Syntheses and chemistry of the diynyl complexes M(C≡CC≡CH)(CO)3(η-C5H5) (M = Mo, W): Crystal structures of W(C≡CC≡CSiMe3)(CO)3(η-C5H 5), W{C≡CC[CH=C(CN)2]=C(CN)2}(CO) 3(η-C5H5)

Article abstract of DOI:10.1021/om980031r

Reactions of buta-1,3-diyne with appropriate metal halides, carried out in the presence of CuI in NHEt₂, have given high yields of M(C≡CC≡CH)(CO)_nCp [M = W (1-W), Mo (1-Mo), n = 3; M = Fe, n = 2 (2)]. Complex 1-W was metalated with LiNPrⁱ₂; subsequent reactions with SiClMe₃ or PClPh₂ gave W(C≡CC≡CR)(CO)₃Cp [R = SiMe₃ (3) or P(O)Ph₂ (4)] in modest to high yield. Coupling of 1 with iodoarenes, catalyzed by a mixed Cu^I-Pd⁰ catalyst, gave M(C≡CC≡CAr) (CO)₃Cp [M = W, Ar = Ph (5-W), tol (6), C₆H₄OMe-4 (7), C₆H₄CO₂Me-4 (8); M = Mo, Ar = Ph (5-Mo)]. Oxidative coupling of 1 (CuCl-tmed-O₂) gave {M(CO)₃Cp}₂(μ-C₈) [M = W (9-W), Mo (9-Mo)]. Addition of tetracyanoethene to 1-W occurred at the C≡C triple bond further from the metal atom, to give W{C≡CC[=C(CN)₂]CH=C(CN)₂}(CO)3Cp (10). Substitution of CO by PPh₃ was difficult, but the Me₃NO-induced reaction with 5-W afforded cis-W(C≡CC≡CPh)(CO)₂(PPh₃)Cp (11) in low yield. The X-ray crystal structures of 3 and 10, together with that of cis-W(C≡CPh)(CO)₂(PPh₃)Cp (12), are reported.

Full text of DOI:10.1021/om980031r

Organometallics 1998, 17, 3539-3549
3539
Syn th eses a n d Ch em istr y of th e Diyn yl Com p lexes
M(CtCCtCH)(CO)3(η-C5H5) (M ) Mo, W): Cr ysta l
Str u ctu r es of W(CtCCtCSiMe3)(CO)3(η-C5H5),
W{CtCC[CH)C(CN)2])C(CN)2}(CO)3(η-C5H5), a n d
cis-W(CtCP h )(CO)2(P P h 3)(η-C5H5)
Michael I. Bruce,*,† Mingzhe Ke,† Paul J . Low,† Brian W. Skelton,‡ and
Allan H. White‡
Department of Chemistry, The University of Adelaide, Adelaide, SA 5005, Australia, and
Department of Chemistry, The University of Western Australia, Nedlands, WA 6907, Australia
Received J anuary 21, 1998
Reactions of buta-1,3-diyne with appropriate metal halides, carried out in the presence of
CuI in NHEt2, have given high yields of M(CtCCtCH)(CO)nCp [M ) W (1-W), Mo (1-Mo),
n ) 3; M ) Fe, n ) 2 (2)]. Complex 1-W was metalated with LiNPri ; subsequent reactions
2
with SiClMe3 or PClPh2 gave W(CtCCtCR)(CO)3Cp [R ) SiMe3 (3) or P(O)Ph2 (4)] in modest
to high yield. Coupling of 1 with iodoarenes, catalyzed by a mixed CuI-Pd0 catalyst, gave
M(CtCCtCAr) (CO)3Cp [M ) W, Ar ) Ph (5-W), tol (6), C6H4OMe-4 (7), C6H4CO2Me-4 (8);
M ) Mo, Ar ) Ph (5-Mo)]. Oxidative coupling of 1 (CuCl-tmed-O2) gave {M(CO)3Cp}2(µ-C8)
[M ) W (9-W), Mo (9-Mo)]. Addition of tetracyanoethene to 1-W occurred at the CtC triple
bond further from the metal atom, to give W{CtCC[)C(CN)2]CHdC(CN)2}(CO)3Cp (10).
Substitution of CO by PPh3 was difficult, but the Me3NO-induced reaction with 5-W afforded
cis-W(CtCCtCPh)(CO)2(PPh3)Cp (11) in low yield. The X-ray crystal structures of 3 and
10, together with that of cis-W(CtCPh)(CO)2(PPh3)Cp (12), are reported.
In tr od u ction
nylphosphino)acetylene (Ph2PCtCPPh2, dppa)12 and
1,4-bis(diphenylphosphino)buta-1,3-diyne (Ph2PCtCCt
CPPh2, bdpp)13 as precursors to cluster complexes
containing the ligands C2 and C4, respectively. The
open pentanuclear cluster Ru5(µ5-C2)(µ-SMe)2(µ-PPh2)2-
(CO)11, in particular, is a rich source of novel and
interesting transformations.14 The binuclear diyndiyl
complex {Cp(Ph3P)2Ru}CtCCtC{Ru(PPh3)2Cp} has
been obtained from Ru(thf)(PPh3)2Cp and LiCtCCt
CLi,15 or from RuCl(PPh3)2Cp and SiMe3CCtCSiMe3,9
and exhibits an unusually large range of oxidation
states.9 Many other complexes containing C4 or related
diynyl ligands have been obtained from reactions of
SiMe3CtCCtCR (R ) H, SiMe3).16
The study of metal complexes containing all-carbon
ligands is now an area of intense activity.1-4 In addition
to their inherent interest these compounds are consid-
ered as precursors to potentially useful new materials
and nanoscale devices. For example, poly-yndiyl com-
plexes, in which an unsaturated Cn chain links two
metal centers, have attracted the attention of several
groups as possible models of and potential precursors
to one-dimensional molecular wires.5-8 Several groups
have revealed the rich electrochemistry of these sys-
tems.5,9,10 Their unsaturation also makes them poten-
tially attractive monomers in as yet unrealized oligo-
merization and polymerization reactions.11
In seeking to extend these studies, we required access
to a range of diynyl complexes, {LnM}CtCCtCR, and
diyndiyl complexes, {LnM}CtCCtC{MLn}. Several
examples of such complexes have been described. Syn-
thetic routes of general application include (i) reactions
of diynyl anions with metal complexes containing a
readily displaced ligand, such as halide or triflate;15,17-19
Previous reports from this group have described the
use of the bis(tertiary phosphine) ligands 1,2-bis(diphe-
† The University of Adelaide.
‡ The University of Western Australia.
(1) Beck, W.; Neimer, B.; Wieser, M. Angew. Chem. 1993, 105, 969;
Angew. Chem., Int. Ed. Engl. 1993, 32, 923.
(2) Bunz, U. H. F. Angew. Chem. 1996, 108, 1047; Angew. Chem.,
Int. Ed. Engl. 1996, 35, 969.
(3) Lang, H. Angew. Chem. 1994, 106, 569; Angew. Chem., Int. Ed.
Engl. 1994, 33, 547.
(11) Lavastre, O.; Dixneuf, P. H.; Pacreau, A.; Vairon, J . P. Orga-
nometallics 1994, 13, 2500.
(12) Adams, C. J .; Bruce, M. I.; Skelton, B. W.; White, A. H. J . Chem.
Soc., Dalton Trans. 1997, 2937.
(13) Adams, C. J .; Horn, E.; Skelton, B. W.; Tiekink, E. R. T.; White,
A. H. J . Chem. Soc., Dalton Trans. 1993, 3299.
(14) Bruce, M. I. J . Cluster Chem. 1997, 8, 293.
(15) Bruce, M. I.; Hinterding, P.; Tiekink, E. R. T.; Skelton, B. W.;
White, A. H. J . Organomet. Chem. 1993, 450, 209.
(16) Bruce, M. I.; Low, P. J .; Werth, A.; Skelton, B. W.; White, A.
H. J . Chem. Soc., Dalton Trans. 1996, 1551.
(4) Akita, M.; Moro-oka, Y. Bull. Chem. Soc. J pn. 1995, 68, 420.
(5) Weng, W.; Bartik, T.; Brady, M.; Bartik, B.; Ramsden, J . A.; Arif,
A. M.; Gladysz, J . A. J . Am. Chem. Soc. 1995, 117, 11922.
(6) Brady, M.; Weng, W.; Zhou, Y.; Seyler, J . W.; Amoroso, A. J .;
Arif, A. M.; Bo¨hme, M.; Frenking, G.; Gladysz, J . A. J . Am. Chem. Soc.
1997, 119, 775.
(7) Coat, F.; Lapinte, C. Organometallics 1996, 15, 477.
(8) Bruce, M. I.; Ke, M.; Low, P. J . Chem. Commun. 1996, 2405.
(9) Bruce, M. I.; Denisovich, L. I.; Low, P. J .; Peregudova, S. M.;
Ustynyuk, N. A. Mendeleev Commun. 1996, 200.
(10) Le Narvor, N.; Toupet, L.; Lapinte, C. J . Am. Chem. Soc. 1995,
117, 7129.
(17) Kim, P. J .; Hasai, M.; Sonogashira, K.; Hagihara, N. Inorg.
Nucl. Chem. Lett. 1970, 6, 181.
S0276-7333(98)00031-4 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 07/10/1998

3540 Organometallics, Vol. 17, No. 16, 1998
Bruce et al.
Sch em e 1
(ii) oxidative addition of 1,3-diynes to electron-rich metal
centers, such as RhCl(PPri ) ;20 (iii) reactions between
3 2
metal halide complexes and trimethyltin diynes Me3-
SnCtCCtCR,20d,21 sometimes in the presence of pal-
ladium(0) catalysts;22 (iv) deprotonation of intermediate
vinylidene or metallacumulene complexes;21,23 and (v)
reactions of 1,3-diynes with metal halides in the pres-
ence of Cu(I) catalysts.24 Despite the growing number
of complexes of this type which have been made, their
reactivity remains relatively unexplored. Given the
extensive chemistry associated with the CtC triple
bond in both organic and organometallic chemistry,
transition metal complexes containing diynyl ligands
would be expected to exhibit a wide range of reactions.
One of the drawbacks to the preparation of diynyl
complexes {LnM}CtCCtCR (R ) H, alkyl, aryl, etc.)
by the above methods is the requirement for prior
synthesis of the corresponding 1,3-diynes, HCtCCtCR.
Examples include the synthesis of Ni(CtCCtCH)-
(PPh3)Cp from BrMgCtCCtCH, which was prepared
and to remove the HCl as diethylammonium chloride.
The complex is readily characterized from its spectral
properties and elemental analysis. The IR spectrum of
1-W contained strong ν(CO) absorptions at 2044 and
1958 cm-1, characteristic of the W(CO)3Cp fragment.
The terminal CtCH group gave rise to weak ν(tCH)
and ν(CtC) bands at 3260 and 2145 cm-1, respectively.
Sharp singlet resonances in the H NMR spectrum at δ
2.03 and 5.66 are assigned to the terminal tCH and
the Cp protons, respectively.
1
Besides resonances which could be assigned to the Cp
carbons at δ 91.51 and the three CO groups between δ
210 and 227, four signals in the 13C NMR spectrum
between δ 63.3 and 110.5 arise from the carbons of the
C4 chain (Table 1). In assigning these carbon reso-
nances, we note that those for CR, Câ, and Cγ (CR is
bonded to W) show satellite signals arising from cou-
pling to 183W. Previous assignments of the 13C reso-
nances in buta-1,3-diynyl complexes have been based
on trends found in values for J CP in phosphine-
from HCtCCtCH,17 RhHCl(CtCCtCPh)(PPri ) from
3 2
{RhCl(PiPr3)2}n and HCtCCtCPh20b and Re(CtCCtC
SiMe3)(PPh3)(NO)Cp* from [Re(ClC6H5)(PPh3)(NO)Cp*]-
BF4 and HCtCCtCSiMe3 in the presence of KOBut.5
An attractive alternative would be to functionalize buta-
1,3-diynyl complexes {MLn}CtCCtCH by reactions of
the diyne proton. We have found that buta-1,3-diyne,
HCtCCtCH, is a suitable reagent for the preparation
of these complexes and have further demonstrated that
the 1,3-diynyl ligand is indeed readily amenable to
substitution, making these complexes convenient ma-
terials for the preparation of substituted diynyl com-
plexes. In addition, the metal center and the CtC triple
bond are also reaction centers. The present paper
describes the development of a simple and reliable
synthetic approach to these complexes, as exemplified
by the tungsten, molybdenum, and iron derivatives,
M(CtCCtCH)(CO)nCp (M ) Mo, W, n ) 3; M ) Fe, n
) 2). Some of this work has been described in prelimi-
nary fashion.8
2
4
3
substituted complexes, so that J CP > J CP > J CP,5 or
from the H-coupled 13C NMR spectra obtained for
{MLn}CtCCtCH.7 Arguments that the chemical shift
moves downfield as the metal center is approached have
also been employed.7 In the case of 1-W, the diynyl
resonance at lowest field (δ 110.52) exhibits only
unresolved coupling to 183W, while the resonances at δ
71.60 and 70.13 show measurable coupling constants
of 88 and 94 Hz, respectively. We have tentatively
assigned the lowest field resonance to CR in keeping
with the established patterns for these systems (Table
1) and have assumed the magnitude of J CW for the Câ
and Cγ carbons follows the trend previously observed
for J CP in Fe(CtCCtCR)(dppe)Cp* (R ) H, SiMe3),7 so
4
3
that J CW [to Cγ; 94 Hz] > J CW [to Câ; 88 Hz].
The electrospray mass spectrum (ES MS) of a solution
of 1-W in aqueous NCMe at low cone voltages showed
the ions [M + MeCN - nCO]+ (n ) 0-2); similar
solvated [M + solvent]+ ions are frequently encountered
with this technique. At higher cone voltages only [M +
H - 3CO]+ was observed.
Resu lts a n d Discu ssion
Syn t h esis of 1,3-Diyn yl Com p lexes. The bright
yellow, air stable, and mildly light sensitive diynyl
complex W(CtCCtCH)(CO)3Cp (1-W, Scheme 1) was
obtained in excellent (90%) yield from the CuI-catalyzed
reaction between WCl(CO)3Cp and buta-1,3-diyne
(Scheme 1). The reactions were carried out in tetrahy-
drofuran solution containing diethylamine, which serves
both to generate the active diynylcopper intermediate
The dark yellow molybdenum analogue Mo(CtCCt
CH)(CO)3Cp (1-Mo) was prepared from MoI(CO)3Cp and
buta-1,3-diyne (60%) in an analogous manner. The
spectral properties of 1-Mo were not significantly dif-
ferent from those of 1-W. The absence of a spin-active
metal nucleus resulted in the observation of four sharp
singlets in the 13C NMR spectrum for the four-carbon
chain, which are assigned by analogy with those found
for 1-W. The tCH proton was found at δ 2.04 in the
1H NMR spectrum. The molybdenum complex is con-
siderably more light sensitive than 1-W, becoming
discolored after only a few minutes exposure to labora-
tory fluorescent lighting.
(18) Wong, A.; Kang, P. C. W.; Tagge, C. D.; Leon, D. R. Organo-
metallics 1990, 9, 1992.
(19) Lang, H.; Weber, C. Organometallics 1995, 14, 4415.
(20) (a) Fyfe, H. B.; Mlekuz, M.; Zararian, D.; Taylor, N. J .; Marder,
T. B.; J . Chem. Soc., Chem. Commun. 1991, 188. (b) Rappert, T.;
Nurnberg, O.; Werner, H. Organometallics 1993, 12, 1359. (c) Werner,
H.; Gervert, O.; Steinert, P.; Wolf, J . Organometallics 1995, 14, 1786.
(d) Gervert, O.; Wolf, J .; Werner, H. Organometallics 1996, 15, 2806.
(21) Touchard, D.; Pirio, N.; Toupet, L.; Fettouhi, M.; Ouahab, L.;
Dixneuf, P. H. Organometallics 1995, 14, 5263.
(22) Crescenzi, R.; Lo Sterzo, C. Organometallics 1992, 11, 4301.
(23) (a) Romero, A.; Peron, D.; Dixneuf, P. H. J . Chem. Soc., Chem.
Commun. 1990, 1410. (b) Le Bozec, H.; Dixneuf, P. H. Russ. Chim.
Bull. 1995, 44, 801.
The diynyl-iron complex Fe(CtCCtCH)(CO)2Cp (2)
was obtained from the diyne and FeCl(CO)2Cp. The
spectral data obtained for 2 were in good agreement
with those previously reported for the same complex
(24) (a) Sonogashira, K.; Yatake, T.; Tohda, Y.; Takahashi, S.;
Hagihara, N. J . Chem. Soc., Chem. Commun. 1977, 291. (b) Sonogash-
ira, K.; Kataoka, S.; Takahashi, S.; Hagihara, N. J . Organomet. Chem.
1978, 160, 319.

Tungsten Diynyl Complex W(CtCCtCH)(CO)3(η-C5H5)
Organometallics, Vol. 17, No. 16, 1998 3541
Ta ble 1. 13C NMR Da ta for Diyn yl Com p lexes, {MLn }CrtCâCγtCδ-R
chemical shift (J , Hz)
complex MLn
W(CO)3Cp
R
number
CR
Câ
Cγ
70.13
Cδ
notes
ref
H
1-W
110.52 (br)
71.60
63.60
this work
(J CW 88)
87.25
110.8
(J CW 94)
70.27
72.4
Mo(CO)3Cp
Re(NO)(PPh3)Cp*
Fe(CO)2Cp
H
H
H
1-Mo 110.46
62.10
65.2
54.35
this work
5
18, 22;
102.1
2
96.80
89.85
70.88
this work
Fe(CO)(PPh3)Cp
H
109.4
99.1
72.1
54.3
a
18
(J CP 39.4)
106.4
136.6
Fe(CO)2Cp*
Fe(dppe)Cp*
H
H
92.8
100.7
(J CH 5)
71.9
75.1
(J CP 3;
J CH 50)
73.9
53.5
50.5
(J CH 248)
33
7
b
(J CP 38)
Ru(PPh3)2Cp
H
H
116.4
(J CP 24.6)
101.3
96.8
111.74 (br)
105.8
94.4
128.4
15
Ru(CO)2(PEt3)2
Re(NO)(PPh3)Cp* Me
W(CO)3Cp
Re(NO)(PPh3)Cp* SiMe3
91.7
72.1
69.1
90.04
93.5
54.5
71.9
73.59
80.6
28
5
111.6
110.86
112.3
SiMe3
3
this work
5
b
(J CP 15.9)
106.3
98.14
(J CP 2.7)
94.7
91.1
Fe(CO)2Cp*
Fe(dppe)Cp*
SiMe3
SiMe3
96.5
91.9
102.3
(J CP 2)
96.11
103.0
69.5
71.0
64.7
b
a
b
7
19
7
142.2
96.2
(J CP 38)
95.95 (br)
121.3
(J CP 3)
67.11
93.2
trans-RuCl(dppm)2 SiMe3
a
c
e
20d
Rh(CO)(PPri
)
SiMe3
SiMe3
SiMe3
P(O)Ph2
Ph
77.2
75.5
71.4
d
3
2
(J CRh 43.3; J CP 22.1) (J CRh 13.1; J CP 2.5)
80.0
(J CP 11.2)
85.1
(J CP 11.4)
110.57
(J CW 16)
111.03
(J CW 22)
IrHCl(PPri
)
2
94.4
95.6
91.32
d
92.5
85.0
d
c
c
f
3
IrHCl(py)(PPri
W(CO)3Cp
)
f
3
4
this work
this work
W(CO)3Cp
5-W
76.19
73.78
Mo(CO)3Cp
W(CO)2(PPh3)Cp
Ph
Ph
5-Mo 110.92
d
76.42
72.75
72.59
72.2
this work
this work
11
113.27
(J CW 8)
126.33
100.14
Rh(CO)(PPri
W(CO)3Cp
)
2
Ph
102.22
79.15 (br) 71.95
(J PC 2.1)
60.91
c
20c
3
(J CRh 43.4; J CP 21.6) (J CRh 12.7; J CP 3.2)
CtCCtC
{W(CO)3Cp}
CtCCtC
{Mo(CO)3Cp}
CtCCtC
{Re(NO)(PPh3)Cp*}
CtCCtC
9-W
112.39
91.60
92.22
113.3
94.8
63.70
63.47
this work
Mo(CO)3Cp
9-Mo 112.24
59.95
64.5
51.4
50.6
this work
Re(NO(PPh3)Cp*
Fe(CO)2Cp*
109.7
(J CP 16.9)
110.8
66.6
(J CP 2.72)
61.61
32
33
7
{Fe(CO)2Cp*}
CtCCtC
Fe(dppe)Cp*
139.45
101.8
62.7
c
{Fe(dppe)Cp*}
(J CP 42)
(J CP 3)
a
b
2
Not individually assigned. Assignment based on J CP > 4J CP > 3J CP
.
c Assignment based on δ being further downfield as C is closer
d
to Fe, also on values of J CP
.
Not observed. e Dahlenburg, L.; Weiss, A.; Bock, M.; Zahl, A. J . Organomet. Chem. 1997, 541, 465. f Werner,
H.; Lass, R. W.; Gevert, G.; Wolf, J . Organometallics 1997, 16, 4077.
obtained from the Pd(0)-catalyzed reaction between Me3-
SnCtCCtCH and FeI(CO)2Cp22 or by treating Fe(Ct
CCtCSiMe3)(CO)2Cp with fluoride ion.18
(a ) Meta la tion w ith Lith iu m Diisop r op yla m id e
(LDA). Metalation of 1-alkynes with organolithium
reagents provides a convenient route to organolithium
compounds which can then be used as reactive inter-
mediates in further syntheses. Reactions of 1-W with
LiBun resulted in extensive decomposition of the diynyl
complex. Complex 2 has been reported to react slug-
gishly with LiBun and cleaner results were obtained
using the bulkier reagent LiBus.18 It seems likely that
the reactions of 1-W and 2 with LiBun are complicated
by nucleophilic attack at the carbonyl ligands. In
contrast, the carbonyl-free diynyl complex Re(Ct
CCtCH)(NO)(PPh3)Cp* 5 is readily metalated by LiBun.
F u n ction a liza tion a n d Rea ctivity Stu d ies. Es-
tablished methods for the preparation of asymmetrically
substituted organic diynes generally involve cross-
coupling of smaller acetylenic fragments.25 In contrast,
most diynyl complexes {MLn}CtCCtCR have been
prepared using reactions in which a preformed diyne is
the source of the diynyl ligand. We have found that the
readily available stable 1,3-diynyl complexes described
above can be used to synthesize a range of substituted
diynyl complexes, {MLn}CtCCtCR (Scheme 2). The
reaction conditions used to effect the various transfor-
mations are described below.
Complex 1-W was cleanly metalated by treatment
with 1 equiv of LiNPri (LDA) at -78 °C (Scheme 2),
2
when the initially yellow solution rapidly darkened to
orange. Quenching of this solution, which is assumed
(25) Eglinton, G.; McRae, W. Adv. Org. Chem. 1963, 4, 225.

3542 Organometallics, Vol. 17, No. 16, 1998
Bruce et al.
Sch em e 2
to contain W(CtCCtCLi)(CO)3Cp, with SiClMe3 af-
forded W(CtCCtCSiMe3)(CO)3Cp (3, Scheme 2) in high
yield (80%). We have also obtained complex 3, albeit
in only 36% yield, from the reaction between WCl-
(CO)3Cp and LiCtCCtCSiMe3 in a manner similar to
that described by Wong and co-workers for complex 2.18
Characterization of 3 followed from elemental analysis
and from its spectral properties. The IR spectrum
contained two weak ν(CtC) bands at 2174 and 2127
cm-1, together with three ν(CO) absorptions at 2045,
2026, and 1957 cm-1. The 1H NMR spectrum contained
the expected Cp and SiMe3 resonances at δ 5.66 and
0.20, respectively. In the 13C NMR spectrum, four
resonances between δ 73.6 and 111.7 were assigned to
the four carbons of the C4 chain; the Me and Cp signals
are at δ 0.00 and 91.53, respectively. The FAB mass
spectrum contained M+ at m/z 454.
Molecu la r Str u ctu r e of W(CtCCtCSiMe3)(CO)3-
Cp (3). The molecular structure of 3 has been con-
firmed by a single-crystal X-ray structural determina-
tion. Yellow needles of 3 were obtained from the
minimum volume of CH2Cl2 and n-hexane at -20 °C. A
plot of the molecular structure is of 3 is shown in Figure
1, selected bond lengths and angles are given in Table
2, and crystal and refinement data are given in Table
3. The methyl groups attached to Si are disordered over
two sites. There is a plane of symmetry passing through
C(1)-W-C(11). The molecule is a conventional piano
stool structure, the structural features of the W(CO)3Cp
group being unexceptional and closely similar to those
found in WPh(CO)3Cp26 and {W(CO)3Cp}2(µ-C2),27 for
example. The important feature is the coordination of
the diynyl ligand. The W-C(1) bond is 2.124(8) Å [cf.
2.172(22) Å in {W(CO)3Cp}2(µ-C2),27 and successive C-C
separations along the C(1)-C(2)-C(3)-C(4) chain are
1.22, 1.36, and 1.22(1) Å, indicating that the CtC triple
bonds are largely localized between C(1) and C(2) and
between C(3) and C(4). However, the CtC triple bonds
F igu r e 1. Plot of a molecule of W(CtCCtCSiMe3)(CO)3-
(η-C5H5) (3), showing atom numbering scheme. In this and
the following figures, non-hydrogen atoms are shown as
20% thermal ellipsoids; hydrogen atoms have arbitrary
radii of 0.1 Å.
are longer than that in W(CtCPh)(CO)2(PPh3)Cp (see
below), suggesting some electron delocalization, which
is facilitated by the SiMe3 group.28 The C(4)-Si separa-
tion [1.82(1) Å] is normal. The six-atom W-C(1)-C(2)-
C(3)-C(4)-Si chain is essentially linear, with angles at
C(1-4) of 179.0(8), 179(1), 177(1), and 177(1)°, again
consistent with the diynyl formulation. These dimen-
sions are comparable to those found in trans-Ru-
(CtCCtCSiMe3)2(CO)2(PEt3)2.28
Sequential treatment of 1-W with LDA and PClPh2
resulted in the formation of a large amount of black
material, presumably polymeric, possibly carbon, which
could not be characterized. However, extensive chro-
matographic purification of the reaction mixture af-
forded a yellow solid in low yield (16%). This compound,
initially reported as the tertiary alkynylphosphine,8
proved to be the corresponding phosphine oxide, W{Ct
CCtCP(O)Ph2}(CO)3Cp (4). In addition to the usual ν-
(CtC) and ν(CO) bands from the tungsten-diynyl
fragment, found at 2138 and at 2051, 2031, and 1962
(26) Semion, V. A.; Struchkov, Yu. T. Zh. Strukt. Khim. 1968, 9,
1046.
(27) Chen, M.-C.; Tsai, Y.-J .; Chen, C.-T.; Lin, Y.-C.; Tseng, T.-W.;
Lee, G.-H.; Wang, Y. Organometallics 1991, 10, 0. 378.
(28) Sun, Y.; Taylor, N. J .; Carty, A. J . Organometallics 1992, 11,
4293.

Tungsten Diynyl Complex W(CtCCtCH)(CO)3(η-C5H5)
Ta ble 2. Selected Bon d P a r a m eter s for Com p lexes 3, 10, a n d 12
10
Organometallics, Vol. 17, No. 16, 1998 3543
3
12
2.141(8)
2.278(8)-2.403(9)
2.33
Bond Distances (Å)
2.102(6)
W-C(1)
W-C(cp)
(av)
2.124(8)
2.295(6)-2.347(7)
2.32
2.297(8)-2.34(1)
2.32
W-C(11)
W-C(12)
W-C(13)
W-P
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(3)-C(5)
C(5)-C(6)
C(4)-Si
2.01(1)
2.013(7)
2.007(8)
1.965(8)
1.99(1)
1.975(8)
1.937(9)
2.491(2)
1.19(1)
1.43(1)
1.22(1)
1.36(1)
1.22(1)
1.207(9)
1.395(9)
1.381(9)
1.44(1)
1.35(1)
1.82(1)
Bond Angles (deg)
W-C(1)-C(2)
179.0(8)
179(1)
177(1)
177(1)
177.5(6)
173.8(7)
120.5(6)
178.1(7)
177.3(8)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
C(3)-C(4)-Si
C(2)-C(3)-C(5)
C(3)-C(5)-C(6)
C(1)-W-C(11)
C(1)-W-C(12)
C(1)-W-C(13)
C(11)-W-C(12)
C(11)-W-C(13)
C(12)-W-C(13)
121.5(6)
127.0(6)
129.8(3)
75.3(3)
75.4(6)
77.6(3)
77.2(3)
112.6(4)
127.1(4)
75.3(2)
129.9(3)
76.9(3)
75.1(2)a
75.7(3)
76.7(2)
80.2(2)a
115.8(2)a
114.1(3)
a
For C(13), read P(1).
Ta ble 3. Cr ysta l Da ta a n d Refin em en t Deta ils for
Com p lexes 3, 10, a n d 12
compounds M(CtCCtCPh)(CO)3Cp [M ) W (5-W); Mo
(5-Mo)] were prepared by treating diisopropylamine
solutions of 1 with an excess of iodobenzene in the
presence of catalytic amounts of Pd(PPh3)4 and CuI
(Scheme 2). Both complexes exhibit very similar spec-
tral properties. Most significantly, the 13C NMR spectra
contained distinct resonances for each of the four carbon
nuclei of the C4 chain between δ 72.6 and 111.0. The
FAB mass spectrum of 8 contained M+ at m/z 458
together with [M - CO]+. The electrospray mass
spectrum of 9 was obtained in the presence of NaOMe31
and contained [M + OMe]- as highest mass ion at m/z
402.
3
10
12
formula
mol wt
cryst syst
space group
a, Å
C
454.2
monoclinic
P21/m
6.532(5)
9.561(9)
13.701(10)
101.55(7)
838
15H14O3SiW
C18H6N4O3W
510.1
orthorhombic orthorhombic
C33H25O2PW
668.4
Pbca
Pbca
20.542(7)
13.653(3)
12.372(3)
20.285(8)
19.458(8)
13.709(6)
b, Å
c, Å
â, deg
V, Å3
3470
8
1.95
1920
5411
8
1.64
2624
Z
2
1.80
432
Dc, g cm-3
F(000)
cryst size, mm 0.56 × 0.50 × 0.28 × 0.32 × 0.25 × 0.25 ×
A* (min, max) 1.17, 10.7
Similar reactions of 1-W with 4-iodotoluene, 4-io-
doanisole, and methyl 4-iodobenzoate in the presence
of the mixed catalyst gave the substituted derivatives
W(CtCCtCC6H4R)(CO)3Cp [R ) Me 6 (35%), OMe 7
(51%), CO2Me 8 (89%) (Scheme 2)]. All complexes were
characterized from their spectral properties which
resembled those of 5-W. In addition, appropriate reso-
nances for the OMe, Me, and CO2Me groups were also
present in their 1H NMR spectra. Thus a variety of
aryl-substituted derivatives M(CtCCtCC6H4R)(CO)3-
Cp can be obtained, of which the diynyl ligands are all
derived from buta-1,3-diyne as the diynyl precursor,
thus avoiding the need to use separate 1-substituted
diynes as precursors for each complex.
(c) Oxid a tive Cou p lin g Rea ction s. Symmetrically
substituted conjugated poly-ynes are readily obtained
by oxidative coupling of alkynylcoppers (Glaser, Eglin-
ton, and Hay reactions). A variety of oxidizing agents
has been employed, and the Cu(I) derivative often needs
to be present in only trace amounts.25 Recently the
0.02
0.60
3.3, 5.1
67
0.60
2.00, 3.0
44
µ, cm-1
70
60
3643
2518
0.045
0.047
2θmax, deg
60
56
N
No
R
4954
2889
0.036
0.037
5124
3333
0.040
0.041
Rw
cm-1, respectively, the IR spectrum of 4 contained a
strong ν(PO) band near 1200 cm-1, while the 31P
spectrum contained a single resonance at δ 5.6. The
latter is in the region associated with P(V) compounds
and may be compared with the value for P(O)(CtCBut)-
Ph2 at δ 1.1.29 It is likely that oxidation of the desired
phosphine occurred during the extensive pruification
process, during which air was not rigorously excluded.
(b) P a lla d iu m (0)/Cop p er (I)-Ca ta lyzed Cou p lin g
Reaction s with Iodoar en es an d -alkyn es. 1-Alkynes
undergo facile cross-coupling reactions with aryl and
vinyl halides in the presence of basic amines and a
mixed Cu(I)-Pd(0) catalyst (Sonogashira reaction).30
Complexes 1 readily enter into this reaction. The
(30) (a) Heck, R. F. Palladium Reagents in Organic Synthesis;
Academic Press Inc.: Orlando, FL, 1985. (b) Tsuji, J . Palladium
Reagents and Catalysis; J ohn Wiley and Sons: New York, 1995.
(31) Henderson, W.; McIndoe, J . S.; Nicholson, B. K.; Dyson, P. J .
Chem. Commun. 1996, 1183.
(29) Fogg, D. E.; Taylor, N. J .; Meyer, A.; Carty, A. J . Organome-
tallics 1987, 6, 2252.

3544 Organometallics, Vol. 17, No. 16, 1998
Bruce et al.
complexes such as Ti(CtCPh)2(η-C5H4SiMe3)2,19,35 it is
interesting to speculate about the possibility of related
complexes being formed between 1 and group 11 cat-
ions: experiments to test this hypothesis are under way.
(d ) Rea ction s w ith Tetr a cya n oeth en e. The reac-
tions of tetracyanoethene (tcne) and related electron-
deficient fluoro-olefins with alkynyl complexes of several
metals have been studied in detail.36-40 In general, the
reactions proceed via intensely colored short-lived para-
magnetic intermediates to give cyclobutenyl complexes.
Subsequent ring-opening and chelate-forming reactions
have given a series of buta-1,3-dien-2-yl and allylic
complexes (Scheme 4).
Sch em e 3
dimetalated tetraynes {MLn}CtCCtCCtCCtC{MLn}
[MLn ) Re(NO)(PPh3)Cp*,32 Fe(dppe)Cp* 7] were pre-
pared by Eglinton coupling of the appropriate diynyl
precursors. This method utilizes a stoichiometric amount
of Cu(OAc)2, and the reactions are typically performed
in pyridine at elevated temperatures.25 However, similar
attempts to couple the diynyl ligands in 1 resulted only
in extensive decomposition of the diynyl reagent.
The reaction between 1-W and tcne in CH2Cl2 pro-
ceeded similarly via a short-lived, deep green intermedi-
ate to give a deep purple solution from which crystals
of W{CtCC[)C(CN)2]CHdC(CN)2}(CO)3Cp (10) were
obtained. The IR spectrum of 10 contained the expected
Homocoupling of the diynyl ligand in 1 was achieved
through use of the milder Hay conditions [CuCl/
N,N,N′,N′-tetramethylethylenediamine (tmed)/O2] and
the corresponding tetrayne-diyl complexes {Cp-
(CO)3M}CtCCtCCtCCtC{M(CO)3Cp} [M ) W (9-W);
Mo (9-Mo)] were obtained in good yield (Scheme 3). The
very recent report by Akita and co-workers described
the use of similar conditions in the preparation of
another carbonyl-containing tetrayne-diyl complex
[Cp*(OC)2Fe}CtCCtCCtCCtC{Fe(CO)2Cp*}.33
Both of these complexes are rather more light sensi-
tive than their diynyl precursors. The spectral proper-
ties of both complexes are similar, with each complex
having a single, weak ν(CtC) band (2190 cm-1, 9-W;
2140 cm-1, 9-Mo) together with strong ν(CO) bands
(2043 and 1959 cm-1, 9-W; 2049, 1973 cm-1, 9-Mo). In
addition to the expected resonances from the Cp (δ
91.66) and CO ligands (δ 210.3 and 227.3), the four
magnetically inequivalent carbon nuclei of the tet-
rayne-diyl bridge were found as well-resolved peaks of
low intensity near δ 112 (CR), 92 (Câ), 64 (Cγ), and 61
(Cδ) (Table 1). In the case of 9-W, the resonance at
lowest field is broadened by coupling to 183W; the
remainder of the resonances were assigned by analogy
with those in 1. The relatively low chemical shift found
for C(4) follows the trend previously found for other
complexes of this type and previously, for organic long-
chain poly-ynes which approach a limiting value of δ
60 ppm.33
ν(CN) (2221 cm-1), ν(CtC) (2078 cm-1) and ν(CO) bands
(2030 and 1970 cm-1). The 13C NMR spectrum con-
tained singlet resonances at δ 221.0, 148.7, 94.4, and
91.9 which were assigned to the carbon atoms of the
butadienyl part of the ligand by comparison with the
spectrum of W{C[dC(CN)2C(Ph)dC(CN)2}(CO)3Cp.38
A
1
low-field resonance (δ 7.63) in the H NMR spectrum
was assigned to the butadienyl proton and suggested
that reaction had occurred at the outer CtC triple bond.
The organic ligand is probably formed by cycloaddition
of the tcne molecule to the outer CtC triple bond,
followed by opening of the resulting cyclobutenyl ring
to give a trans-butadienyl group. This conclusion was
confirmed by a single-crystal X-ray diffraction study, the
details of which are reported below. The reaction of tcne
with the triple bond removed from the metal center
indicates that this external CtC bond is still rather
electron rich.
The ES MS spectra were obtained in the presence of
a small amount of Ag+, which has previously been
shown to increase the viability of this technique with
organometallics.34 The spectra of 9-W contained peaks
at high mass numbers corresponding to silver-contain-
ing aggregate ions, including [Ag2{W2(C8)(CO)6Cp2}]+
and [Ag(NCMe){W2(C8)(CO)6Cp2}]+. At higher cone
voltages, fragment ions formed by successive loss of CO
groups were formed. For 9-Mo, the ion [Ag(NCMe)-
{Mo2(C8)(CO)6Cp2}]+ was the only high mass ion ob-
served. In light of the formation of complexes contain-
ing group 11 cations attached to molecular tweezer
Molecu lar Str u ctu r e of W{CtCC[)C(CN)2]CHdC-
(CN)2}(CO)3Cp (10). A molecule of 10 is shown in
Figure 2, and selected bond lengths and angles are given
in Table 2. The structural features of the W(CO)3Cp
group are similar to those found for 3. The W-C(1) and
C(1)-C(2) bond lengths are 2.102(6) and 1.207(9) Å,
with W-C(1)-C(2) and C(1)-C(2)-C(3) angles of 177.5-
(6) and 173.8(7)°, respectively. Within the organic
ligand, distances and angles are consistent with sp2
(35) (a) Lang, H.; Herres, M.; Zsolnai, L. Organometallics 1993, 12,
5008. (b) Hahashi, Y.; Osawa, M.; Kobogashi, K.; Wakatsuki, Y. Chem.
Commun. 1996, 1617. (c) Varga, V.; Mach, K.; Miller, J .; Thewalt, U.
J . Organomet. Chem. 1996, 506, 109.
(36) Davison, A.; Solar, J . P. J . Organomet. Chem. 1979, 166, C13.
(37) Bruce, M. I.; Hambley, T. W.; Snow, M. R.; Swincer, A. G.
Organometallics 1985, 4, 494.
(38) Bruce, M. I.; Hambley, T. W.; Snow, M. R.; Swincer, A. G.
Organometallics 1985, 4, 501.
(32) (a) Brady, M.; Weng, W.; Gladysz, J . A. J . Chem. Soc., Chem.
Commun. 1994, 2655. (b) Bartik, T.; Bartik, B.; Brady, M.; Dembinski,
R.; Gladysz, J . A. Angew. Chem. 1996, 108, 467; Angew. Chem., Int.
Ed. Engl. 1996, 35, 414.
(33) Huntsman, W. D. In The Chemistry of the Carbon-Carbon
Triple Bond; Patai, S. Ed.; Wiley: New York, 1978; p 553.
(34) Henderson, W.; Nicholson, B. K. J . Chem. Soc., Chem. Commun.
1995, 2531.
(39) Bruce, M. I.; Liddell, M. J .; Snow, M. R.; Tiekink, E. R. T.
Organometallics 1988, 7, 343.
(40) Bruce, M. I.; Hambley, T. W.; Liddell, M. J .; Snow, M. R.;
Swincer, A. G.; Tiekink, E. R. T. Organometallics 1990, 9, 96.

Tungsten Diynyl Complex W(CtCCtCH)(CO)3(η-C5H5)
Organometallics, Vol. 17, No. 16, 1998 3545
Sch em e 4
thermal, photochemical, and chemical methods. Oxida-
tive decarbonylation by trimethylamine N-oxide (tmno)
in the presence of the ligand has become established as
a convenient route for the preparation of a wide range
of substituted metal carbonyls.42 We therefore chose to
examine the use of this reagent in the synthesis of
tertiary phosphine-substituted derivatives of 1-W.
A mixture of W(CtCCtCPh)(CO)3Cp (5-W) and PPh3
in CH2Cl2 was treated with tmno to give cis-W(Ct
CCtCPh)(CO)2(PPh3)Cp (11) in low yield (20%). The
simple acetylide analogue cis-W(CtCPh)(CO)2(PPh3)-
Cp (12), which has been reported briefly by others,43 was
obtained in a similar manner from W(CtCPh)(CO)3Cp
and fully characterized by a single-crystal X-ray study,
the details of which are reported below. The composi-
tions of 11 and 12 were established from microanalytical
data and the usual spectral techniques, including elec-
trospray mass spectra which were obtained from meth-
anolic NaOMe solutions, and contained [M + Na]+ as
highest ions. We have observed many similar [M +
Na]+ ions in the ES mass spectra of diyndiyl com-
plexes.8,44 These curious species are the subject of
further investigations.
Both cis and trans isomers of WX(CO)2(L)Cp′ are
known, and in some instances the reactions produce a
mixture of isomers, the proportions of which depend on
the nature of X, the incoming ligand L, and the
preparative method employed. Although the factors
controlling the relative stabilities of the isomers are not
always clear, it has been suggested that the position of
the equilibrium may be a delicate balance between the
trans influence of the ligands and the steric interactions
F igu r e 2. Plot of a molecule of W{CtCC[CHdC(CN)2])C-
(CN)2}(CO)3(η-C5H5) (10), showing atom numbering scheme.
hybridization for C(3-6). This part of the ligand closely
resembles that found in Ru{C[dC(CN)2]CPhdC(CN)2}-
(dppe)Cp, formed by a similar addition of tcne to Ru-
(CtCPh)(dppe)Cp.38 The cyanocarbon ligand is essen-
tially planar, and, given the intense color of this
complex, it seems reasonable to suggest that extensive
electron delocalization occurs throughout this part of the
molecule.
Attempts to add a second equivalent of tcne to 10 were
unsuccessful. As tcne adds readily to the triple bonds
in more sterically congested acetylide complexes such
as Ru(CtCPh)(PPh3)2Cp and W(CtCPh)(CO)3Cp, it is
unlikely that steric factors are involved. Instead it
seems more probable that the electron-withdrawing
cyano groups, which are conjugated with the CtC triple
bond in 10, deactivate this site thereby precluding
further [2+2] cycloaddition. We note that tcne also adds
to electron-rich CdC double bonds, such as those found
in vinyl ethers, vinyl sulfides, enamines, and N-vinyl-
sulfonamides, for example.41
(42) For example, see: (a) Koelle, U. J . Organomet. Chem. 1978,
155, 53. (b) J ohnson, B. F. G.; Lewis, J .; Pippard, D. A. J . Chem. Soc.,
Dalton Trans. 1981, 407. (c) Foulds, G. A.; J ohnson, B. F. G.; Lewis,
J . J . Organomet. Chem. 1985, 296, 147. (d) Drake, S. R.; Khattar, R.
Organomet. Synth. 1988, 4, 234. (e) Adams, C. J .; Bruce, M. I.; Horn,
E.; Tiekink, E. R. T. J . Chem. Soc., Dalton Trans. 1992, 1157. (f) Bruce,
M. I.; Low, P. J . J . Organomet. Chem. 1996, 519, 221.
(43) Ustynyuk, N. A.; Vinogradova, V. N.; Korneva, V. N.; Kravtsov,
D. N.; Andrianov, V. G.; Struchkov, Yu. T. J . Organomet. Chem. 1984,
277, 285.
(e) Tr im eth yla m in e N-Oxid e Assisted Ca r bon yl-
P h osp h in e Exch a n ge Rea ction s of W{(CtC)n P h }-
(CO)3Cp . Substitution reactions of the carbonyl ligands
in WX(CO)3Cp′ complexes (X ) H, halide, alkyl; Cp′ )
Cp, Cp*) have been examined using a variety of
(41) Williams, J . K.; Wiley: D. W.; McKusick, B. C. J . Am. Chem.
Soc. 1962, 84, 2210.
(44) Bruce, M. I.; Low, P. J .; Nicholson, B. K. Unpublished results.

3546 Organometallics, Vol. 17, No. 16, 1998
Bruce et al.
Con clu sion
We have demonstrated that the Cu(I)-catalyzed cou-
pling of buta-1,3-diyne with several metal halides
affords the corresponding buta-1,3-diyn-1-yl complexes
in high yield. Application of conventional organic
reactions to the tungsten complex has allowed the
preparation of related diynyl, diyndiyl, and octayndiyl
complexes in high yield. In addition, substitution of CO
with a tertiary phosphine ligand at the metal center
proceeds with retention of the diynyl ligand. In all these
cases, the poly-yne ligands are obtained from easily
accessible buta-1,3-diyne as the precursor.
Exp er im en ta l Section
Gen er a l Rea ction Con d ition s. All reactions were carried
out under dry, high purity nitrogen using standard Schlenk
techniques. Solvents were dried, distilled, and degassed before
use. Light petroleum refers to a fraction of bp 60-80 °C.
Elemental analyses were by the Canadian Microanalytical
Service (Delta, BC, Canada). Preparative TLC was carried
out on glass plates (20 × 20 cm) coated with silica gel (Merck
60 GF254, 0.5 mm thick).
In str u m en ta l Con d ition s. Infrared: Perkin-Elmer 1700X
FT-IR. NMR: Bruker ACP300 (1H at 300.13 MHz, 13C at 75.47
MHz) and Varian Gemini 200 (1H at 199.98 MHz, 13C at 50.29
MHz) spectrometers. For the 13C data, all signals are singlets
unless otherwise indicated. Listed values of J CW refer to the
doublet signals arising from the presence of 183W (ca. 15%
natural abundance), which appear about the singlet. Chemical
shifts are referenced to SiMe4 (1H and 13C) and external H3-
PO4 (31P). FAB mass spectra: VG ZAB 2HF spectrometer (3-
nitrobenzyl alcohol as matrix; exciting gas, Ar; FAB gun
voltage, 7.5 kV; current, 1 mA; accelerating potential, 7 kV).
ES mass spectra: The samples were dissolved in acetonitrile/
water (1/1), unless otherwise indicated, and injected into a 10
µL injection loop attached to a VG Platform II mass spectrom-
eter. Nitrogen was used as the drying and nebulizing gas.
Samples were examined over a range of cone voltages (20-90
V) to find the best conditions. Chemical aids to ionization were
used when required.31,34
R ea gen t s. The compounds HCtCCtCH,50 SiMe3Ct
CCtCSiMe3,51 WCl(CO)3Cp,52 MoI(CO)3Cp,53 FeCl(CO)2Cp,54
LiNPri2 (LDA),55 Pd(PPh3)4,56 and 4-MeOC6H4I57 were prepared
by literature methods. N,N,N′,N′-Tetramethylethylenedi-
amine (Merck), C6H5I and 4-MeC6H4I (Aldrich), trimethy-
lamine N-oxide (Aldrich), and PClPh2 (Aldrich) were purchased
and purified by standard methods prior to use. CuCl (Ajax),
CuI (Ajax), PPh3 (Strem), and SiClMe3 (Aldrich) were pur-
chased and used as received.
P RECAUTIONARY WARNING! While no problems have
been experienced in the preparation, manipulation and reac-
tions of buta-1,3-diyne in this laboratory, this compound must
be handled with the necessary degree of respect at all times,
especially in the presence of Cu(I). Neat HCtCCtCH should
never be isolated. As a matter of routine precaution, solutions
of this reagent (2-3 M) were kept cold (ca. -78 °C) under dry
nitrogen and used within 5 days of preparation. All manipula-
F igu r e 3. Plot of a molecule of W(CtCPh)(CO)2(PPh3)(η-
C5H5) (12), showing atom numbering scheme.
between the ligands L and X.45 Both isomers of WX-
(CO)2(L)Cp give similar two-band ν(CO) patterns in the
IR region, although the spectra of the trans isomers
typically show less intense symmetric and more intense
antisymmetric ν(CO) bands than the cis isomers.46,47
The IR ν(CO) spectra of both complexes prepared here
have similar two-band patterns. The stronger, sym-
metric stretch was found at 1953 (11) or 1949 (12) cm-1
,
while the antisymmetric vibration gave rise to a weaker
absorption at 1875 or 1863 cm-1, respectively.
However, it is the 13C carbonyl resonances which
provide the simplest method of distinguishing between
the isomers, as the trans form contains only a single
13CO resonance, while the inequivalent carbonyl ligands
in the cis isomer give rise to two resonances.48 The 13C
NMR spectra of 11 and 12 each contained two distinct
resonances arising from the inequivalent carbonyl ligands
in a cis geometry.
Molecu la r St r u ct u r e of cis-W(CtCP h )(CO)2-
(P P h 3)Cp (12). A molecule of 12 is shown in Figure 3
and selected bond lengths and angles are given in Table
2. The structure determination confirms the cis ar-
rangement of CO groups [angles C(11)-W-C(12), 75.7-
(3); P-W-C(1), 75.1(2)°]. The presence of the bulky
phosphine ligand results in some distortion of the
normal coordination about the metal atom, with P-W-
C(11, 12) angles of 80.2 and 115.8(2)°, respectively
compressed and enlarged compared with the usual
values of ca. 127 and 75° found in 5-W and 10 above.
The W-P distance is 2.491(2) Å [cf. 2.457(1) Å in trans-
W{C(O)Me}(CO)2(PPh3)Cp49], and the W-C(1) separa-
tion is 2.141(8) Å, somewhat longer than those found
in 5-W and 10. Conversely, the W-CO distances [1.975,
1.937(8) Å] are shorter, due to increased electron back-
bonding as a result of the presence of the PPh3 ligand.
The phenylethynyl ligand has C(1)-C(2) of 1.19(1) Å
and C(2)-C(3) of 1.43(1) Å, which are within the normal
ranges; angles at C(1) and C(2) are 178.1(7) and 177.3-
(8)°.
(50) Brandsma, L. Preparative Organic Chemistry, 2nd ed.; Elsevier
Science Publishers B.V.: Amsterdam, The Netherlands, p 179.
(51) J ones, G. E.; Kendrick, D. A.; Holmes, A. B. Organic Syntheses;
Wiley: New York, 1993; Collect Vol. 8, p 63.
(45) Faller, J . W.; Anderson, A. S. J . Am. Chem. Soc. 1970, 92, 5852.
(46) Bainbridge, A.; Craig, P. J .; Green, M. J . Chem. Soc. A 1968,
2717.
(47) Beach, D. L.; Barnett, K. W. J . Organomet. Chem. 1975, 97,
C27.
(52) Hoffman, N. W. Inorg. Chim. Acta 1984, 88, 59.
(53) Abel, E. W.; Singh, A.; Wilkinson, G. J . Chem. Soc. 1960, 1321.
(54) Fischer, E. O.; Moser, E. Inorg. Synth. 1970, 12, 35.
(55) Spitzner, D.; Engler, A. Organic Syntheses; Wiley: New York,
1993; Collect. Vol. 8, p 219.
(48) Sakaba, H.; Ishida, K.; Horino, H. Chem. Lett. 1995, 1145.
(49) Chen, J .-D.; Wu, C.-K.; Wu, I.-Y.; Huang, B.-C.; Lin, Y.-C.;
Wang, Y. J . Organomet. Chem. 1993, 454, 173.
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Chem. Soc., Perkin Trans. 1 1984, 2623.

Tungsten Diynyl Complex W(CtCCtCH)(CO)3(η-C5H5)
Organometallics, Vol. 17, No. 16, 1998 3547
tions of this compound were performed behind an explosion-
proof shield.
73.59 (s, Cδ); 0.00 (s, SiMe3). FAB MS (m/z): 454, M+; 426,
[M - CO]+; 370, [M - 3CO]+.
Complex 3 was also prepared as follows: a solution of WCl-
(CO)3Cp (200 mg, 0.54 mmol) in thf (10 mL) was cooled to -78
°C and treated dropwise with LiCtCCtCSiMe3 [0.12 M, 5 mL,
0.6 mmol; solution prepared from 1,4-bis(trimethylsilyl)buta-
1,3-diyne (250 mg, 1.23 mmol) in thf (10 mL) at -78 °C treated
dropwise with MeLi‚LiBr (1.5 M solution in Et2O, 0.860 mL,
1.23 mmol)].18,58 After warming to room temperature over 1
h preparative TLC (light petroleum/acetone, 7/3) afforded
W(CtCCtCSiMe3)(CO)3Cp (3) (88 mg, 36%) from the yellow
band (Rf ) 0.7) after crystallization (CH2Cl2/hexane at -20
°C) and unchanged WCl(CO)3Cp (orange band, Rf ) 0.6, 50
mg, 25%).
P r ep a r a t ion of Bu t a -1,3-d iyn -1-yl Com p lexes. W-
(CtCCtCH)(CO)3Cp (1-W). WCl(CO)3Cp (2.5 g, 6.79 mmol)
was dissolved in mixture of thf (20 mL) and NHEt2 (50 mL).
To this solution was added CuI (150 mg, 0.79 mmol), followed
immediately by buta-1,3-diyne (7 mL of a 3M solution in thf).
The reaction mixture rapidly changed color from red to yellow-
orange, and a white precipitate of [NH2Et2]Cl formed. After
5 min, the solution was filtered and the solvent was removed.
The residue was extracted (CH2Cl2) and loaded onto a column
of alumina. Elution with light petroleum/acetone (7/3) gave
a bright yellow band. Concentration of the eluant (ca. 10 mL)
resulted in the precipitation of W(CtCCtCH)(CO)3Cp (1-W)
(2.3 g, 89%) as a bright yellow powder, which was collected,
washed with cold hexane, and air-dried. The compound was
best stored in the dark at -18 °C. Anal. Found for
P r ep a r a tion of W{CtCCtCP (O)P h 2}(CO)3Cp (4).
A
cold (-78 °C) solution of 1-W (1.0 g, 2.60 mmol) in thf (100
mL) was treated dropwise with lithium diisopropylamide (0.5
M solution in thf/hexane, 5.5 mL, 2.8 mmol) and stirred for
10 min. Freshly distilled PClPh2 (0.5 mL, 2.8 mmol) was
added slowly, and the solution was allowed to warm to room
temperature over 2 h. Solvent was removed, and the residue
taken up in CH2Cl2 and loaded onto a squat Al2O3 column.
The column was washed initially with CH2Cl2 to remove any
unchanged W(CtCCtCH)(CO)3Cp and then with acetone to
give crude W{CtCCtCP(O)Ph2}(CO)3Cp (4) (250 mg, 16%),
which was purified further by preparative TLC (light petroleum/
acetone, 6/4) and crystallization (CH2Cl2/hexane). Anal. Found
for C24H15O4PW: C, 49.11; H, 2.63. Calcd: C, 49.40; H, 2.57.
IR (CH2Cl2): ν(CtC) 2138 m, ν(CO) 2051 s, 2031 m, 1962 (br);
C
12H6O3W: C, 37.38; H, 1.54. Calcd: C, 37.72; H, 1.57. IR
(CH2Cl2): ν(tCH) 3260 m, ν(CtC) 2145 m, ν(CO) 2044 s, 1958
s (br) cm-1 1H NMR (CDCl3): δ 5.66 (s, 5H, Cp); 2.03 (s, 1H,
.
tCH); (C6D6) 4.42 (s, 5H, Cp), 1.80 (s, 1H, tCH). 13C NMR
(CDCl3): δ 227.41 (d, J CW ) 70 Hz, CO), 210.87 (d, J CW ) 70
Hz, CO), 110.52 (br, CR), 91.51 (s, Cp), 71.60 (d, J CW ) 88 Hz,
Câ), 70.13 (d, J CW ) 94 Hz, Cγ), 63.30 (s, Cδ). ES MS (low cone
voltage) (m/z): 396, [M - CO + NCMe + H]+; 368, [M - 2CO
+ NCMe + H]+; 355, [M - CO + H]+; (high cone voltage) 299,
[M - 3CO + H]+.
Mo(CtCCtCH)(CO)3Cp (1-Mo). In a reaction similar to
that described for the tungsten analogue, dark yellow Mo-
(CtCCtCH)(CO)3Cp (1-Mo) was isolated in 60% yield (0.95
g) from MoI(CO)3Cp (2 g, 5.4 mmol) and buta-1,3-diyne. The
compound was eluted with light petroleum/acetone (9/1). Anal.
Found for C12H6O3Mo: C, 49.02; H, 2.63. Calcd: C, 48.69; H,
2.03. IR (CH2Cl2): ν(CtC) 2145 m, ν(CO) 2050 s, 1970 br
(Nujol) ν(PO) 1199 cm-1 1H NMR (CDCl3): δ 7.89-7.47 (m,
.
10H, PPh2), 5.69 (s, 5H, Cp). 13C NMR (CDCl3): δ 225.43 (s,
CO); 210.23 (d, J CW ) 71 Hz, CO), 134.33-128.45 (Ph), 110.57
(d, J CW ) 16 Hz, CR), 91.64 (s, Cp), 91.32 (s, Câ). FAB MS
(m/z): 583, M+; 555, [M - CO]+; 498, [M - 3CO]+.
P r ep a r a tion of W(CtCCtCP h )(CO)3Cp (5-W). Dry
cm-1
.
1H NMR (CDCl3): δ 5.58 (s, 5H, Cp), 2.04 (s, 1H,
NHPri (50 mL) was introduced into a flame-dried Schlenk
CtCH). 13C NMR (CDCl3): δ 237.39 (s, CO), 221.86 (s, CO),
110.46 (s, CR), 92.94 (s, Cp), 87.25 (s, Câ), 70.27 (s, Cγ), 62.10
(s, Cδ). FAB MS (m/z): 293, M+; 266-210, [M - nCO]+ (n )
1-3).
2
flask and rigorously deoxygenated by three freeze-pump-
thaw sequences. Solid 1-W (1.0 g, 2.62 mmol) was added
followed by freshly distilled iodobenzene (801 mg, 3.93 mmol),
Pd(PPh3)4 (151 mg, 0.13 mmol) and CuI (50 mg, 0.26 mmol)
in that order. The solution was stirred in the dark for 16 h.
The yellow precipitate obtained was filtered, washed with
several portions of cold hexane, dissolved in the minimum
volume of CH2Cl2, and purified on a squat column of Al2O3
(30 × 50 mm). Elution with light petroleum/acetone (7/3) gave
a bright yellow fraction, which was concentrated to give
W(CtCCtCPh)(CO)3Cp (5-W) as a bright yellow microcrys-
talline powder (650 mg). Similar treatment of the filtrate from
the reaction mixture on a longer Al2O3 column gave a further
140 mg of 5-W. The total yield was 790 mg (66%). The
microanalytical sample was recrystallized from acetone/hex-
ane. Anal. Found for C18H10O3W: C, 46.80; H, 2.29. Calcd:
C, 47.20; H, 2.18. IR (CH2Cl2): ν(CtC) 2183 m, 2059 m, ν-
F e(CtCCtCH)(CO)2Cp (2). A solution of FeCl(CO)2Cp
(200 mg, 0.83 mmol) in NHEt2 (20 mL) was treated with a
catalytic amount of CuI, followed by buta-1,3-diyne (4 mmol
as a 3 M thf solution). The deep red solution darkened, was
stirred for 5 min, and filtered though Celite. The volatiles
were removed, and the residue was purified by preparative
TLC (light petroleum/acetone, 7/3). The first band (maroon,
Rf ) 0.8) contained a trace amount of {Fe(CO)2Cp}2. The
major band (yellow, Rf ) 0.6) contained Fe(CtCCtCH)(CO)2-
Cp (2) (67 mg, 32%). IR (CH2Cl2) ν(CtC): 2149 m, ν(CO) 2050
s, 2003 s cm-1 1H NMR (CDCl3): δ 5.07 (s, 5H, Cp), 1.47 (s,
.
1H, CtCH) [lit.22 2149.5, 2049.9, 2002.5 cm-1; δ 5.02, 1.41].
Rea ction s of M(CtCCtCH)(CO)3Cp (1-M). P r ep a r a -
tion of W(CtCCtCSiMe3)(CO)3Cp (3). A solution of 1-W
(200 mg, 0.52 mmol) in thf (15 mL) was cooled to -78 °C, and
lithium diisopropylamide (0.5 M solution in thf/hexane, 1.04
mL, 0.52 mmol) was added dropwise to the stirred solution.
The solution became orange and was allowed to stir for 5 min
before SiClMe3 (66 µL, 57 mg, 0.52 mmol) was added. The
solution was allowed to warm to room temperature over 20
min, and solvent was removed. The filtered (Celite) extracts
(CH2Cl2) were concentrated to ca. 10 mL and diluted with a
similar volume of n-hexane. Further concentration resulted
in the precipitation of W(CtCCtCSiMe3)(CO)3Cp (3) as a pale
yellow powder, which was washed with several portions of cold
hexane and air-dried (190 mg, 80%). Anal. Found for C15H14O3-
SiW: C, 39.18; H, 3.11. Calcd: C, 39.68; H, 3.08. IR (CH2-
Cl2): ν(CtC) 2174 w, 2127 w, ν(CO) 2045 vs, 2026 m, 1957 br
(CO) 2038 vs, 1956 br cm-1 1H NMR (CDCl3): δ 7.27-7.46
.
(m, 5H, Ph), 5.68 (s, 5H, Cp). 13C NMR (CDCl3): δ 227.60 (d,
J CW ) 60 Hz, CO), 210.64 (d, J CW ) 71 Hz, CO), 132.38 (s,
o-C), 128.16 (s, m-C), 127.97 (s, p-C), 123.05 (s, i-C), 111.03
(d, J CW ) 22 Hz, CR), 91.62 (s, Cp), 76.19, 73.78 (2 × s, Cγ and
Cδ). FAB MS (m/z): 458, M+; 430, [M - CO]+.
P r ep a r a tion of Mo(CtCCtCP h )(CO)3Cp (5-Mo). Using
conditions similar to those described above for 5-W, a solution
of Mo(CtCCtCH)(CO)3Cp (100 mg, 0.34 mmol) in dry, de-
gassed NHPri2 was treated with PhI (100 mg, 0.50 mmol), Pd-
(PPh3)4 (20 mg, 0.017 mmol), and CuI (7 mg, 0.03 mmol) and
stirred for 16 h in the dark. Preparative TLC (light petroleum/
acetone, 7/3) separated many bands. A bright yellow band (Rf
) 0.57) yielded very light-sensitive Mo(CtCCtCPh)(CO)3Cp
cm-1 1H NMR (CDCl3): δ 5.66 (s, 5H, Cp), 0.20 (s, 9H, SiMe3).
.
(58) Holmes, A. B.; J ennings-White, C. L. D.; Schulthess, A. H.;
Akinde, B.; Walton, D. R. M. J . Chem. Soc., Chem. Commun. 1979,
840.
13C NMR (CDCl3): δ 227.53 (s, CO), 210.56 (d, J CW ) 77 Hz,
CO), 111.74 (br, CR), 110.86 (s, Câ), 91.53 (s, Cp), 90.04 (s, Cγ),

3548 Organometallics, Vol. 17, No. 16, 1998
Bruce et al.
(5-Mo) (50 mg, 40%) after crystallization (CH2Cl2/hexane).
Other bands were not investigated further. Anal. Found for
treated with tmed (150 µL, 117 mg, 1.01 mmol), and stirred
for 15 min. The finely divided suspension of unreacted CuCl
was allowed to settle prior to use in the coupling reactions.
P r ep a r a tion of {Cp (CO)3W}(CtC)4{W(CO)3Cp } (9-W).
The Hay catalyst was added in small portions to a solution of
1-W (500 mg, 1.3 mmol) in acetone (40 mL) while a stream of
O2 or air was bubbled through the reaction mixture until the
reaction was judged complete (TLC). Solvent was removed,
and the residue was purified by column chromatography on
Al2O3. A light petroleum/acetone gradient (6/4 to 4/6) was used
to elute a yellow-orange band, which yielded {Cp(CO)3W}-
(CtC)4{W(CO)3Cp} (9-W) (420 mg, 85%) as an orange, micro-
crystalline solid. The analytical sample was crystallized as
the 0.2CH2Cl2 solvate (NMR) from CH2Cl2/hexane. Anal.
Found for C24H10O6W2‚0‚2CH2Cl2: C, 37.22; H, 1.57. Calcd:
C, 37.31; H, 1.35. IR (CH2Cl2): ν(CtC) 2190 w, ν(CO) 2043 s,
C
18H10O3Mo: C, 57.70; H, 2.73. Calcd: C, 58.38; H, 2.70. IR
(CH2Cl2): ν(CtC) 2183 m, ν(CO) 2059 m, 2042 vs, 1970 br
cm-1
.
1H NMR (CDCl3): δ 7.46-7.27 (m, 5H, Ph), 5.58 (s, 5H,
Cp). 13C NMR (CDCl3): δ 237.50 (s, CO), 221.77 (s, CO),
132.31 (s, o-C), 128.15 (s, m-C), 127.92 (s, p-C), 123.15 (s, i-C),
110.92 (s, CR), 93.02 (s, Cp), 76.42 (s, Cδ), 72.59 (s, Cγ). ES
MS (with added NaOMe; low cone voltage) (m/z): 402, [M +
OMe]-.
P r ep a r a t ion of W(CtCCtCC6H 4Me-4)(CO)3Cp (6).
NHiPr2 (5 mL) was added to a solid mixture of 1-W (100 mg,
0.26 mmol), 4-MeC6H4I (60 mg, 0.28 mmol), Pd(PPh3)4 (15 mg),
and CuI (5 mg). The mixture was degassed and was stirred
at 50 °C for 24 h. After removal of solvent, the solid residue
was chromatographed on Al2O3 with benzene as eluant. An
orange solution was obtained. The product was precipitated
from benzene/hexane, washed with hexane, and dried in vacuo
at room temperature to give W(CtCCtCC6H4Me-4)(CO)3Cp
(6) (55 mg, 51%), mp 168-170 °C (dec). Anal. Found for
1959 vs cm-1
.
1H NMR (CDCl3): δ 5.67 (s, Cp). 13C NMR
(CDCl3): δ 227.32 (s, CO), 210.26 (s, CO), 112.39 (br, CR), 91.66
(s, Cp), 91.60 (s, Câ), 63.70 (s, Cγ), 60.91 (s, Cδ). ES MS (with
Ag+) (m/z): 1631, [2M + Ag]+; 1575, [2M + Ag - 2CO]+; 911-
854, [M + Ag + NCMe - nCO]+ (n ) 0-2); 813, [M + Ag -
2CO]+.
C
19H12O3W: C, 48.21; H, 2.55. Calcd: C, 48.33; H, 2.56. IR
(Nujol): ν(CtC) 2180 m; ν(CO) 2056 m, 2030 s, 1956 (sh), 1936
s cm-1 1H NMR (CDCl3): δ 2.32 (s, 3H, Me), 5.64 (s, 5H, Cp),
.
P r ep a r a tion of {Cp (CO)3Mo}(CtC)4{Mo(CO)3Cp } (9-
Mo). Similarly, 1-Mo (200 mg, 0.68 mmol) in acetone (25 mL)
gave {Cp(CO)3Mo}(CtC)4{Mo(CO)3Cp} (9-Mo) as a highly
light-sensitive, burnt orange powder (80-120 mg, 40-60%).
7.04 (d, 2H, J HH ) 8 Hz, Hm or Ho of C6H4), 7.31 (d, 2H, J HH
)
8 Hz, Ho or Hm of C6H4). FAB MS (m/z): 472, M+; 444, [M -
CO]+; 388, [M - 3CO]+.
P r ep a r a tion of W(CtCCtCC6H4OMe-4)(CO)3Cp (7). A
similar reaction with 1-W (100 mg, 0.26 mmol), 4-MeOC6H4I
(90 mg, 0.38 mmol), Pd(PPh3)4 (10 mg, 0.009 mmol), and CuI
IR (CH2Cl2): ν(CtC) 2140w, ν(CO) 2049s, 1973vs cm-1 1H
.
NMR (CDCl3): δ 5.78 (s, 5H, Cp); 13C NMR (CDCl3): δC 237.22,
221.41 (2 x s, CO), 112.24 (s, CR), 93.12 (s, Cp), 92.22 (s, Câ),
63.47 (s, Cγ), 59.95 (s, Cδ). ES MS (with Ag+) (m/z): 734, [M
+ Ag + NCMe]+.
(7 mg) in NHPri (5 mL) at 40 °C overnight afforded orange
2
W(CtCCtCC6H4OMe-4)(CO)3Cp (7) (47 mg, 35%), mp 148-
151 °C (dec). Anal. Found for (C19H12O4W‚0.2CH2Cl2): C,
45.54; H, 2.38. Calcd: C, 45.65; H, 2.47. IR (Nujol): ν(CtC)
P r ep a r a tion of cis-W(CtCCtCP h )(CO)2(P P h 3)Cp (11).
A solution of W(CtCCtCPh)(CO)3Cp (5-W) (240 mg, 0.52
mmol) and PPh3 (145 mg, 0.55 mmol) in CH2Cl2 (50 mL) was
purged with nitrogen and treated with tmno in portions until
the reaction was complete (IR). The solution was filtered
through a pad of silica gel and then further purified by
preparative TLC to give yellow W(CtCCtCPh)(CO)2(PPh3)Cp
(11) (67 mg, 20%) after crystallization (CH2Cl2/MeOH). Anal.
Found for C35H25O2PW: C, 61.01; H, 3.89. Calcd: C, 60.71;
H, 3.61. IR (CH2Cl2): ν(CtC) 2172 m, ν(CO) 2039 w, 1953
2174 w, ν(CO) 2052 m, 2031 s, 1951 s, 1934 s cm-1 1H NMR
.
(CDCl3): δ 3.78 (s, 3H, Me), 5.64 (s, 5H, Cp), 6.79 (d, 2H, J HH
) 9 Hz, Hm or Ho of C6H4), 7.36 (d, 2H, J HH ) 9 Hz, Ho or Hm
of C6H4). FAB MS (m/z): 488, M+; 460, [M - CO]+.
P r ep a r a tion of W(CtCCtCC6H4CO2Me-4)(CO)3Cp (8).
A similar reaction with 1-W (100 mg, 0.26 mmol), 4-IC6H4-
CO2CH3 (105 mg, 0.40 mmol), Pd(PPh3)4 (10 mg, 0.009 mmol),
and CuI (5 mg) in NHPri (5 mL) at 65 °C for 5 h gave yellow
2
W(CtCCtCC6H4CO2Me-4)(CO)3Cp (8) (120 mg, 89%), mp
161-164 °C (dec). Anal. Found for C20H12O5W.0.1CH2Cl2: C,
45.89; H, 2.49. Calcd: C, 46.02; H, 2.34. IR (Nujol): ν(CtC)
2179 m, ν(CO) 2058 m, 2030 s, 1966 s, 1931 s; ν(CO2) 1713 m,
vs, 1875 s cm-1 1H NMR (CDCl3): δ 7.52-7.20 (m, 20H, PPh3
.
and Ph), 5.44 (s, 5H, Cp). 13C NMR (CDCl3): δ 243.15 (d, J CP
) 22 Hz,CO), 222.63 (d, J CP ) 20 Hz, CO), 135.05-124.00 (m,
Ph), 113.27 (d, J CW ) 8 Hz, CR), 100.14 (s, Câ), 91.23 (s, Cp),
72.75, 72.2 (2 × s, Cγ and Cδ). 31P NMR (CDCl3): δP 21.00 (t,
J PW ) 121.5 Hz, PPh3). ES MS (low cone voltage with NaOMe)
(m/z): 715, [M + Na]+.
1601 m cm-1 1H NMR (CDCl3): δ 3.89 (s, 3H, Me), 5.66 (s,
.
5H, Cp), 7.45 (d, 2H, J HH ) 8.5 Hz, Hm or Ho of C6H4), 7.93 (d,
2H, J HH ) 8.5 Hz, Ho or Hm of C6H4). ES MS (MeCN/H2O with
Ag+) (m/z): 516, M+; 488, [M - CO]+; 450, [M - 2CO]+; 432,
[M - 3CO]+; 373, [M - 3CO - CO2Me]+; 136, [HC6H4CO2Me]+.
P r ep a r a tion of W[CtCC{CHdC(CN)2}C{dC(CN)2}H]-
(CO)3Cp (10). A solution of 1-W (200 mg, 0.52 mmol) in CH2-
Cl2 (15 mL) was treated with tetracyanoethene (67 mg, 0.52
mmol) and stirred for 5 min. The initially yellow solution
acquired an intense purple color during this time. Solvent was
removed, and the residue was extracted with the minimum
volume of fresh CH2Cl2 and then filtered dropwise into rapidly
stirred hexane. The resulting purple precipitate was collected
and crystallized (CH2Cl2/hexane) to give W{CtCC[dC(CN)2]C-
[dC(CN)2]H}(CO)3Cp (10) as dark purple blocks (225 mg, 84%).
Crystals suitable for the X-ray study were obtained from 1,2-
dichloroethane/hexane. Anal. Found for C18H6O3N4W: C,
42.21; H, 1.32. Calcd: C, 42.35; H, 1.18. IR (CH2Cl2): ν(CN)
P r ep a r a tion of cis-W(CtCP h )(CO)2(P P h 3)Cp (12): A
solution of W(CtCPh)(CO)3Cp (100 mg, 0.23 mmol) and PPh3
(70 mg, 0.27 mmol) in CH2Cl2 (20 mL) was purged with
nitrogen and treated with freshly sublimed tmno in several
portions until the reaction was judged complete (IR; the ν-
(CO) 2038 cm-1 band of the starting material was monitored).
Preparative TLC (light petroleum/acetone, 7/3) gave bright
yellow needles of W(CtCPh)(CO)2(PPh3)Cp (12) (67 mg, 44%)
from the major band. Anal. Found for C33H25O2PW: C, 59.51;
H, 3.20. Calcd: C, 59.29; H, 3.74. IR (CH2Cl2): ν(CtC) 2089
w, ν(CO) 1949 vs, 1863 s cm-1
.
1H NMR (CDCl3): δ 7.53-
6.53 (m, 20H, Ph), 5.46 (s, 5H, Cp). 13C NMR (CDCl3):
δ
244.54 (br, CO), 228.79 (d, J CP ) 5 Hz, CO), 133.82-124.75
(m, Ph), 91.22 (s, Cp). ES MS (m/z): (low cone voltage) 668,
M+; (low cone voltage with NaOMe) 691, [M + Na]+; (high cone
voltage) 668-612, [M - nCO]+ (n ) 0-2).
Cr ysta llogr a p h y. Unique room-temperature four-circle
diffractometer data sets were recorded (monochromatic Mo KR
radiation, λ ) 0.71073 Å; T ∼ 295 K) and used in the full-
matrix least-squares refinements after analytical absorption
correction. Anisotropic thermal parameter forms were refined
2221 w, ν(CtC) 2078 m, ν(CO) 2030 s, 1970 br cm-1 1H NMR
.
(CDCl3): δ 7.62 (s, 1H, CHd), 5.80 (s, 5H, Cp). 13C NMR
(CDCl3): δ 221.05 [s, C(3)], 209.15 (s, CO), 148.70 [s, C(2)],
94.41 [s, C(4)], 92.19 (s, Cp), 91.90 [s, C(1)]. FAB MS (m/z):
510, M+.
Oxid a tive Cou p lin g of M(CtCCH)(CO)3Cp . P r ep a r a -
tion of th e Ha y Ca ta lyst (Cu Cl/tm ed ). Cuprous chloride
(100 mg, 1.01 mmol) was suspended in dry acetone (5 mL),
for the non-hydrogen atoms; (x, y, z, Uiso
)
were included
H
constrained at estimated values. Conventional residuals R,

Tungsten Diynyl Complex W(CtCCtCH)(CO)3(η-C5H5)
Organometallics, Vol. 17, No. 16, 1998 3549
Rw on |F| at convergence are given, statistical weights deriva-
tive of σ2(I) ) σ2(Idiff) + 0.0004σ4(Idiff) being employed. Neutral
atom complex scattering factors were employed, and computa-
tions were made using the XTAL 3.4 program system59
implemented by S. R. Hall. Pertinent results are given in
the figures and tables; material deposited comprises all
coordinates and thermal parameters and full molecular non-
hydrogen geometries.
F or Com p ou n d 12. Merging of a redundant data set
measured over a quadrant of reciprocal space after absorption
correction yielded Rint ) 0.045.
Ack n ow led gm en t. Support of this work by the
Australian Research Council is gratefully acknowledged.
P.J .L. was the holder of an Australian Post-Graduate
Award. We thank Professor Brian Nicholson (University
of Waikato, Hamilton, New Zealand) for the electrospray
mass spectra.
Ab n or m a l F ea t u r es/Va r ia t ion s in P r oced u r e. F or
Com p ou n d 3. Methyl groups were modeled over two sets of
sites, disordered about the mirror plane and necessarily of
equal occupancy in the present space group. Deterioration of
the crystal by ca. 12% over the course of data collection was
compensated for by scaling.
Su p p or tin g In for m a tion Ava ila ble: X-ray crystallo-
graphic files, in CIF format, for 3, 10, and 12 are available
through the Internet only. Access information is given on any
current masthead page. Crystallographic data have also been
deposited with Cambridge and can be obtained by referencing
102116 for 3, 102117 for 10, and 102118 for 12.
(59) Hall, S. R., King, G. S. D., Stewart, J . M., Eds. The XTAL 3.4
Users Manual; University of Western Australia: Lamb, Perth, 1994.
OM980031R