) angles in complexes 1, 2, 3 and 5
are comparable to related derivatives (Table 8) and fall
within the range previously observed for tungsten–car-
bon triple bonds [3]. The structure of 1 consists of one
diethyl ether molecule for two complex molecules. The
Ppy3 ligand coordinates to the metal atom via only two

F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
195
Fig. 3. Perspective view of [(p3-HCpy3)(CO)2WꢀCPh]+ (50% probability ellipsoids).
Fig. 4. Perspective view of [{CH3C(CH2PPh2)3}(CO)2WꢀCPh]+ (40% probability ellipsoids).
pyridyl nitrogen atoms. The crystal structures of 2 and
3 both consist of one ethanol molecule per complex
cation. The W atoms are in distorted octahedral envi-
ronments and are bonded to two carbonyl groups, one
phenylcarbyne moiety and three Ppy3 or HCpy3 nitro-
gen atoms, respectively. The W(1)–N(3) bond distances
in 2 and 3 are significantly longer than the W(1)–N(1)
and W(1)–N(2) contacts, and this is attributed to the

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F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
Table 3
Crystal data for 1·0.5Et2O, 2·EtOH, 3·EtOH and 5
1·0.5Et2O
2·EtOH
3·EtOH
5
Formula
Mr
C26H22ClN3O2.5PW
666.76
C50H43BN3O3PW
959.54
C51H44BN3O3W
941.59
C50H44F6O2P4W
1098.63
Crystal system
Space group
Triclinic
Triclinic
Triclinic
Monoclinic
P21/c (No. 14)
12.39 6(4)
13.60 9(3)
27.62 0(4)
(
(
(
P1 (No. 2)
P1 (No. 2)
P1 (No. 2)
˚
a (A)
12.188(3)
12.532(3)
10.255(3)
109.19(2)
111.90(2)
101.80(2)
1273.2(7)
2
13.256(2)
14.450(3)
12.863(1)
102.50(1)
102.09(1)
101.91(3)
2268.9(7)
2
14.170(9)
14.304(2)
11.638(1)
107.62(1)
94.41(2)
83.83(3)
2232(1)
2
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
91.86(2)
3
˚
V (A )
4656(1)
4
1.567
26.84
2192
Z
Dc (g cm−3
)
1.666
47.40
650
1.404
26.27
964
1.401
26.34
948
v (Mo–Kh) (cm−1
F(000)
)
No. of parameters refined
298
532
532
604
R, wR
0.029, 0.037
0.032, 0.044
0.065, 0.078
0.031, 0.037
stronger trans influence exerted by the carbyne moiety
compared to CO. The W–C(carbyne) distance in 2
group.
The
crystal
structures
[13]
of
and
[trans-
[trans-
(Ph3P)(CO)4CrꢀCNEt2]BF4
˚
(1.811(7) A) is slightly shorter than that in 3 (1.835(8)
(Me3P)(CO)4CrꢀCMe]BCl4 [14] have been reported.
The highly flexible tripodal ligand CH3C(CH2PPh2)3
allows optimum orientation of the phosphine sub-
stituents and phenyl rings such that repulsion between
CPh and the three PPh2 groups is minimized. The W–P
bond trans to CPh is significantly longer than the
remaining cis-(W–P) bonds as expected. These W–P
contacts are similar to those in Cl(CO)2(dppf)WꢀCPh
(2.583(2) and 2.585(2) A; dppf=1,1’-bis(diphenylphos-
phino)ferrocene)
(PPh2)2}WꢀCC6H4Me-4 (2.512(1) and 2.528(2) A) [16],
hence the cationic charge on complex 5 does not appear
to have a significant impact on the W–P interaction.
˚
A), while correspondingly, the trans W(1)–N(3) contact
˚
in 2 (2.326(5) A) is marginally longer than that in 3
˚
(2.278(9) A). However, the two remaining W–
N(pyridyl) distances are similar in 2 and 3. This is in
accordance with the observation by Mayr that changes
in the interaction along the X–WꢀCPh axis does not
significantly affect the bonding parameters between the
metal and the four ligands perpendicular to the X–
WꢀCPh axis [3b].
The octahedral geometry around the tungsten atom
in 5 is highly distorted. Complex 5 is a rare example of
a structurally characterized group 6 cationic complex
containing a phosphine donor atom trans to a carbyne
˚
[15]
and
trans-Br(CO)2{o-Ph-
˚
Table 4
Table 5
˚
˚
Selected bond lengths (A) and angles (°) for 1·0.5Et2O
Selected bond lengths (A) and angles (°) for 2·EtOH
W(1)–Cl(1)
W(1)–N(1)
W(1)–N(2)
W(1)–C(1)
W(1)–C(2)
W(1)–C(3)
2.542(2)
2.254(5)
2.255(5)
1.993(8)
1.988(8)
1.806(6)
W(1)–N(1)
W(1)–N(3)
W(1)–C(2)
P(1)–C(14)
P(1)–C(20)
2.237(5) W(1)–N(2)
2.326(5) W(1)–C(1)
1.974(7) W(1)–C(3)
1.838(6) P(1)–C(15)
1.835(7)
2.231(5)
1.989(8)
1.811(7)
1.829(7)
N(1)–W(1)–N(2)
N(1)–W(1)–C(1)
N(1)–W(1)–C(3)
N(2)–W(1)–C(1)
N(2)–W(1)–C(3)
N(3)–W(1)–C(2)
C(1)–W(1)–C(2)
C(2)–W(1)–C(3)
83.0(2)
173.1(2)
101.6(2)
93.1(2)
103.3(2)
87.1(2)
87.8(3)
82.5(3)
N(1)–W(1)–N(3)
85.2(2)
95.6(2)
87.2(2)
174.2(2)
89.0(2)
168.1(2)
84.7(3)
168.3(5)
Cl(1)–W(1)–N(1)
Cl(1)–W(1)–C(1)
Cl(1)–W(1)–C(3)
N(1)–W(1)–C(1)
N(1)–W(1)–C(3)
N(2)–W(1)–C(2)
C(1)–W(1)–C(2)
C(2)–W(1)–C(3)
86.6(1)
91.1(2)
Cl(1)–W(1)–N(2)
Cl(1)–W(1)–C(2)
N(1)–W(1)–N(2)
N(1)–W(1)–C(2)
N(2)–W(1)–C(1)
N(2)–W(1)–C(3)
C(1)–W(1)–C(3)
W(1)–C(3)–C(4)
86.1(1)
89.3(2)
82.5(2)
95.7(2)
95.0(3)
99.1(2)
82.3(3)
167.5(5)
N(1)–W(1)–C(2)
N(2)–W(1)–N(3)
N(2)–W(1)–C(2)
N(3)–W(1)–C(1)
N(3)–W(1)–C(3)
C(1)–W(1)–C(3)
W(1)–C(3)–C(4)
171.9(2)
176.7(2)
100.1(2)
175.1(2)
86.6(3)
85.7(3)
W(1)–N(1)–C(10) 118.7(4)
W(1)–N(2)–C(15) 123.0(4)
W(1)–N(3)–C(20) 122.0(4)
W(1)–N(1)–C(14) 124.4(4)
W(1)–N(2)–C(19) 119.1(4)
W(1)–N(3)–C(24) 120.0(5)
W(1)–N(1)–C(10) 119.1(4)
W(1)–N(2)–C(19) 118.8(4)
W(1)–N(1)–C(14) 122.3(4)
W(1)–N(2)–C(15) 122.0(4)
W(1)–C(1)–O(1)
174.5(7)
W(1)–C(2)–O(2)
177.3(6)
W(1)–C(1)–O(1)
179.0(7)
W(1)–C(2)–O(2)
177.1(6)

F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
197
were referenced to tetramethylsilane (1H and 13C) and
85% H3PO4 (31P). Expected coupling constants are
omitted. Assignments for 13C-NMR data were made
with reference to related compounds [7]. FAB Mass
spectra were obtained from a Finnigan Mat 95 mass
spectrometer. UV/VIS absorption spectra were mea-
sured on a Perkin Elmer Lambda 19 UV/VIS/NIR
spectrometer. Steady-state emission spectra were
recorded on a SPEX 1681 FLUOROLOG-2 series
F111AI spectrometer. The emission lifetimes were de-
termined and flash-photolysis measurements were per-
formed with a Quanta Ray DCR-3 pulsed Nd-YAG
laser system (pulse output 355 nm, 8 ns). The emission
signals were detected by a Hamamatsu R928 photomul-
tiplier tube and recorded on a Tektronix model 2430
digital oscilloscope.
Table 6
Selected bond lengths (A) and angles (°) for 3·EtOH
˚
W(1)–N(1)
W(1)–N(3)
W(1)–C(2)
C(14)–C(15)
C(15)–C(21)
2.227(9) W(1)–N(2)
2.278(9) W(1)–C(1)
2.229(9)
2.02(1)
1.835(8)
1.53(2)
2.00(1)
1.53(2)
1.53(2)
W(1)–C(3)
C(15)–C(16)
N(1)–W(1)–N(2)
N(1)–W(1)–C(1)
N(1)–W(1)–C(3)
N(2)–W(1)–C(1)
N(2)–W(1)–C(3)
N(3)–W(1)–C(2)
C(1)–W(1)–C(2)
C(2)–W(1)–C(3)
80.9(4)
171.8(4)
105.9(5)
94.6(4)
101.2(5)
91.8(5)
87.2(5)
86.7(6)
N(1)–W(1)–N(3)
N(1)–W(1)–C(2)
N(2)–W(1)–N(3)
N(2)–W(1)–C(2)
N(3)–W(1)–C(1)
N(3)–W(1)–C(3)
C(1)–W(1)–C(3)
W(1)–C(3)–C(4)
80.8(4)
96.3(5)
80.3(4)
172.0(5)
91.8(4)
173.3(4)
81.6(5)
174(1)
W(1)–N(1)–C(10) 121.2(8)
W(1)–N(2)–C(16) 122.6(8)
W(1)–N(3)–C(21) 122.2(7)
W(1)–N(1)–C(14) 122.0(8)
W(1)–N(2)–C(20) 120.6(9)
W(1)–N(3)–C(25) 123.2(8)
W(1)–C(1)–O(1)
178(1)
W(1)–C(2)–O(2)
175(1)
3.2. Cl(p2-Ppy3)(CO)2WꢀCPh (1)
3. Experimental details
A solution of Ppy3 (0.11 g, 0.40 mmol) and
Clpy2(CO)2WꢀCPh (0.21 g, 0.40 mmol) in THF (8 ml)
was stirred at 50°C for 6 h. The orange solution turned
cloudy with subsequent formation of a yellow precipi-
tate, which was collected upon cooling and washed with
cold THF (1 ml) to remove trace amounts of pyridine.
The product was recrystallized by diffusion of diethyl
ether into an ethanol solution to afford yellow crystals.
Yield: 90% (0.23 g). FAB-MS: m/z 594 (M+ –Cl).
1H-NMR (CD3CN): l 9.36 (d, 2H, H6-py); 8.89 (d, 1H,
H6’-py); 8.10, 8.01 (m, 3H, H3,3’-py); 7.75 (m, 2H,
3.1. General procedures
All operations were carried out using standard
Schlenk techniques under an atmosphere of argon.
Details for purification of solvents have been given
elsewhere [4]. Cl(CO)2py2MꢀCPh (M=Mo, W) were
prepared as described for the bromo analogue [7] ex-
cept oxalyl chloride was used. Water was doubly dis-
tilled over potassium permanganate. HCpy3 and Ppy3
were prepared by literature methods [9]. TTCN and
CH3C(CH2PPh2)3 were purchased from Aldrich.
H5-py); 7.60 (m, 1H, H5’-py); 7.45–7.26 (m, 8H, H4,4’
-
py and CPh). 13C{1H}-NMR (CD3CN): l 266.3,
(WꢀC); 223.2 (CO), 158.9, 157.7 (C6,6’-py); 153.6 (br,
C2,2’-py); 150.4 (ipso-CPh); 143.1, 142.2 (d, C3,3’-py,
Elementary analyses were performed by the Butter-
worth Laboratory, UK. IR spectra were recorded on a
BIO-RAD FTS-7 FTIR spectrophotometer. H-, 13C-
1
J
C–P=17.2 Hz); 130.4, 130.3, 129.6 (o,m,p-CPh); 128.6,
128.1 (C5,5’-py); 126.9, 124.6 (C4,4’-py). 31P{1H}-NMR
(CD3CN): l 5.2. IR (KBr, cm−1): 1980s, 1885s w(CO).
UV-VIS umax, nm (log mmax) in CH3CN: 315 (4.19).
Anal. Calcd. for C24H17ClN3O2PW: C, 45.75; H, 2.70;
N, 9.37. Found: C, 45.81; H, 2.77; N, 9.32%.
and 31P-NMR spectra were recorded on Bruker
SPX300 or SPX500 Spectrometers. Chemical shifts
Table 7
˚
Selected bond lengths (A) and angles (°) for 5
W(1)–P(1)
W(1)–P(3)
W(1)–C(2)
2.568(1) W(1)–P(2)
2.646(1) W(1)–C(1)
2.009(5) W(1)–C(3)
2.550(1)
2.027(6)
1.836(5)
3.3. [(p3-Ppy3)(CO)2WꢀCPh]BPh4 (2)
NaBPh4 (0.22 g, 0.64 mmol) was added to Cl(p2-
Ppy3)(CO)2WꢀCPh (0.40 g, 0.64 mmol) in CH3CN (10
ml) and the mixture was stirred at 50°C for 2 h to yield
a bright orange solution and white precipitate. After
cooling to ambient temperature, the solution was
filtered and all volatile components were removed in
vacuo. The solid residue was extracted with acetone
and the filtrate was evaporated to dryness. Red crystals
were obtained by diffusion of diethyl ether into an
ethanol solution. Yield: 86% (0.50 g). FAB-MS: m/z
P(1)–W(1)–P(2)
P(1)–W(1)–C(1)
P(1)–W(1)–C(3)
P(2)–W(1)–C(1)
P(2)–W(1)–C(3)
P(3)–W(1)–C(2)
C(1)–W(1)–C(2)
C(2)–W(1)–C(3)
W(1)–P(1)–C(12) 114.6(1)
W(1)–P(1)–C(21) 112.1(1)
W(1)–P(2)–C(27) 117.1(2)
W(1)–P(3)–C(14) 111.6(2)
W(1)–P(3)–C(45) 110.2(2)
82.57(4)
172.6(1)
96.9(1)
91.6(2)
104.6(1)
87.9(1)
86.1(2)
82.3(2)
P(1)–W(1)–P(3)
80.62(4)
99.1(1)
85.28(4)
172.6(1)
94.5(1)
169.5(1)
88.9(2)
171.4(4)
P(1)–W(1)–C(2)
P(2)–W(1)–P(3)
P(2)–W(1)–C(2)
P(3)–W(1)–C(1)
P(3)–W(1)–C(3)
C(1)–W(1)–C(3)
W(1)–C(3)–C(4)
W(1)–P(1)–C(15) 119.3(2)
W(1)–P(2)–C(13) 115.1(2)
W(1)–P(2)–C(33) 113.8(2)
W(1)–P(3)–C(39) 121.9(2)
594 ((Ppy3)(CO)2WꢀCPh)+; 538 ((Ppy3)WꢀCPh)+. H-
NMR (CDCl3): l 9.67 (dd, 2H, H6-py); 9.17 (d, 1H,
1
W(1)–C(1)–O(1)
176.0(5)
W(1)–C(2)–O(2)
173.1(4)
H6’-py); 8.39 (m, 3H, H3,3’-py); 8.10 (m, 2H, H5-py);

198
F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
Table 8
Selected structural parameters of related Group 6 carbyne complexes
˚
˚
Compounds
M–(carbyne), A
M–X, A (trans to carbyne)
Carbyne angle, °
Reference
[(Me3TACN)(CO)2MoꢀCPh]BPh4
[(Me3TACN)(CO)2WꢀCPh]BPh4
[{p3-B(pz)4}(CO)2WꢀCC6H4Me-4]
[Cl(p2-Ppy3)(CO)2WꢀCPh], 1
1.797(6)
1.800(6)
1.821(7)
1.806(6)
1.811(7)
1.835(8)
1.836(5)
N:2.351(4)
N:2.316(5)
N:2.284(6)
Cl:2.542(2)
N:2.326(5)
N:2.278(9)
P:2.646(1)
174.7(5)
174.4(4)
164.0(6)
167.5(5)
168.3(5)
174(1)
[4]
[4]
[20]
[(p3-Ppy3)(CO)2WꢀCPh]BPh4, 2
[(p3-HCpy3)(CO)2WꢀCPh]BPh4, 3
[{p3-CH3C(CH2PPh2)3}(CO)2-WꢀCPh]PF6, 5
171.4(4)
8.00 (m, 1H, H5’-py); 7.60–7.45 (m, 8H, H4,4’-py and
CPh); 7.26, 6.99, 6.89 (m, 20H, BPh). 13C{1H}-NMR
(CD3CN): l 286.3 (WꢀC); 221.1 (CO); 158.9, 157.8
(C6,6’-py); 152.9, 152.4 (d, C2,2’-py, JC–P=18.1 Hz);
149.6 (ipso-CPh); 143.0, 142.2 (d, C3,3’-py, JC–P=17.3
Hz); 136.7 (B-Ph); 130.7 (o-CPh); 130.5 (m-CPh); 129.6
(p-CPh); 128.8, 128.1 (C5,5’-py); 126.6 (br, B-Ph and
C4,4’-py); 122.8 (B-Ph). 31P{1H}-NMR (CD3CN): l 7.1.
Calcd. for C49H38BN3O2W: C, 65.70; H, 4.24; N, 4.69.
Found: C, 65.77; H, 4.30; N, 4.60%.
3.5. [(p3-Ppy3)(CO)2MoꢀCPh]BPh4 (4)
Ppy3 (0.12 g, 0.46 mmol) was dissolved in THF (10
ml) at ambient temperature and Cl(CO)2py2MoꢀCPh
(0.2 g, 0.46 mmol) was added. The resulting orange red
solution was stirred at 50°C for 6 h with subsequent
formation of a yellow precipitate. The product was
filtered after cooling, washed with THF (2ml) and
diethyl ether (10 ml×2) and dried in vacuo. Acetoni-
trile (10 ml) was added to dissolve the solid and
NaBPh4 (0.157 g, 0.46 mmol) was added. The cloudy
solution was stirred at 55°C for 2 h. After cooling to
ambient temperature, the bright orange-yellow solution
was filtered and evaporated to dryness in vacuo. The
residue was washed with diethyl ether (10 ml×3) and
recrystallized by diffusion of diethyl ether into an
ethanol solution to give a bright yellow microcrystalline
solid. Yield: 60% (0.23 g). FAB-MS: m/z 508
IR (KBr, cm−1): 1984s, 1899vs w(CO). UV-VIS umax
,
nm (log mmax) in CH3CN: 274 (4.46); 342 (4.01); 420
(3.74). Anal. Calcd. for C48H37BN3O2PW: C, 63.09; H,
4.05; N, 4.60. Found: C, 63.15; H, 4.18; N, 4.48%.
3.4. [(p3-HCpy3)(CO)2WꢀCPh]BPh4 (3)
HCpy3 (0.094 g, 0.38 mmol) was added to a solution
of Clpy2(CO)2WꢀCPh (0.20 g, 0.38 mmol) in THF (10
ml) at ambient temperature. The clear solution was
stirred at 50°C for 6 h to afford a yellow precipitate,
which was collected upon cooling and washed with
THF (1 ml) and diethyl ether (10 ml×3). The yellow
solid was dissolved in acetonitrile (8 ml) and NaBPh4
(0.13 g, 0.38 mmol) was added. The resulting mixture
was heated at 45°C for 3 h to give an orange red
solution with white precipitate. The solution was cooled
to ambient temperature and filtered. All volatile com-
ponents were removed in vacuo to give an orange
crystalline solid which was washed with diethyl ether
and air dried. The product can be recrystallized from
ethanol/diethyl ether to give red crystals. Yield: 86%
(0.29 g). FAB-MS: m/z 576 ((HCpy3)(CO)2WꢀCPh)+.
1H-NMR (CD3CN): l 9.55 (d, 2H, H6-py); 9.05 (d, 1H,
H6’-py); 8.38 (m, 2H, H3-py); 8.36 (m, 1H, H3’-py); 8.30
(d, 2H, H5-py); 8.27 (d, 1H, H5’-py); 7.70–7.42 (m, 8H,
1
((Ppy3)(CO)2MoꢀCPh)+. H-NMR (CDCl3): l 9.54 (d,
2H, H6-py); 9.05 (d, 1H, H6’-py); 8.31 (m, 3H, H3,3’-py);
8.07–7.85 (m, 3H, H5,5’-py); 7.57–7.41 (m, 8H, H4,4’-py,
CPh); 7.27, 6.99, 6.83 (m, 20H, BPh). 13C{1H}-NMR
(CD3CN): l 297.2 (MoꢀC); 223.1 (CO); 158.0, 156.4
(C6,6’-py); 153.4, 151.3 (d, C2,2’-py, JC–P=18.2 Hz);
148.7 (ipso-CPh); 141.5, 141.0 (d, C3,3’-py, JC–P=17.4
Hz); 136.7 (B-Ph); 131.2 (o-CPh); 130.1 (m-CPh); 129.5
(p-CPh); 128.0, 127.2 (C5,5’-py); 126.7, 125.7 (C4,4’-py);
126.6, 122.8 (B-Ph). 31P{1H}-NMR (CDCl3): l 9.89.
IR(KBr, cm−1): 1998, 1918 w(CO). UV-VIS umax, nm
(log mmax) in CH3CN: 252 (4.39); 350 (3.69); 496 (3.26).
Anal. Calcd. for C48H37BMoN3O2P: C, 69.82; H, 4.48;
N, 5.09. Found: C, 69.90; H, 4.50; N, 5.01%.
H4,4’-py, CPh), 7.26 (m, 8H, BPh), 7.05 (s, 1H, H6 Cpy3),
6.99, 6.89 (m, 12H, BPh). 13C{1H}-NMR (CD3CN): l
288.1 (WꢀCPh, J(183W–C)=192 Hz); 222.0 (CO,
J(183W–C)=170 Hz); 156.7, 155.3 (C6,6’-py); 154.1,
3.6. [{CH3C(CH2PPh2)3}(CO)2WꢀCPh]PF6 (5)
153.9 (C2,2’-py); 150.1 (ipso-CPh); 144.1, 143.4 (C3,3’
-
A mixture of Cl(CO)2py2WꢀCPh (0.20 g, 0.38 mmol),
CH3C(CH2PPh2)3 (0.24 g, 0.38 mmol) and AgPF6
(0.097 g, 0.39 mmol) in CH3CN (10 ml) was stirred at
50°C for 18 h to give a brown solution and white
precipitate. After filtration, the solvent was removed in
vacuo. The residue was washed with diethyl ether (20
py), 136.7 (B-Ph), 130.4 (o-CPh), 130.3 (m-CPh); 129.5
(p-CPh); 128.2, 127.6 (C5,5’-py); 126.6 (B-Ph), 126.4,
125.9 (C4,4’-py); 122.8 (B-Ph), 61.7 (HCpy3). IR(KBr,
cm−1): 1988s, 1894s w(CO). UV-VIS umax, nm (log mmax
)
in CH3CN: 267 (4.46), 339 (4.11) 488sh (2.95). Anal.

F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
199
ml×2), extracted with acetonitrile and recrystallized by
diffusion of diethyl ether into an acetonitrile solution to
yield large orange–yellow crystals. Yield: 80% (0.33 g).
Crystal data of 3. {[WO2N3C25H18]B(C6H5)4 ·EtOH};
yellow crystal, dimensions 0.30×0.20×0.30 mm; for-
(
mula weight=941.59, triclinic, space group P1 (No. 2),
˚
FAB-MS:
m/z
953
({CH3C(CH2PPh2)3}
a=14.170(9), b=14.304(2), c=11.638(1) A, h=
3
W(CO)2(ꢀCPh))+. 1H-NMR (CD3CN): l 7.67 (m, 35H,
aromatic H); 2.87–2.63 (m, 6H, CH2); 1.72 (s, 3H,
CH3). 13C {1H}-NMR (CD3CN): l 294.8 (m, WꢀC);
211.6 (m, CO); 149.8 (br, ipso-PPh); 149.7 (ipso-CPh);
˚
107.62(1), i=94.41(2), k=83.83(3)°, V=2232(1) A ,
Z=2, Dc=1.401 g cm−3, v (Mo–Kh)=26.34 cm−1
F(000)=948, T=301 K.
,
Crystal data collection was made at 28°C on a
Rigaku AFC7R diffractometer with graphite
133.3–129.6 (aromatic C); 39.1 (m, C
CH3C); 33.5 (m, C
H3). 31P {1H}-NMR (CD3CN): l
1.53 (JP–W=216 Hz), 1.43 (JP–W=216 Hz). IR (KBr,
cm−1): 1999s, 1934s w(CO). UV-VIS umax, nm (log mmax
6 H2); 34.6 (m,
˚
monochromatized Mo–Kh radiation (u=0.71073 A)
6
6
using ꢀ−2q scans. Intensity data (in the range
2qmax=46 (1); 50 (2); 50° (3)) were corrected for decay
and for Lorentz and polarization effects, and empirical
absorption corrections were based on the „-scan of five
(four for complex 1) strong reflections. The numbers of
unique reflections measured: 1, 3544; 2, 7976; 3, 6018;
and the numbers of observed reflections with I\3| (I):
1, 3039; 2, 6588; 3, 4699; were used in the structural
analyses. The space group was determined based on a
statistical analysis of intensity distribution and the suc-
cessful refinement of the structure solved by direct
methods (SIR92 [17]), expanded by Fourier method
and refined by full-matrix least-squares using the soft-
ware package TeXsan [18] on a Silicon Graphics Indy
computer. For 1, 2 and 3, one formula unit constitutes
a crystallographic asymmetric unit.
In the least-squares refinement of 1, all 32 non-H
atoms were refined anisotropically, atoms of the diethyl
ether were refined isotropically and 22 H atoms at
calculated positions with thermal parameters equal to
1.3 times that of the attached C atoms were not refined.
Convergence for 298 variable parameters by least-
squares refinement on F with w=4 F2o/|2 (Fo2), where
|2 (Fo2)=[|2(I)+(0.035 F2o)2] was reached at R=0.029
and wR=0.037 with a goodness-of-fit of 1.16. The final
)
in CH3CN: 260 (4.40), 336 (3.87), 488 (3.17). Anal.
Calcd. for C50H44F6O2P4W: C, 54.64; H, 4.01. Found:
C, 54.71; H, 4.11%.
3.7. [(TTCN)(CO)2WꢀCPh]PF6 (6)
A mixture of Cl(CO)2py2WꢀCPh (0.20 g, 0.38 mmol),
TTCN (0.068 g, 0.38 mmol) and AgPF6 (0.097 g, 0.39
mmol) in acetonitrile (15 ml) was refluxed for 12 h.
After cooling, the orange yellow solution was filtered
and evaporated to dryness in vacuo. The residue was
washed with diethyl ether and recrystallized by diffu-
sion of diethyl ether into an acetonitrile solution to
afford a yellow microcrystalline solid. Yield: 76% (0.19
g). FAB-MS: m/z 509 ((TTCN)W(CO)2(ꢀCPh))+; 453,
((TTCN)WꢀCPh)+. 1H-NMR (CH3CN): l 7.41 (m,
5H, Ph); 3.58 (m, 4H, CH2); 3.38 (m, 4H, CH2); 3.26
(m, 4H, CH
(WꢀC); 214.0 (CO); 149.5 (ipso-Ph); 131.3 (o-Ph); 130.3
(m-Ph); 129.3 (p-Ph); 37.6, 35.5, 33.8 (CH2). IR(KBr,
cm−1): 2007s, 1925s w(CO). UV-VIS umax, nm (log mmax
6
2). 13C{1H}-NMR (CH3CN): l 293.1
6
)
in CH2Cl2: 250 (4.21), 336 (2.53), 472 (2.94). Anal.
Calcd. for C15H17F6PO2S3W: C, 27.52; H, 2.60. Found:
C, 27.70; H, 2.68%.
difference Fourier map was featureless, with maximum
−3
˚
positive and negative peaks of 1.08 and 0.67 e A
,
respectively.
For 2, the hydroxyl H atom in the solvent molecule
was not found. In the least-squares refinement, all 59
non-H atoms were refined anisotropically and 42 H
atoms at calculated positions were not refined. Conver-
gence for 532 variable parameters by least-squares
refinement on F with w=4 F2o/|2 (Fo2), where |2 (F2o)=
[|2(I)+(0.013 F2o)2] was reached at R=0.032 and
wR=0.044 with a goodness-of-fit of 2.37. The final
difference Fourier map was featureless, with maximum
3.8. Structural determination of 1 ·0.5Et2O, 2 ·EtOH
and 3 ·EtOH
Crystal data of 1. {[WClPO2N3C24H17]·0.5Et2O}, or-
ange crystal, dimensions: 0.20×0.15×0.25 mm, for-
(
mula weight=666.76, triclinic, space group P1 (No. 2),
˚
a=12.188(3), b=12.532(3), c=10.255(3) A, h=
109.19(2), i=111.90(2), k=101.80(2)°, V=1273.2(7)
3
A , Z=2, Dc=1.666 g cm−3, v (Mo–Kh)=47.40
−3
˚
˚
positive and negative peaks of 0.95 and 0.58 e A
respectively.
,
cm−1, F(000)=650, T=301 K.
Crystal
data
of
2.
{[WPO2N3C24H17]B(C6-
For 3, the H atom of the ethanol solvent molecule
was not found. In the least-squares refinement, all 59
non-H atoms were refined anisotropically and 43 H
atoms at calculated positions were not refined. Conver-
gence for 532 variable parameters by least-squares
refinement on F with w=4 F2o/|2 (Fo2), where |2 (F2o)=
[|2(I)+(0.033 F2o)2] was reached at R=0.065 and
H5)4 ·EtOH}; red crystal, dimensions: 0.20×0.20×
0.30 mm; formula weight=959.54, triclinic, space
group P1 (No. 2), a=13.256(2), b=14.450(3), c=
(
˚
12.863(1) A, h=102.50(1), i=102.09(1), k=
3
−3
˚
101.91(3)°, V=2268.9(7) A , Z=2, Dc=1.404 g cm
,
v (Mo–Kh)=26.27 cm−1, F(000)=964, T=301 K.

200
F.-W. Lee et al. / Journal of Organometallic Chemistry 563 (1998) 191–200
Acknowledgements
wR=0.078 with a goodness-of-fit of 2.94. The final
difference Fourier map was featureless, with maxi-
mum positive and negative peaks of 2.10 and 1.99
We thank The University of Hong Kong and the Hong
Kong Research Grants Council for financial support. M.
C.-W. C. is grateful for a University Postdoctoral Fellow-
ship from the University of Hong Kong.
e A−3, respectively.
˚
3.9. Structural determination of 5
Crystal
data.
{[WP3O2C50H44]PF6};
formula
References
weight=1098.63, monoclinic, space group P21/c (No.
14), a=12.396(4) A, b=13.609(3) A, c=27.620(4) A,
i=91.86(2)°, V=4656(1) A , Z=4, Dc=1.567
˚
˚
˚
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Herdtweck, Angew. Chem. Int. Ed. Engl. 34 (1995) 924. (b) A.C.
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(1998) 1946.
3
˚
g cm−3, v (Mo–Kh)=26.84 cm−1, F(000)=2192,
T=301 K. An orange crystal of dimensions 0.15×
0.10×0.40 mm mounted on a glass fibre was used
for data collection at 28°C on a Nonius-Enraf CAD4
diffractometer with graphite monochromatized Mo–
˚
Kh radiation (u=0.71073 A) using ꢀ−2q scans. In-
tensity data (in the range 2qmax=48°) were corrected
for decay and for Lorentz and polarization effects,
and empirical absorption corrections were based on
the „-scan of four strong reflections. 7096 unique
reflections were measured, 5425 reflections of which
with I\3|(I) were considered observed and used in
the structural analysis. The structure was solved by
Patterson and Fourier methods (PATTY [19]) and
refinement by full-matrix least squares using the soft-
ware package TeXsan [18] on a Silicon Graphics Indy
computer. The PF6− anion was disordered, with the F
atoms placed at ten positions, having occupation
numbers 1.0, 1.0, 0.65, 0.65, 0.65, 0.75, 0.25, 0.35,
0.35, 0.35, respectively. All non-H atoms were refined
anisotropically and 44 H atoms of the complex cation
at calculated positions with thermal parameters equal
to 1.3 times that of the attached C atoms were not
refined. Convergence for 604 variables by least-
squares refinement on F with w=4F2o/|2 (Fo2), where
|2(Fo2)=[|2(I)+(0.033 F2o)2] was reached at R=
0.031 and wR=0.037 with a goodness-of-fit of 2.23.
The final difference Fourier map was featureless, with
maximum positive and negative peaks of 0.94 and
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1.09 e A−3, respectively.
˚
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4. Supplementary material
Listings of crystal data and refinement, atomic co-
ordinates, calculated coordinates, anisotropic displace-
ment parameters, bond lengths and angles and
structure factors for 1·0.5Et2O, 2·EtOH, 3·EtOH
and 5 are available as Supplementary Material from
the authors.
[19] PATTY: P.T. Beurskens, G. Admiraal, G. Beurskens, W.P.
Bosman, S. Garcia-Granda, R.O. Gould, J.M.M. Smits, C.
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.