η2-alkynyl and vinylidene transition metal complexes. 6. Reaction of tungsten vinylidene complexes with chlorophosphines as nucleophile. Preparation and crystal structural analysis of neutral η2-phosphinovinyl complexes

Article abstract of DOI:10.1021/om000659d

The reaction of vinylidene complexes [(η⁵-C₅H₅)(CO)(NO)WqqCqqCHR] [R = H (1a), CH₃ (1b), C₆H₅ (1c)] with chlorodiphenylphosphine (2) leads to neutral {(η⁵-C₅H₅

Full text of DOI:10.1021/om000659d

Organometallics 2000, 19, 5281-5286
5281
η2-Alk yn yl a n d Vin ylid en e Tr a n sition Meta l Com p lexes.
6.1 Rea ction of Tu n gsten Vin ylid en e Com p lexes w ith
Ch lor op h osp h in es a s Nu cleop h ile. P r ep a r a tion a n d
Cr ysta l Str u ctu r a l An a lysis of Neu tr a l η2-P h osp h in ovin yl
Com p lexes
J unes Ipaktschi,*,† Thomas Klotzbach,† and Ansgar Du¨lmer‡
Institute of Organic Chemistry and Institute of Inorganic and Analytical Chemistry,
J ustus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany
Received J uly 31, 2000
The reaction of vinylidene complexes [(η5-C5H5)(CO)(NO)WdCdCHR] [R ) H (1a ), CH3
(1b), C6H5 (1c)] with chlorodiphenylphosphine (2) leads to neutral {(η5-C5H5)(Cl)(NO)W(Cd
CHR)[P(C6H5)2]} [R ) H (3a ), CH3 (3b), C6H5 (3c)]. Analogously the reaction of chlorodi-
tert-butylphosphine (4) with [(η5-C5H5)(CO)(NO)WdCdCH2] (1a ) gives rise to chloro(η5-
cyclopentadienyl)nitrosyl(η2-di-tert-butylphosphinovinyl)tungsten (5). The formation of these
metallacyclopropane rings is rationalized by the nucleophilic attack of chlorophosphine on
the CR carbon of the vinylidene, followed by substitution of the carbonyl ligand. Single-
crystal X-ray diffraction data of 3a -c and 5 are reported.
In tr od u ction
Intending to explore the reactivity of neutral tungsten
as well as molybdenum vinyliden complexes, we inves-
tigated the reaction of vinylidene complexes 1a -c with
chlorophosphines 2 and 4. We observed a nucleophilic
addition of phophines to the R-carbon atom, which gives
rise to the mononuclear η2-phosphinovinyl complexes
3a -c and 5 with high yield.
The addition of nucleophiles to unsaturated ligands
such as alkyne or alkene, activated by coordination to
transition metals, has proven to be useful for the
preparation of new organometallic complexes and is a
versatile methodology in organic synthesis.2 Although
useful for synthetic purposes, so far the nucleophilic
addition to the vinylidene moiety has hardly been
studied.3 Theoretical studies predict the electron defi-
ciency at the R-carbon and the localization of electron
density in the MdC double bond and at the â-carbon.4,5
Chemical reactivity is oriented toward electrophilic
attack at the â-carbon atom and nucleophilic attack at
the R-carbon atom.4,5 Several examples of addition of
nucleophiles, including amines,6 water,7 alcohols,7a,e,g,8
thiols,7e,9 as well as the addition of tert-phosphines10 to
cationic vinylidene complexes have been reported.
Although three-membered metallacycles with the
M-P-C unit were often the subject of investigation,11
only a few examples of mononuclear complexes12 with
a M-P-CdC skeleton have been reported.
(7) (a) Bianchini, C.; Marchi, A.; Marvelli, L.; Peruzzini, M.; Rome-
rosa, A.; Rossi, R. Organometallics 1996, 15, 3804-3816, and refer-
ences therein. (b) Bianchini, C.; Casares, J . A.; Peruzzini, M.; Rome-
rosa, A.; Zanobini, F. J . Am. Chem. Soc. 1996, 118, 4585-4594. (c)
Knaup, W.; Werner, H. J . Organomet. Chem. 1991, 411, 471-489. (d)
Mountassir, C.; Ben-Hadda, T.; Le Bozec, H. J . Organomet. Chem.
1990, 388, C13-C16. (e) Boland-Lussier, B. E.; Hughes, R. P. Orga-
nometallics 1982, 1, 635-639. (f) Sullivan, B. P.; Smythe, R. S.; Kober,
E. M.; Meyer, T. J . J . Am. Chem. Soc. 1982, 104, 4701-4703. (g) Bruce,
M. I.; Swincer, A. G. Aust. J . Chem. 1980, 33, 1471-1483.
(8) Bruce, M. I.; Swincer, A. G.; Wallis, R. C. J . Organomet. Chem.
1979, 171, C5-C8.
(9) Bianchini, C.; Glendenning, L.; Peruzzini, M.; Romerosa, A.;
Zanobini, F. J . Chem. Soc., Chem. Commun. 1994, 2219-2220.
(10) (a) Bianchini, C.; Meli, A.; Peruzzini, M.; Zanobini, F.; Zanello,
P. Organometallics 1990, 9, 241-250 (b) Senn, D. R.; Wong, A.; Patton,
A. T.; Marsi, M.; Strouse, C. E.; Gladysz, J . A. J . Am. Chem. Soc. 1988,
110, 6096-6109. (c) Boland-Lussier, B. E.; Churchill, M. R.; Hughes,
R. P.; Rheingold, A. L. Organometallics 1982, 1, 628-634.
† Institute of Organic Chemistry.
‡ Institute of Inorganic and Analytical Chemistry.
(1) Ipaktschi, J .; Mirzaei, F.; Reimann, K.; Beck, J .; Serafin, M.
Organometallics 1998, 17, 5086-5090.
(2) Hegedus, L. S. Transition Metals in the Synthesis of Complex
Organic Molecules; University Science Books, Mill Valley, CA, 1994.
(3) (a) Del R´ıo, I.; van Koten, G. Tetrahedron Lett. 1999, 40, 1401-
1404. (b) Buriez, B.; Cook, D. J .; Harlow, K. J .; Hill, A. F.; Welton, T.;
White A. J . P.; Williams, D. J .; Wilton-Ely, J . D. E. T. J . Organomet.
Chem. 1999, 578, 264-267. (c) Wolf, J .; Stu¨er, W.; Gru¨nwald, C.;
Werner, H.; Schwab, P.; Schulz, M. Angew. Chem. 1998, 110, 1165-
1167. (d) Terry, M. R.; Mercando, L. A.; Kelley, C.; Geoffroy, G. L.;
Nombel, P.; Lugan, N.; Mathieu, R.; Ostrander, R. L.; Owens-
Waltermire, B. E.; Rheingold, A. L. Organometallics 1994, 13, 843-
865.
(4) Kostic, N. M.; Fenske, R. F. Organometallics 1982, 1, 974-982.
(5) For general reviews see: (a) Werner, H. Nachr. Chem., Technol.
Lab. 1992, 40, 435-444. (b) Bruce, M. I. Chem. Rev. 1991, 91, 197-
257. (c) Werner, H. Angew. Chem. 1990, 102, 1109-1121; Angew.
Chem., Int. Ed. Engl. 1990, 29, 1077. (d) Davies, S. G.; McNally, J . P.;
Smallridge, A. J . Adv. Organomet. Chem. 1990, 30, 1-76. (e) Antonova,
A. B.; J ohansson, A. A.; Russ. Chem. Rev. 1989, 58, 693-710. (f) Bruce,
M. I.; Swincer, A. G. Adv. Organomet. Chem. 1983, 22, 59-128.
(6) Bianchini, C.; Masi, D.; Romerosa, A.; Zanobini, F.; Peruzzini,
M. Organometallics 1999, 18, 2376-2386.
(11) (a) Reisacher, H.-U.; Duesler, E. N.; Paine, R. T. J . Organomet.
Chem. 1997, 539, 37-44. (b) Baker, R. T.; Calabrese, J . C.; Harlow, R.
L.; Williams, I. D. Organometallics 1993, 12, 830-841. (c) Weber, L.;
Matzke, T.; Boese, R. Chem. Ber. 1990, 123, 739-745. (d) Carrano, C.
J .; Cowley, A. H.; Nunn, C. M.; Pakulski, M.; Quashie S. J . Chem.
Soc., Chem. Commun. 1988, 170-171. (e) Carriedo, G. A.; Riera, V.
Luz Rodriguez, M. J . Organomet. Chem. 1986, 314, 139-149. (f)
Lindner, E.; Ku¨ster, E. U.; Hiller, W.; Fawzi, R. Chem. Ber. 1984, 117,
127-141. (g) Lindner, E.; Starz, K. A.; Eberle, H.-J .; Hiller, W. Chem.
Ber. 1983, 116, 1209-1218.
10.1021/om000659d CCC: $19.00 © 2000 American Chemical Society
Publication on Web 11/05/2000

5282 Organometallics, Vol. 19, No. 25, 2000
Ipaktschi et al.
Resu lts a n d Discu ssion
The treatment of vinylidene complexes [(η5-C5H5)-
(CO)(NO)WdCdCHR] [R ) H (1a ), CH3 (1b), C6H5 (1c)]
with chlorodiphenylphosphine (2) and of 1a with chlo-
rodi-tert-butylphosphine (4) in THF at -30 °C to +15
°C yields after workup the neutral complexes [(η5-C5H5)-
(Cl)(NO)W(CdCHR)(PR′2)] 3a -c [R ) H, R′ ) C6H5
(3a ), R ) CH3, R′ ) C6H5 (3b), R ) R′ ) C6H5 (3c)] and
5 [R ) H, R′ ) C(CH3)3 (5)] as orange crystals with 50-
1
87% yield. Controlling the reaction by H NMR experi-
ments demonstrates the quantitative formation of 3a -c
and 5.
The solid compounds 3a -c and 5 can be stored under
inert gas at -20 °C. The solutions of 3b and 3c
decompose at room temperature.
Figu r e 1. Molecular structure and atom-numbering scheme
The structures of 3a -c and 5 are confirmed by
spectroscopic as well as X-ray crystal structure analysis
(see Experimental Section). According to the NMR
spectra, 3b and 3c in solution undergo an E/ Z isomer-
ization, which can be pursued by 31P NMR spectroscopy.
At ambient temperature the E/Z isomer ratios of 3b and
3c are 3:1 and 1:1.2, respectively. The 31P resonances
are accompanied by 183W satellites (1J P-W ) 118-133
for {(η5-C5H5)(Cl)(NO)W(CdCH2)[P(C6H5)2]} (3a ) with H
atoms. Thermal ellipsoids shown at the 30% probability
level.
1
Hz). The J (183W-31P) coupling constants of 3a -c and
5 are comparable to those found in the complexes {(η5-
C5H5)(CO)2W(CdCH2)[P(C6H5)2]}12 (135.5 Hz), {WMoCl2-
[µ2-(C6H5)2PCdCH(C6H5)][µ2-P(C6H5)2](η5-C5H5)2}13a (115
Hz), and {W2Cl2[µ2-(C6H5)2PCdCH(C6H5)][µ2-P(C6H5)2]-
(η5-C5H5)2}13b (121.8 Hz).14
1
The H NMR spectra of 3a and 5 show characteristic
signals of the magnetically nonequivalent methylene
3
protons. Because of their different J (31P-1H) coupling
constants [3a , δ 7.65 ppm (3J H-P ) 15 Hz) and 6.55 ppm
(3J H-P ) 35 Hz); 5, δ 7.47 ppm (3J H-P ) 13 Hz) and 6.49
ppm (3J H-P ) 32 Hz)], they can be assigned to the cis-
and trans-position relative to the phosphor atom.12b,15
The 3J (31P-13C) coupling constants16 of the E and Z
isomers of 3b and 3c also differ significantly: the carbon
atoms of the Z isomers of 3b and 3c couple in both cases
Figu r e 2. Molecular structure and atom-numbering scheme
for {(η5-C5H5)(Cl)(NO)W[CdCH(CH3)][P(C6H5)2]} (3b) with
H atoms. Thermal ellipsoids shown at the 30% probability
level.
3
with J C-P ) 17 Hz, while the E isomers have a coupling
constant of 9 and 6 Hz, respectively.
Molecu la r Str u ctu r es of 3a -c a n d 5. Suitable
single crystals of 3a -c and 5 were grown from a
dichloromethane solution by slow diffusion of pentane
at ambient temperature. The crystallization of 3b and
3c provides the E and Z isomer, respectively, which was
confirmed by 1H NMR spectra recorded shortly after the
crystalline compounds have been dissolved and by their
molecular structures.
It is interesting to note that for 3a -c and 5 the
resonances of the Cp rings split into doublets with a
coupling constant of 1.5 Hz due to a J C-P coupling.
The formation of metallacyclopropane rings 3a -c and
5 can be explained by the initial nucleophilic attack of
the phosphine on the vinylidene R-carbon atom, forming
the intermediate 6, followed by the substitution of
chloride to 7 and the elimination of a carbonyl group.
2
The single crystal of compound 5 is an axis twin along
[100]. The crystal parameters, data collection param-
eters, and conditions for structure refinement are sum-
marized in Table 1. Selected bond distances and angles
are given in Table 2. A view of the molecules 3a -c and
5 is shown in Figures 1-4. The X-ray diffraction study
confirmed the structures of the molecules as pseudo
four-legged piano stool complexes with a W atom bonded
to a η5-Cp ring, to a terminal nitrosyl group and a
terminal chlorine standing cis to each other, and to a
phosphinovinyl ligand building a strained three-mem-
bered metallacycle.
(12) (a) Lehotkay, Th.; Ostermeier, J .; Ogric, C.; Kreissl, F. R. J .
Organomet. Chem. 1996, 520, 59-62. (b) Ostermeier, J .; Hiller, W.;
Kreissl, F. R. J . Organomet. Chem. 1995, 491, 283-289.
(13) (a) Acum, G. A.; Mays, M. J .; Raithby, P. R.; Solan, G. A. J .
Chem. Soc., Dalton Trans. 1995, 3049-3056. (b) Mays, M. J .; Reinisch,
P. F.; Solan, G. A.; McPartlin, M.; Powell, H. R. J . Chem. Soc., Dalton.
Trans. 1995, 1597-1606. (c) Conole, G.; Hill, K. A.; McPartlin, M.;
Mays, M. J .; Morris, M. J . J . Chem. Soc., Chem. Commun. 1989, 688-
690. (d) Grist, N. J .; Hogarth, G.; Knox, S. A. R.; Lloyd, B. R.; Morton,
D. A. V.; Orpen, A. G. J . Chem. Soc., Chem. Commun. 1988, 673-675.
(14) Due to thermal sensitivity of 3b and 3c, the thermodynamic
parameters of the E/Z isomerization could not be determined by
dynamic 1H NMR spectroscopy.
(15) L’vova, S. D.; Kozlov, Yu. P.; Gunar, V. I. Zh. Obshch. Khim.
1977, 47, 1251-1256; J . Gen. Chem. USSR 1977, 47 (2), 1153-1157.
(16) Duncan, M.; Gallagher, M. J . Org. Magn. Reson. 1981, 15, 37-
42.
The most notable features of the metallacyclic sys-
tems 3a -c and 5 are the long W-P bonds on one hand

Neutral η2-Phosphinovinyl Complexes
Organometallics, Vol. 19, No. 25, 2000 5283
Ta ble 1. Cr ysta l Da ta a n d Con d ition s for Cr ysta llogr a p h ic Da ta Collection a n d Str u ctu r e Refin em en t
3a
3b
3c
5 (axis twin along [100])a
formula
cryst size, mm
fw
C19H17NOPClW
0.31 × 0.15 × 0.27
525.630
C20H19NOPClW
0.35 × 0.27 × 0.34
539.657
C25H21NOPClW
0.35 × 0.46 × 0.42
601.729
C15H25NOPClW
0.08 × 0.08 × 0.23
485.648
color
orange, transparent
orthorhombic
Pbca (No. 61)
orange, transparent
monoclinic
P21/ n (No. 14)
a ) 15.157(1) Å
orange-red, transparent
monoclinic
Cc (No. 15)
yellow, transparent
monoclinic
P21/ c (No. 14)
a ) 13.138(1) Å
b ) 12.995(2) Å, â ) 91.61(1)°
c ) 10.420(1) Å
cryst syst
space group
lattice constants
a ) 15.144(1) Å
a ) 17.123(3) Å
b ) 15.281(1) Å
b ) 7.850(1) Å,
â ) 110.32 (1)°
c ) 17.645(1) Å
1968.87 Å3
Z ) 4
b ) 9.713(2) Å,
â ) 116.84(3)°
c ) 15.258(3) Å
2264.09 Å3
Z ) 4
c ) 16.001(2) Å
3784.84 Å3
Z ) 8
volume
formula units per unit cell
density calc
linear abs coeff
diffractometer
radiation
monochromator
2θ range
1778.29 Å3
Z ) 4
1.89 g/cm3
64.7 cm-1
1.82 g/cm3
1.77 g/cm3
1.81 g/cm3
67.3 cm-1
60.9 cm-1
53.1 cm-1
Image Plate Diffractometer System (STOE)
Mo KR
graphite
9.5° e 2θ e 56.3°
-19 e h e 19,
-10 e k e 10,
-23 e l e 23
17 792
Mo KR
graphite
Mo KR
graphite
Mo KR
graphite
9.5° e 2θ e 56.3°
-19 e h e 18,
-19 e k e 20,
-21 e l e 21
34 172
8.1° e 2θ e 52.1°
-20 e h e 20,
-11 e k e 11,
-18 e l e 18
8294
8.1° e 2θ e 52.1°
-14 e h e 14,
-14 e k e 14,
-12 e l e 12
5659
no. of rflns measd
no. of indep rflns
Rint
4452
0.102
4715
0.0785
3921
0.069
1817
0.068
no. of indep rflns with
Fo > 4σ(Fo)
temperature
3103
3988
3731
1448
293 K
293 K
293 K
293 K
applied corrections
structure determination
and refinement
Lorentz and polarization coefficients for 3a -c and 5
W, Cl, and P positional parameters from direct methods (program SHELXS-97b);
further atoms from ∆F synthesis (program SHELXL-97c), structure refinement by
the anisotropic full-matrix least-squares procedure for all non-hydrogen atoms; hydrogen
position refinement by “riding” model
no. of parameters
wR2
R1
217
226
272
181
0.0686
0.0508
0.0292
1.59
0.0979
0.0468
0.0387
3.24
0.0897
0.0361
0.0347
2.34
0.0688
0.0383
0.0274
0.62
R1[Fo > 4σ(Fo)]
max and min in
∆σ (e Å-3
)
-1.57
-1.98
-2.96
-0.73
a
b
For integration the IPDS-software TWIN of the firm STOE was applied. Sheldrick, G. M. SHELXS-97, Program for the Solution of
Crystal Structures; Universita¨t Go¨ttingen, 1997. c Sheldrick, G. M. SHELXL-97, Program for Crystal Structure Refinement; Universita¨t
Go¨ttingen, 1997.
Figu r e 4. Molecular structure and atom-numbering scheme
for {(η5-C5H5)(Cl)(NO)W(CdCH2)[P(CMe3)2]} (5) with H
atoms. Thermal ellipsoids shown at the 30% probability
level.
Figu r e 3. Molecular structure and atom-numbering scheme
for {(η5-C5H5)(Cl)(NO)W[CdCH(C6H5)][P(C6H5)2]} (3c) with
H atoms. Thermal ellipsoids shown at the 30% probability
level.
bond lengths of 3b,c and 5, ranging from 1.75 to 1.76
Å, indicate a bond order higher than unity and suggest
an alternative view of the ligand as a Ph2PdCdCHR
unit.11g,13c,d The average W-P-C(1) angle of 3a -c and
5 (59.0°), the P-W-C(1) angle (44.5°), and P-C(1)-W
angle (76.5°) show a significant deformation of the
and the short W-C(1) and P-C(1) bonds on the other
hand, indicating that complex 8 is the preferred struc-
ture in the solid state (Scheme 4). Similar bond lengths
were found in binuclear complexes.13a-d The P-C(1)

5284 Organometallics, Vol. 19, No. 25, 2000
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles (d eg) for 3a -c a n d 5
Ipaktschi et al.
3a
3b
3c
5
Distances
W-P
2.437(1)
2.448(1)
2.434(2)
2.178(7)
1.760(9)
1.775(8)
2.440 (2)
1.328(11)
1.808(9)
1.820(8)
2.467(2)
W-C(1)
P-C(1)
2.171(5)
1.771(5)
1.774(4)
2.455(1)
1.312(8)
1.813(4)
1.807(4)
2.139(5)
1.755(6)
1.778(5)
2.444(2)
1.325(9)
1.809(6)
1.815(6)
1.487(12)
2.142(8)
1.760(7)
1.766(7)
2.437(2)
1.327(11)
1.907(8)
1.864(11)
W-N
W-Cl
C(1)-(C2)
P-C(11)
P-C(21)
C(2)-C(3)
C(2)-C (31)
range W-C(Cp)
1.448(13)
2.289(11)-2.365(11)
2.298(6)-2.366(6)
2.282(6)-2.379(7)
2.307(10)-2.421(11)
Angles
44.4(2)
77.2 (2)
58.4(2)
94.6(1)
131.6(2)
91.0(2)
124.7(2)
122.3(2)
170.7(4)
147.8(5)
134.9(5)
126.6(8)
P-W-C(1)
44.8(1)
75.6(2)
59.6(2)
95.7(2)
130.8(1)
91.8(2)
122.5(2)
124.7(2)
168.2(4)
148.7(4)
135.2(4)
44.4(2)
75.5(3)
60.0(3)
94.0(3)
130.7(2)
87.2(3)
120.1(3)
127.2(3)
170.5(8)
149.1(7)
134.8(7)
44.2(2)
77.07(3)
58.1(3)
98.0(3)
129.6(2)
95.1(3)
119.3(3)
124.1(4)
165.0(7)
145.2(7)
136.8(7)
P-C(1)-W
C(1)-P-W
N-W-Cl
C(1)-W-Cl
C(1)-W-N
W-P-C(11)
W-P-C(21)
W-N-O
W-C(1)-C(2)
P-C(1)-C(2)
C(1) -C(2) - C(3)
C(1)-C(2)-C(31)
C(1) - P - C(11)
C(1)-P-C(21)
C(11)-P-C(21)
128.8(9)
113.1(4)
116.8(4)
109.2 (4)
111.7(2)
118.2(2)
109.4(2)
113.2(3)
116.4(3)
110.1(3)
111.1(4)
114.2(4)
114.5(5)
Sch em e 1
Sch em e 2
to use. Literature methods were used to prepare [(η5C5H5)-
(CO)(NO)WdCdCHR] 1a ,c,17 [(η5-C5H5)(CO)2(NO)W],18 and
propynyllithium.19 All other compounds were commercially
available. NMR spectra were obtained on Bruker AM 400 and
AC 200 spectrometers. Proton and carbon chemical shifts are
referred to tetramethylsilane, phosphorus chemical shifts to
formal three-membered heterocyclic structure, also in
favor of structure 8. The small P-W-C(1) angle simul-
taneously expands the N-W-Cl angle to 95.6° on
average.
Exp er im en ta l Section
(17) Ipaktschi, J .; Demuth-Eberle, G. J .; Mirzaei, F.; Mu¨ller, B. G.;
Beck, J .; Serafin, M. Organometallics 1995, 14, 3335-3341.
(18) Chin, T. T.; Hoyano, J . K.; Legzdins, P.; Malito, J . T. Inorg.
Synth. 1990, 28, 196-198.
Gen er a l Con sid er a tion s. All reactions were carried out
under an argon atmosphere (99.99%, by Messer-Griesheim)
with the use of standard Schlenk techniques. Solvents were
purified by standard methods and distilled under argon prior
(19) Suffert, J .; Toussaint, D. J . Org. Chem. 1995, 60, 3550-3553.

Neutral η2-Phosphinovinyl Complexes
Organometallics, Vol. 19, No. 25, 2000 5285
N, 2.95. 31P NMR (162 MHz, CDCl3, H3PO4 as external
Sch em e 3
1
standard): δ -85.5 [s, J P-W ) 131 Hz, P(C6H5)2]. 1H NMR
(400 MHz, CDCl3): δ 7.80-7.30 (m, 10H, C6H5), 7.65 (d, 1H,
cis-3J H-P ) 15 Hz, CdCH2), 6.55 (d, 1H, trans-3J H-P ) 35 Hz,
CdCH2), 5.85 (s, 5H, Cp). 13C NMR (100 MHz, CDCl3): δ 163.1
1
1
2
(d, J C-P ) 51 Hz, J C-W ) 51 Hz, W-CR), 133.5 (d, J C-P ) 9
2
Hz, Câ), 133.8 and 133.6 [two d, J C-P ) 12 Hz, C6H5 (ortho)],
4
131.2 and 130.8 [two d, J C-P ) 3 Hz, C6H5 (para)], 129.0 and
3
128.9 [two d, J C-P ) 12 Hz, C6H5 (meta)], 128.5 and 127.0
1
2
[two d, J C-P ) 50 Hz, C6H5(ipso)], 102.7 (d, J C-P ) 1.5 Hz,
Cp). IR (KBr): ν˜ (cm-1) 1610 (N≡O). MS (70 eV): m/e 525 (M+,
184W), 495 (M+ - NO); high-resolution mass spectrum calcd
for C19H17NOPCl182W (M+) m/e 523.0219, found m/e 523.0248.
{(η5-C5H 5)(Cl)(NO)W[CdCH(CH 3)][P (C6H 5)2]} (3b ). A
0.87 g (2.5 mmol) sample of tungsten vinylidene complex 1b
was dissolved in 15 mL of THF and cooled to -30 °C. To the
orange solution was added dropwise 0.46 mL (2.5 mmol, 55
mg) of chlorodiphenylphosphine (2). After complete addition
the cooling bath was removed immediately. When the forma-
tion of CO gas was complete, the THF was removed as fast as
possible under vacuum to avoid decomposition. Chromatog-
raphy on silica gel with 1:1 pentane/ether yielded 0.67 g (50%)
of 3b as a yellow solid. Crystallization from CH2Cl2 and
pentane produced orange crystals of the E isomer, mp 180-
182 °C dec. Anal. Calcd for C20H19NOPClW: C, 44.51; H, 3.55;
N, 2.60. Found: C, 44.59; H, 3.32; N, 2.91. Two isomers, E:Z
) 3:1 at room temperature: 31P NMR (162 MHz, CDCl3, H3-
Sch em e 4
1
PO4 as external standard): δ -80.5 and -87.0 [two s, J P-W
) 124 and 126 Hz, P(C6H5)2, E and Z]. 1H NMR (400 MHz,
3
CDCl3): δ 8.18 [dq (overlapping), 1H, J H-H ) 7 Hz, cis-3J H-P
) 14 Hz, 3J H-W ) 7 Hz, CdCHR, Z], 7.80-7.33 (m, 10H, C6H5),
3
δ 6.72 (dq, 1H, J H-H ) 7 Hz, trans-3J H-P ) 34 Hz, CdCHR,
E), 5.85 and 5.84 [two s (overlapping), 5H, Cp, Z and E], 2.11
orthophosphoric acid as the external standard. MS measure-
ments (70 eV) were performed on a Varian MAT 311-A. IR
spectra were recorded on a Bruker FT-IR IFS 85. Microanaly-
ses were done on a Carlo Erba 1104 elemental analyzer.
P r ep a r a tion of Com p ou n d s. [(η5-C5H5)(CO)(NO)WdCd
CH(CH3)] (1b). At -40 °C, a suspension of 23.1 mmol
propynyllithium in 45 mL of THF was added dropwise to the
orange solution of [(η5-C5H5)(CO)2(NO)W] (2.00 g, 6.0 mmol)
in THF (60 mL). After stirring at -30 °C for 6 h, 20 mL of
saturated aqueous sodium bicarbonate was added to the deep
green reaction mixture, which immediately changed its color
to wine red. The THF was removed under reduced pressure,
the residue extracted with diethyl ether, and the organic phase
dried over magnesium sulfate. Chromatography of the red-
brown oil on silica gel with 5:1 pentane/ether yielded 1.24 g
(60%) of 1b as a red-brown oil. Anal. Calcd for C9H9NO2W:
C, 31.15; H, 2.61; N, 4.04. Found: C, 31.02; H, 2.24; N, 3.94.
Two rotamers: 1H NMR (400 MHz, CDCl3): δ 5.87 (s, 5H, Cp),
5.75 and 5.70 (two q, 4:3, 1H, CâH), 1.70 and 1.65 (two d, 3:4,
3H, CH3). 13C NMR (100 MHz, CDCl3): δ 340.1 and 339.6 (two
CR), 210.7 and 210.4 (two CO), 123.5 and 123.2 (two Câ), 96.2
3
4
and 1.96 (dd and d, 3H, J H-H ) 7 Hz, J H-P ) 1 Hz, CH3, E
and Z). 13C NMR (100 MHz, CDCl3): δ 149.0 and 148.9 (two
1
1
d, J C-P ) 46 and 52 Hz, J C-W ) 51 and 52 Hz, W-CR, Z and
2
E), 147.2 and 145.6 (two d, J C-P ) 7 and 9 Hz, Câ, Z and E),
4
134.0-133.5 [m, C6H5 (ortho)], 131.1 and 130.8 [two d, J C-P
) 3 Hz, C6H5 (para), E], 131.1 and 130.7 [two d, 4J C-P ) 3 Hz,
C6H5 (para), Z], 129.3-128.8 [m, C6H5 (meta)], 129.0 and 127.6
1
[two d, J C-P ) 49 Hz, C6H5(ipso), Z], 128.1 and 126.5 [two d,
1J C-P ) 51 and 50 Hz, C6H5(ipso), E], 102.7 and 101.6 (two d,
2J C-P ) 1.5 Hz, Cp, E and Z), 26.0 and 20.6 (two d, J C-P ) 9
3
and 17 Hz, CH3, E and Z). IR (KBr): ν˜ (cm-1) 1611 (N≡O);
MS (70 eV) m/e 539 (M+, 184W), 509 (M+ - NO); high-resolution
mass spectrum calcd for C20H19NOPCl182W (M+) m/e 537.0375,
found m/e 537.0338.
{(η5-C5H5)(Cl)(NO)W[CdCH(C6H5)][P (C6H5)2]} (3c). The
preparation was carried out as described for 3a , however using
tungsten vinylidene complex 1c instead of 1a . Chromatogra-
phy on silica gel with 1:1 pentane/ether at the beginning and
pure diethyl ether at the end yielded 1.62 g (60%) of 3c as a
yellow solid. Crystallization from CH2Cl2 and pentane pro-
duced orange crystals of the Z isomer, mp 206-208 °C dec.
Anal. Calcd for C25H21NOPClW: C, 49.90; H, 3.52; N, 2.33.
Found: C, 49.92; H, 3.17; N, 2.66. Two isomers, E:Z ) 1:1.2
at room temperature: 31P NMR (162 MHz, CDCl3, H3PO4 as
and 95.9 (two Cp), 11.5 and 10.8 (2 CH3). IR (KBr): ν˜ (cm-1
)
1993 (s, CdO), 1617 (s, NtO); MS (70 eV) m/e 347 (M+, 184W),
319 (M+ - CO), 289 (M+ - CO - NO); high-resolution mass
spectrum calcd for C9H9NO2182W (M+) m/e 345.0116, found
m/e 345.0107.
1
external standard): δ -70.4 and -87.2 [two s, J P-W ) 129
1
{(η5-C5H5)(Cl)(NO)W(CdCH2)[P (C6H5)2]} (3a ). At -30 °C,
a solution of 0.84 mL (4.5 mmol) of chlorodiphenylphosphine
(2) in 20 mL of THF was added dropwise to the orange solution
of 1a (1.5 g, 4.5 mmol) in THF (40 mL). The progress of the
reaction was monitored by TLC (silica gel, diethyl ether). The
mixture was stirred at -30 °C for 1 h and then warmed to
+15 °C and stirred for another 20 min. During this time the
color changed from orange to wine red. The solvent was
removed by vacuum evaporation, and crystallization of the
residue from CH2Cl2 and pentane yielded 1.56 g (66%) of 3a
and 133 Hz, P(C6H5)2, E and Z]. H NMR (400 MHz, CDCl3):
3
δ 9.18 (d, 1H, cis-3J H-P ) 15 Hz, J H-W ) 7 Hz, CdCHR, Z),
7.82 (m, 2H, C6H5, Z), 7.77-7.14 [m, 11H, C6H5 (10H) and
CdCHR (E, 1H)], 5.88 and 5.71 (two s, 5H, Cp, E and Z). 13C
NMR (100 MHz, CDCl3): δ 154.0 and 150.0 (two d, 1J C-P ) 50
1
Hz, J C-W ) 55 Hz, W-CR, Z and E), 150.3 and 147.6 (two d,
2J C-P ) 6 and 11 Hz, Câ, Z and E), 139.1 and 138.6 [two d,
3J C-P ) 17 and 6 Hz, Câ(C6H5), Z and E], 133.9-133.5 [m, C6H5
4
(ortho)], 131.4 and 131.1 [two d, J C-P ) 3 Hz, C6H5 (para),
4
E], 131.3 and 130.8 [two d, J C-P ) 3 Hz, C6H5 (para), Z],
1
as orange crystals, mp 203-205 °C dec. Anal. Calcd for C19H17
NOPClW: C, 43.42; H, 3.26; N, 2.67. Found: C, 43.39; H, 2.96;
-
129.6-127.1 [m, C6H5 (meta)], 126.0 [d, J C-P ) 50 Hz, C6H5-
(ipso), Z], 103.0 and 102.8 [s(broad) and d, 2J C-P ) 1.5 Hz, Cp,

5286 Organometallics, Vol. 19, No. 25, 2000
Ipaktschi et al.
2
1
E and Z]. IR (KBr): ν˜ (cm-1) 1607 (N≡O); MS (70 eV) m/e 601
(M+, 184W), 571 (M+ - NO); high-resolution mass spectrum
calcd for C25H21NOPCl182W (M+) m/e 599.0532, found m/e
599.0514.
(d, J C-P ) 1.5 Hz, Cp), 40.1 and 33.7 [two d, J C-P ) 10 Hz,
2
C(CH3)3], 31.0 (two d, J C-P ) 3 and 4 Hz, CH3). IR (KBr): ν˜
(cm-1) 1620, 1528 (N≡O). MS (70 eV): m/e 485 (M+, 184W), 455
(M+ - NO); high-resolution mass spectrum calcd for C15H25
NOPClW (M+) m/e 483.0844, found m/e 483.0845.
-
{(η5-C5H 5)(Cl)(NO)W(CdCH 2)(P [C(CH 3)3]2)} (5). The
preparation was carried out as described for 3a ; however
chlorodi-tert-butylphosphine (4) was used instead of chlo-
rodiphenylphosphine (2). Chromatography on silica gel with
3:1 pentane/ether yielded 1.91 g (87%) of 5 as a bright yellow
solid. Crystallization from CH2Cl2 and pentane resulted in
Ack n ow led gm en t. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie, Frankfurt/M, Germany.
orange crystals, mp 157-158 °C dec. Anal. Calcd for C15H25
-
NOPClW: C, 37.10; H, 5.19; N, 2.88. Found: C, 37.19; H, 5.11;
Su p p or tin g In for m a tion Ava ila ble: Data of crystal
structure determination and refinement, tables of atomic
coordinates, interatomic distances and angles, anisotropic
thermal parameters, and hydrogen parameters of the com-
pounds 3a -c and 5. This material is available free of charge
via the Internet at http://pubs.acs.org.
N, 3.11. 31P NMR (162 MHz, CDCl3, H3PO4 as external
standard): δ -46.0 {s, 1J P-W ) 118 Hz, P[C(CH3)3]2}. 1H NMR
3
(400 MHz, CDCl3): δ 7.47 (d, 1H, cis-3J H-P ) 13 Hz, J H-W
)
8.5 Hz, CdCH2), 6.49 (d, 1H, trans-3J H-P ) 32 Hz, CdCH2),
5.82 (s, 5H, Cp), 1.48 and 1.36 {two d, 18H, P[C(CH3)3]2, 3J H-P
) 16 Hz }. 13C NMR (100 MHz, CDCl3): δ 165.5 (d, 1J C-P ) 58
1
2
Hz, J C-W ) 56 Hz, W-CR), 132.8 (d, J C-P ) 9 Hz, Câ), 103.4
OM000659D