Synthesis of the first pentacarbonyltungsten(0) complexes with P-pentamethyl-cyclopentadienyl-substituted 1H-phosphirene ligands: Crystal structure of [{Me5C5PC(H)=CPh}W(CO)5]

Article abstract of DOI:10.1002/zaac.200400045

The tungsten(0) complex [{Me₅C₅PC(Ph)=N}W(CO) ₅] (1) reacts upon heating with alkyne derivatives 3a-e in toluene to form benzonitrile and the complexes [{Me₅C₅PC(R ¹)=C(R²)}-W(CO)5] (4a-e) (4a: R¹ = OEt, R ² = H; 4b: R¹ = OEt, R² = SiMe₃; 4c: R¹ = Ph, R² = H; 4d : R¹ = Ph, R² = Ph; 4e: R¹, R² = Et), which were purified by column chromatography (except 4d). In reaction of 1 with 3d the tungsten(0) complex 5, having a 2,3-dihydro-1,2,3-azadiphosphete ligand, is formed in a competing reaction. Spectroscopic and mass spectrometric data of complexes 4a-c, 4e and 5 are discussed. The structures of complexes 4c and 5 were determined by single-crystal X-ray diffraction In 4c the three-membered ring has a C=C bond length of 1.312(3) A and a C-P-C angle of 43.02(9)°. In 5 the P-P bond length is 2.2866(7) A; the four-membered ring is slightly folded (fold angle 15° about P1-C6).

Full text of DOI:10.1002/zaac.200400045

Synthesis of the first Pentacarbonyltungsten(0) Complexes with P-Pentamethyl-
cyclopentadienyl-substituted 1H-Phosphirene Ligands: Crystal Structure of
[{(Me5C5PTC(H)؍CUPh}W(CO)5]
Rainer Streubela,*, Maren Bodea, Udo Schiemannb, Cathleen Wismachb, Peter G. Jonesb, and Axel Monseesc
a Bonn, Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität
b Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität
c Frankfurt am Main, DEGUSSA AG
Received February 21st, 2004.
Dedicated to Professor Reinhard Schmutzler on the Occasion of his 70th Birthday
Abstract. The tungsten(0) complex [{Me5C5P
(1) reacts upon heating with alkyne derivatives 3a؊e in toluene to
form benzonitrile and the complexes [{Me5C5P
C(R1)ϭC(R2)}-
W(CO)5] (4a؊e) (4a: R1 ϭ OEt, R2 ϭ H; 4b: R1 ϭ OEt, R2
T
C(Ph)ϭN
U
}W(CO)5]
4aϪc, 4e and 5 are discussed. The structures of complexes 4c and 5
were determined by single-crystal X-ray diffraction In 4c the three-
membered ring has a CϭC bond length of 1.312(3) A and a
˚
T
U
ϭ
CϪPϪC angle of 43.02(9)°. In 5 the PϪP bond length is
SiMe3; 4c: R1 ϭ Ph, R2 ϭ H; 4d : R1 ϭ Ph, R2 ϭ Ph; 4e: R1, R2 ϭ
Et), which were purified by column chromatography (except 4d).
In reaction of 1 with 3d the tungsten(0) complex 5, having a 2,3-
dihydro-1,2,3-azadiphosphete ligand, is formed in a competing re-
action. Spectroscopic and mass spectrometric data of complexes
2.2866(7) A; the four-membered ring is slightly folded (fold angle
˚
15° about P1ϪC6).
Keywords: Phosphorus heterocycles; 1H-Phosphirene complexes;
Phosphinidene complexes; Tungsten
Synthese der ersten Pentacarbonylwolfram(0)-Komplexe mit P-Pentamethylcyclo-
penta-dienyl-substituierten 1H-Phosphiren-Liganden: Kristallstruktur von
[{(Me5C5PTC(H)؍CUPh}W(CO)5]
Inhaltsübersicht. Der Wolfram(0)-Komplex [{Me5C5P
W(CO)5] (1) reagiert beim Erwärmen mit den Alkinderivaten 3a؊e in
Toluol zu Benzonitril und den Komplexen [{Me5C5P
C(R1)ϭC(R2)}-
T
C(Ph)ϭN
U
}-
phosphet-Liganden aufweist. Spektroskopische und massen-
spektrometrische Daten der Komplexe 4aϪc, 4e und 5 werden dis-
kutiert. Die Strukturen der Komplexe 4c und 5 konnten durch Ein-
kristall-Röntgendiffraktometrie aufgeklärt werden. In 4c hat der
T
U
W(CO)5] (4a؊e) (4a: R1 ϭ OEt, R2 ϭ H; 4b: R1 ϭ OEt, R2 ϭ SiMe3;
4c: R1 ϭ Ph, R2 ϭ H; 4d : R1 ϭ Ph, R2 ϭ Ph; 4e: R1, R2 ϭ Et), die bis
auf 4d säulenchromatographisch gereinigt und isoliert wurden. Im
Fall der Reaktion von 1 mit 3d entsteht in einer Konkurrenzreak-
tion der Wolfram(0)-Komplex 5, der einen 2,3-Dihydro-1,2,3-azadi-
˚
Dreiring eine CϭC-Bindungslänge von 1.312(3) A und einen
CϪPϪC-Winkel von 43.02(9)°. In 5 weist die PϪP-Bindung eine
˚
Länge von 2.2866(7) A auf; der Vierring ist leicht gefaltet (Falt-
winkel um P1ϪC6: 15°).
1 Introduction
nation properties. In 1999, we obtained a polycyclic phos-
phirane complex and proposed a P-Cp*-substituted 1H-
phosphirene complex as highly reactive intermediate [6]. We
decided to return to this problem and to investigate thermal
The chemistry of 1H-phosphirene complexes [1, 2] dates
back to 1982, when the first synthesis was described by
Marinetti and Mathey [3]. Since then numerous derivatives
have been described including those with P- [4] and C-
bonded [5] functional groups. Surprisingly, no stable deriva-
tive having a pentamethylcyclopentadienyl group (hereafter
denoted as Cp*) bonded to phosphorus has been described,
although such complexes could have interesting coordi-
reactions of the tungsten(0) complex [{Me5C5PTC(Ph)ϭNU}-
W(CO)5] (1) with alkyne derivatives; the results will be re-
ported hereafter. Furthermore, we report the first structure
of a P-Cp*-substituted 1H-phosphirene complex and of a
2,3-dihydro-1,2,3-azadiphosphete complex.
2 Preparative and Spectroscopic Results
* Prof. Dr. R. Streubel
Institut für Anorganische Chemie der Universität
Gerhard-Domagk-Str.1
D-53121 Bonn
E-mail: r.streubel@uni-bonn.de
Fax: ϩ49-228-739616
2.1 Synthesis
Thermal reaction of [{Me5C5PTC(Ph)ϭNU}W(CO)5] (1) [7] in
toluene at 65 °C in the presence of alkynes 3a؊e yielded
benzonitrile and the 1H-phosphirene tungsten complexes
Z. Anorg. Allg. Chem. 2004, 630, 1215Ϫ1219
DOI: 10.1002/zaac.200400045
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1215

R. Streubel, M. Bode, U. Schiemann, C. Wismach, P. G. Jones, A. Monsees
Scheme 1 Synthesis of tungsten complexes 4a-e and 5.
Table 1 31P NMR dataa) of P-Cp*- und P-CH(SiMe3)2-substitu-
ted 1H-phosphirene tungsten complexes 4a-e and 6a [5a], 6b [5b]
and 6c [9] and 6d [9].b)
4a؊e via [2ϩ1]-cycloaddition of the transiently formed ter-
minal phosphinidene complex 2 with 3a؊e [cf. 6, 8]
(Scheme 1); complexes 4a؊c and 4e were isolated using col-
umn chromatography at low temperature (Table 1). Unfor-
tunately, complex 4d was only identified by 31P NMR spec-
troscopy because considerable amounts of complex 5 were
formed in this case, thus leading to separation problems.
Although the competing reaction that leads to complex 5
could be largely suppressed by enhancing the 1:3d ratio
from 1:1 to 1:5 Ϫ thus decreasing the content of 5 from 55
to 25 % Ϫ, we were not able to isolate 4d. It is noteworthy
that if the [2ϩ1]-cycloaddition reaction of the transiently
formed terminal phosphinidene complex 2 is sterically hin-
dered, as in the case of 3d, then the formation of the tung-
sten complex 5 can be favored.
In contrast to complexes 4a,b and 4d,e, which remained
stable under the reaction conditions, complex 4c underwent
further reactions upon prolonged heating, thus yielding two
new products at δ (31P) ϭ Ϫ111.9 (Η1J(W,P)Η ϭ 222.7 Hz)
and Ϫ140.3 (Η1J(W,P)Η ϭ 266.4 Hz), which were not separ-
able. The former might be assigned to a complex with a
polycyclic phosphorus ligand (cf. [6]), whereas the latter is
attributable to a 1H-phosphirene complex with a trans-
formed P-substituent.
4/6
R1
R2
δ
31P
Η1J(183W, 31P)Η
δ
31P
Η1J(183W, 31P)Η
a
b
c
d
e
OEt
OEt
Ph
Ph
Et
H
SiMe3
H
Ph
Et
Ϫ82,8
262,7
264,8
266,0
264,5*)
259,7
Ϫ90,8
Ϫ110,5
Ϫ136,8
Ϫ134,6
Ϫ
268,0
273,5
272,1
268,6
Ϫ
Ϫ100,6
Ϫ129,7
Ϫ129,8*
Ϫ134,7
a) CDCl3, *) toluene with a D6-benzene capillary tube; δ in ppm; J in Hz;
b) 6e is unknown.
Complexes 4 and 6 show characteristically small phos-
phorus-carbon coupling constant magnitudes Ϫ as one
might expect in such cases because only sums of the two
1
2
scalar couplings J(P,C) and J(P,C), most probably having
opposite signs [10], were determined. The 13C resonances of
complexes 4a and 6a clearly indicate a π-donating electron
interaction of the ethoxy-oxygen atom lone pair with
the double bond π-system, e.g., thus leading to strongly
shielded C2 nuclei. This is further supported by a compari-
son of the 1H resonances of 4a and 4c δ (1H) ϭ 6,4,
ΗJ(31P, 1H)Η ϭ 17,2 Hz (4a) and δ (1H) ϭ 8,5, ΗJ(31P, 1H)Η ϭ
20,9 Hz (4c).
2.2 NMR spectroscopic and mass spectrometric results
The 1H-phosphirene complexes show the expected 31P and
13C NMR parameter of the nuclei of the three-membered
ring, which are displayed in Table 1 and 2 together with
those of the closely related complexes 6a [5a], 6b [5b] and
6c [9] and 6d [9]. It is remarkable that, in comparison to 6,
all complexes 4 show more deshielded 31P nuclei and
slightly decreased Η1J(183W, 31P)Η values. Within each series,
steric and electronic effects on the resonances are in accord-
ance with trends of previously reported derivatives [1, 2,
5, 9].
Mass spectrometric investigations (EI) of complexes
4a؊c showed that ring cleavage of the three-membered ring
does not occur upon ionization. There are two major frag-
mentation pathways of the radical cations: 1) extrusion of
one (and subsequently more) CO units and 2) the cleavage
of the exocyclic PϪC bond, leading to the Cp* radical cat-
1216
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1215Ϫ1219

The first Pentacarbonyltungsten(0) Complexes with P-Pentamethyl-cyclopentadienyl-substituted 1H-Phosphirene Ligands
Table 2 Comparison of selected 13C NMR data a) of the nuclei of
the three-membered ring of 1H-phosphirene complexes 4a,c with
those of complexes 6a [5a] and 6c [9].
ted bond lengths and angles see Figures 1 and 2. Character-
istic structural features of the three-membered ring of the
1H-phosphirene complex 4c are the very acute endocyclic
angle at phosphorus of 43,02(9)° and the two endocyclic
˚
PϪC bonds (PϪC6 1,793(2) and PϪC7 1,786(2) A), which
are close in length to the corresponding bonds of 6c (PϪC6
˚
˚
1,799(5) A and PϪC7 1,775(5) A) [5a]. The C6ϪC7 dis-
˚
tance of complex 4c (1,312(3) A) is in the range of values
of “standard” Csp2ϪCsp2 bonds, e.g., in acyclic derivatives
˚
˚
(1,322 A) and cyclopropenes (1,294 A) [11]) and virtually
identical with the value of the corresponding bond of 6b
˚
(1,311(7) A) [5b]).
4/6 R1
R2 δ13C1
(ΗJ(P,C1)Η)
δ13C2
δ13C1
δ13C2
The parameters of the [(Me5C5P)W(CO)5] moiety, such
(ΗJ(P,C2)Η)
(ΗJ(P,C1)Η)
(ΗJ(P,C2)Η)
as the angle WϪPϪC8 (124,38(0)°, the PϪC8 distance
˚
˚
(1,884(2) A) and the WϪP distance (2,5137(5) A), are close
to the values of [{Me5C5PC(Ph)ϭN}W(CO)5] (1)
a
c
OEt
Ph
H
H
156,6 (5,0)
84,3 *)
158,8 (2,0)
88,1 (4,9)
141,6 (19,7) 120,0 (13,0) 145,8 (17,9) 124,7 (6,5)
˚
(127,01(8)°), 1,852(5) and 2,4720(12) A) [7]), but the values
a) CDCl3; δ in ppm; J in Hz; *) multiplet, J was not determined
of 1 point to a different bonding situation; the ground state
of 1 may be best represented by two structures: 1) a side-
on nitrile complex to phosphorus of the phosphinidene
complex moiety and 2) a covalent three-membered ring sys-
tem.
ion and its fragments. In the case of complex 5 two frag-
mentation pathways of the radical cation are especially
interesting: the cleavage of the PϪCp* bond and/or the
PϪW bond (a) yielding m/z 300, which is tentatively as-
The centred structural feature of complex 5 is the four-
membered ring of the 2,3-dihydro-1,2,3-azadiphosphete li-
gand (Figure 2), which is slightly folded (mean deviation
signed to the ion [(Cp*PTPhCϭNPU
)ϩ], and the cleavage of
the four-membered ring (b) to give m/z 197, which is attri-
buted to [(Cp*P2)ϩ]. All assignments are based on the com-
parison of simulated and measured isotope patterns and
masses.
˚
0.07 A; fold angle about P1···C6 15 %, distance of P1 from
˚
the plane NϪC6ϪP2 0.41 A).
3 Crystal Structures of Complexes 4c and 5
The molecular structures of complexes 4c and 5 were unam-
biguously established by X-ray diffraction studies. For selec-
Figure 1 Molecular structure of complex 4c in the crystal (ellip-
Figure 2 Molecular structure of complex 5 in the crystal (ellip-
soids represent 50 % probability, hydrogen atoms (except at C7) are
omitted for clarity). Selected bond lengths [A] and angles [°]:
soids represent 50 % probability, hydrogen atoms are omitted for
clarity). Selected bond lengths [A] and angles [°]:
˚
˚
W-P 2,5137(5), P-C7 1,786(2), P-C6 1,793(2), P-C8 1,884(2), C6-C7 1,312(3),
C6-C18 1,462(3); C6-P-C7 43,02(9), C6-C7-P 68,75(13), C7-C6-P 68,23(13),
C6-P-C8 110,14(9), C7-P-C8 108,81(10).
W-P1 2,5481(5), P1-P2 2,2866(7), P2-C6 1,862(2), P1-N 1,7534(17), C6-N
1,307(3); N-P1-P2 78,36(6), C6-P2-P1 69,61(6), N-C6-P2 108,11(14), C6-N-
P1 101,92(14).
Z. Anorg. Allg. Chem. 2004, 630, 1215Ϫ1219
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R. Streubel, M. Bode, U. Schiemann, C. Wismach, P. G. Jones, A. Monsees
˚
[{Me5C5PTC(OEt)؍CU(SiMe3)}W(CO)5] (4b)
The P1ϪP2 bond (2,2866(7) A) is only slightly widened
˚
in comparison to complex 7 (7: 2,258(8) A [12]), but re-
presents a significantly lengthened PϪP single bond (stand-
ard value 2,21 A [11]). The dihedral angle between the four-
and the six-membered rings is 33°.
Currently, studies on the coordination chemistry of P-
Cp*-substituted 1H-phosphirene complexes are underway.
Starting material: 0,60 g (2,5 mmol) EtOCϵCSiMe3 [13] (3b) (50 %
toluene solution); Yield: 0,09 g (28 %), yellow oil. Elemental analy-
sis for C22H29O6PSiW (632.36 g/mol): Calc. C 41,79; H 4,62; found:
C 41,61; H 4,50 %.
˚
13C{1H}-NMR: δ ϭ 1,0 (s, Si-CH3), 10,4 (d, 3JPC ϭ 2,4 Hz, Cp*(C2/5)-CH3),
3
11,4 (d, JPC ϭ 3,4 Hz, Cp*(C2/5)-CH3), 11,6 (s, Cp*(C3/4)-CH3), 11,8 (s,
Cp*(C3/4)-CH3), 15,2 (s, OCH2CH3) 17,2 (d, JPC ϭ 3,3 Hz, Cp*(C1)-CH3),
2
63,6 (d, JPC ϭ 18,6 Hz, Cp*-CRing(C1)), 70,9 (s, Me3Si-CϭC), 135,1
(d, JPC ϭ 6,0 Hz, Cp*-CRing), 135,6 (d, JPC ϭ 2,8 Hz, Cp*-CRing), 140,5
(d, JPC ϭ 7,0 Hz, Cp*-CRing), 141,0 (d, JPC ϭ 6,1 Hz Cp*-CRing), 166,8
Experimental Part
2
(d, JPC ϭ 8,2 Hz, EtO-CϭC), 196,3 (d, 2J(PC ϭ 7,9 Hz, cis-CO), 198,4
2
1
(d, JPC ϭ 31,9 Hz, trans-CO). 31P{1H}-NMR: δ ϭ Ϫ100,6 (s, JWP
ϭ
All reactions and manipulations were carried out under an atmos-
phere of deoxygenated dry nitrogen, using standard Schlenk tech-
niques with conventional glassware. Solvents were dried according
to standard procedures. Ϫ NMR spectra were recorded on a Bruker
AC-200 spectrometer (200 MHz for 1H; 50.3 MHz for 13C;
81.0 MHz for 31P) using [D]chloroform, [D2]methylenedichloride
and [D6]benzene as solvent and internal standard; shifts are given
relative to ext. tetramethylsilane (1H, 13C) and 85 % H3PO4 (31P);
only coupling constant magnitudes are given. Ϫ Electron impact
(EI) (70 eV) chemical ionization (CI) (ammonia or methane), and
fast atom bombardement (FAB) (Xenon) mass spectra were re-
corded on a double focusing mass spectrometer Finnigan MAT-
8430. Ϫ Infrared spectra were recorded on a Biorad FT-IR 165
(selected data given). Ultraviolett/vis spectra were recorded on a
Hewlett Packard HP 8452. Ϫ Melting points were obtained on a
Büchi 535 capillary apparatus. Ϫ Elemental analyses were per-
formed using a Carlo Erba analytical gaschromatograph. Ϫ The
κP-notation in the nomenclature is intended to differentiate be-
tween P- and N-coordination of the appropriate heterocycle to
the metal.
264,8 Hz).
[{Me5C5PTC(Ph)؍CUH}W(CO)5] (4c)
Starting material: 0,30 mL (2,5 mmol) PhCϵCH (3c); Yield: 0,11 g
(36 %), m.p.: 122 °C (decomp).
Elemental analysis for C23H21O5PW (592,22 g/mol): Calc. C 46,65;
H 3,57; found: C 46,78; H 3,67 %.
1H-NMR: δ ϭ 0,77 (d, JPH ϭ 14,3 Hz, 3H, Cp*(C1)-CH3), 1,97 (m, 12H,
3
2
Cp*-CH3), 7,59 (m, 3 H, Ph), 7,85 (m, 2H, Ph), 8,51 (d, JPH ϭ 20,9 Hz,
1 H, H-CϭC). 13C{1H}-NMR: δ ϭ 10,7 (d, JPC ϭ 3,1 Hz, Cp*(3/4)-CH3),
3
3
2
11,4 (d, JPC ϭ 3,1 Hz, Cp*(3/4)-CH3), 11,7 (d, JPC ϭ 4,9 Hz, Cp*(2/5)-
2
3
CH3), 11,8 (d, JPC ϭ 5,2 Hz, Cp*(2/5)-CH3), 17,9 (d, JPC ϭ 3,1 Hz, Cp*
(C1)-CH3), 62,8 (d, JPC ϭ 15,6 Hz, Cp*(C1)-CRing), 120,0 (d, JPC
1
1
ϭ
2
13,0 Hz, H-CϭC), 127,6 (d, JPC ϭ 7,4 Hz, i-Ph), 129,1 (s, m-Ph), 129,7 (d,
3JPC ϭ 3,0 Hz, o-Ph), 131,0 (s, p-Ph), 135,4 (d, JPC ϭ 10,0 Hz, Cp*(C3/4)-
3
CRing), 135,5 (d, 3JPC ϭ 11,4 Hz, Cp*(C3/4)-CRing), 141,0 (d, 2JPC ϭ 16,5 Hz,
2
Cp*(C2/5)-CRing), 141,1 (d, JPC ϭ 17,3 Hz, Cp*(C2/5)-CRing), 141,6 (d,
1ϩ2
2
J
PC
ϭ 19,7 Hz, Ph-CϭC), 196,1 (d, JPC ϭ 8,2 Hz, cis-CO), 198,1 (d,
2JPC ϭ 32,5 Hz, trans-CO). 31P{1H}-NMR: δ ϭ Ϫ129,7 (sSat, 1JWP 266,0 Hz).
MS (70 eV, 184W): m/z ϭ 592 (27) [Mϩ], 564 (3) [(M-CO)ϩ], 536 (17) [(M-
2CO)ϩ], 508 (13) [(M-3CO)ϩ], 480 (4) [(M-4CO)ϩ], 452 (100) [(M-5CO)ϩ],
429 (37) [(M-Cp*-CO)ϩ], 401 (51) [(M-Cp*-2CO)ϩ], 373 (66) [(M-Cp*-
3CO)ϩ], 317 (44) [(M-Cp*-5CO)ϩ], 135 (27) [(Cp*)ϩ], 119 (37) [(Cp*-Me-
H)ϩ], 105 (32) [(Cp*-2Me)ϩ], 91 (27) [(Cp*-2MeϪCH2)ϩ].
General procedure for the preparation of complexes
[{Me5C5P
T U
C(R1)؍C(R2)}W(CO)5] (4a؊e)
[{Me5C5PTC(Ph)؍CU(Ph)}W(CO)5] 4d
To a solution of 0,30 g (0.5 mmol) [{(Me5C5P
T
C(Ph)ϭNU}W(CO)5]
Starting material: 0.45 g (2,5 mmol) PhCϵCPh (3d): product 4d
was not isolated.
,
31P{1H}-NMR: δ ϭ Ϫ129,3 (sSat 1JWP ϭ 264,5 Hz).
(1), dissolved in toluene (1.8 mL), the appropriate alkyne derivative
3a, 3b [15] or 3c؊e (2,5 mmol each) was added and the solution
heated at 65 °C for 60Ϫ90 min (31P NMR control) with slow stir-
ring. All volatile components were removed in vacuo (ca.
0.01 mbar) and the products separated by low-temperature column
chromatography (neutral Al2O3, Ϫ50 °C, 15 x 2 cm, n-pentane/di-
ethyl ether (1. 95:5 and 2. 90:10)). Evaporation of the first yellow
fractions yielded complexes 4a, c and 4e as yellow solids, 4b as
yellow oil; crystallisation from n-pentane yielded pale-yellow crys-
tals.
[{Me5C5PTC(Et)؍CU(Et)}W(CO)5] (4e)
Starting material: 0.25 mL (2,5 mmol) EtCϵCEt (3e); Yield:
0,09 g (21 %).
Elemental analysis for C21H25O5PW (572,23 g/mol): Calc.: C 44,08,
H 4,40, found: C 44,48, H 4,69 %.
1H-NMR: δ ϭ 0,75 (d, JPH ϭ 13,6 Hz, 3H, Cp*(C1)-CH3), 1,43 (t, JHH
ϭ
3
3
7,5 Hz, 6H, CH2CH3), 1,88 (d, 4JPH ϭ 4,3 Hz, 6H, Cp*(C2/5)-CH3), 1,96 (s,
6H, Cp*(C3/4)-CH3), 2,88 (m, 4H, CH2CH3). 13C{1H}-NMR: δ ϭ 10,9 (s,
Cp*(C2/5)-CH3), 11,7 (s, Cp*(C3/4)-CH3), 12,4 (s, CH2CH3), 17,5 (s, Cp*
(C1)-CH3), 21,4 (d, 2ϩ3JPC ϭ 6.6 Hz, CH2CH3), 134,4 (d, 1ϩ2JPC ϭ 18.1 Hz,
Et-CϭC-Et), 135,6 (d, JPC ϭ 4.3 Hz, Cp*-CRing), 140,3 (d, JPC ϭ 6.4 Hz,
[{Me5C5PTC(OEt)؍CUH}W(CO)5] (4a)
Starting material: 0,30 mL (2,5 mmol) EtOCϵCH (3a); Yield:
0,10 g (34 %), m.p.: 84 °C (decomp).
Elemental analysis for C19H21O6PW (560,18 g/mol): Calc. C 40,74;
H 3,78; found: C 40,62; H 3,70 %.
Cp*-CRing), 196,5 (d, JPC ϭ 8.2 Hz, cis-CO). <cf31>31P{1H}-NMR: δ ϭ
2
Ϫ134,7 (sSat,
1JWP ϭ 259,7 Hz).
1H-NMR: δ ϭ 0,89 (d, 3JPH ϭ 13,6 Hz, 3H, Cp*(C1)-CH3), 1,46 (dt, 3JHH ϭ
Preparation of complex [{Me5C5PTC(Ph)؍NUPC5Me5}W(CO)5] (5)
4
7,1 Hz, JPH ϭ 0,3 Hz, 3H, OCH2CH3), 1,84 (m, 12H, Cp*-CH3), 4,33 (dq,
3
2
3JHH ϭ 7,1 Hz, JPH ϭ 3,0 Hz, 2H, OCH2CH3), 6,37 (d, JPH ϭ 17,2 Hz,
A solution of 0,95 g (1,6 mmol) [{(Me5C5PC(Ph)ϭN}W(CO)5] (1),
dissolved in toluene (6,5 mL), was heated at 65 °C for 120 min with
slow stirring (31P NMR control). All volatile components were re-
moved in vacuo (ca. 0.01 mbar) and the product separated by low-
temperature column chromatography (neutral Al2O3, Ϫ50 °C, 8 x
2 cm, n-pentane/diethyl ether (1. 95:5 and 2. 90:10)). Evaporation
of the first yellow fractions yielded complex 5 as yellow solid; crys-
tallisation from n-pentane yielded pale-yellow crystals. Yield: 0.47 g
(78 %); m.p.: 132 °C (decomp.).
1H, H-CϭC). 13C{1H}-NMR: δ ϭ 10,8 (m, Cp*-CH3), 11,7 (m, Cp*-CH3),
14,8 (s, OCH2CH3 ), 17,2 (m, Cp*(C1)-CH3), 63,6 (d, JPC ϭ 38,6 Hz, Cp*-
CRing(C1)), 71,0 (d, JPC ϭ 3,4 Hz, OCH2CH3), 84,3 (m, H-CϭC), 134,8 (s,
1
3
Cp*-CRing), 135,3 (s, Cp*-CRing), 141,0 (s, Cp*-CRin2g), 141,3 (s, Cp*-CRing),
1ϩ2
156,6 (d,
J
PC
ϭ 5,0 Hz, EtO-CϭC), 196,0 (d, JPC ϭ 8,1 Hz, cis-CO),
198,4 (d, 2JPC ϭ 32,1 Hz, trans-CO) 31P{1H}-NMR: δ ϭ Ϫ82,8 (sSat 1JWP ϭ
,
262,7 Hz). MS (70 eV, 184W): m/z ϭ 560 (16) [Mϩ], 504 (15) [(M-2CO)ϩ],
425 (25) [(M-Cp*)ϩ], 419 (30) [(M-5CO-H)ϩ], 369 (62) [(M-Cp*-2CO)ϩ], 341
(100) [(M-Cp*-3CO)ϩ], 135 (48) [(Cp*)ϩ], 119 (60) [(Cp*-Me-H)ϩ], 105 (50)
[(Cp*-2Me)ϩ], 91 (42) [(Cp*-2MeϪCH2)ϩ].
1218
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1215Ϫ1219

The first Pentacarbonyltungsten(0) Complexes with P-Pentamethyl-cyclopentadienyl-substituted 1H-Phosphirene Ligands
Elemental analysis for C32H35NO5P2W (759.41 g/mol): Calc.: C
50,61, H 4,65, N 1,84; found: C 50,42, H 4,73, N 1,79 %.
obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB21EZ (Fax: (ϩ44) 1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk).
3ϩ4
1H-NMR (CD2Cl2): δ ϭ 1,46 (t,
J
PH
ϭ 6,4 Hz, 6 H, Cp*(C1)-CH3),1,80
(s, 12 H, Cp*-CH3), 1,87 (s, 6 H, Cp*-CH3), 1,96 (s, 6 H, Cp*-CH3).
13C{1H}-NMR (CD2Cl2): δ ϭ 11,5 (m, Cp*-CH3), 11,7 (s, Cp*-CH3), 12,8
(m, Cp*-CH3), 15,4 (m, Cp*-CH3), 64,6 (s, Cp*-CRing), 121,1 (s, Cp*-CRing),
127,5 (s, Ph), 128,0 (s, Ph), 128,5 (s, Ph), 132,2 (s, Ph), 136,0 (s, Cp*-
CRing),137,5-138.5 (m, Cp*-CRing), 140,9 (m, Cp*-CRing), 142,1 (m, Cp*-
CRing), 197,3 (t, JP,C ϭ 3.5 Hz, CO). 31P{1H}-NMR (CD2Cl2): δ ϭ 82.6 (br.
s). MS (70 eV, 184W): m/z ϭ 759 (1) [Mϩ], 624 (4) [(M-Cp*)ϩ], 521 (3) [(M-
PhCN-Cp*)ϩ], 540 (1) [(M-Cp*-3CO)ϩ], 484 (1) [(M-Cp*-5CO)ϩ], 437 (5)
[(M-PhCN-Cp*-3CO)ϩ], 381 (5) [(M-PhCN-Cp*-5CO)ϩ], 300 (4) [(M-Cp*-
W(CO)5)ϩ], 197 (14) [(Cp*P2)ϩ], 135 (100) [(Cp*)ϩ], 119 (24) [(Cp*-Me-
H)ϩ], 105 (16) [(Cp*-2Me)ϩ], 91 (14) [(Cp*-2MeϪCH2)ϩ].
Für die Förderung dieser Arbeit danken wir der Deutschen For-
schungsgemeinschaft und dem Fonds der Chemischen Industrie
sowie der DEGUSSA AG.
References
[1] F. Mathey, in: Phosphorus-carbon heterocyclic chemistry: the
rise of a new domain (ed.: F. Mathey), Pergamon, Amsterdam,
2001, ch. 7, p. 753.
[2] F. Mathey, M. Regitz in Comprehensive Heterocyclic Chemistry
II, (eds.: A. R. Katritzky, C. W. Rees, E. F. V. Sciven), Perga-
mon Press, 1997, p.277.
[3] A. Marinetti, F. Mathey, J. Am. Chem. Soc. 1982, 104, 4484.
[4] O. Wagner, M. Ehle, M. Regitz, Angew. Chem. 1989, 101, 227;
Angew. Chem. Int. Ed. 1989, 28, 225.
[5] a) A. Ostrowski, J. Jeske, F. Ruthe, P. G. Jones, R. Streubel,
Z. Anorg. Allg. Chem. 1997, 623, 1897; b) R. Streubel, H. Wil-
kens, F. Ruthe, P. G. Jones, Z. Anorg. Allg. Chem. 1999, 625,
102.
[6] a) U. Rohde, F. Ruthe, P. G. Jones, R. Streubel, Angew. Chem.
1999, 111, 158; Angew. Chem. Int. Ed. 1999, 38, 215; b) R.
Streubel, H. Wilkens, U. Rohde, A. Ostrowski, J. Jeske, F.
Ruthe, P. G. Jones, Eur. J. Inorg. Chem. 1999, 1567.
[7] R. Streubel, U. Rohde, J. Jeske, F. Ruthe, P. G. Jones, Eur. J.
Inorg. Chem. 1998, 2005.
[8] Reviews of electrophilic terminal phosphinidene (phosphane-
diyl) complexes: a) F. Mathey, Angew. Chem. 1987, 99, 285;
Angew. Chem. Int. Ed. Engl. 1987, 26, 275; b) K. B. Dillon, F.
Mathey, J. F. Nixon, in: Phosphorus: The Carbon Copy, Wiley:
Chichester, 1998, p 19; c) F. Mathey, N. H. Tran Huy, A.
Marinetti, Helv. Chim. Acta 2001, 84, 2938; d) K. Lam-
mertsma, M. J. M. Vlaar, Eur. J. Org. Chem. 2002, 1127.
[9] R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem.
1994, 106, 2564; Angew. Chem. Int. Ed. Engl. 1994, 33, 2427.
[10] S. Berger, S. Braun, H.-O. Kalinowski, NMR-Spektroskopie
von Nichtmetallen, Bd. 3, G. Thieme Verlag, Stuttgart 1993,
p. 119.
X-ray structure analyses
Compound 4c
Mrϭ 592,22, monoclinic, space group P21/c, unit cell dimensions:
˚
a ϭ 9,9214(6), b ϭ 17,9002(10) and c ϭ 13,7381(8) A, β ϭ
3
110,643(3)°, V ϭ 2283,2(2) A , Z ϭ 4; ρcalcd ϭ 1,723 Mg/m3, MoKα
˚
˚
radiation, λ ϭ 0,71073 A, T ϭ 133 K, yellow prism (0,20 x 0,13 x
0,13 mm). Of 37434 reflections collected to 2 θmax x 56.6° on a
Bruker Smart 1000 CCD, 5673 were independent (Rint ϭ 0,0264)
and used for all calculations (program SHELXL-97). Number of
parameters: 276. After absorption correction (multiple scan ), all
non-hydrogen atoms were refined anisotropically using full matrix
least-squares based on F2 to give R1 ϭ 0,0172, wR2 ϭ 0,0442 (all
data). Res. electr. dens: 1.8 e/ A . Hydrogen atoms were included
using a riding model or rigid methyl groups, except for H7 (at C7;
refined freely).
3
˚
Compound 5
¯
Mrϭ 759,40, triclinic, space group P1, unit cell dimensions: a ϭ
9,3828(6), b ϭ 11,2993(8) and c ϭ 16,3614(12) A; α ϭ 84,593(3)°,
˚
˚
3
β ϭ 79,344(3), γ ϭ 67,801(3)°, V ϭ 1577,78(19) A , Z ϭ 2, ρcalcd ϭ
1,598 Mg/m3, MoKα radiation, λ ϭ 0,71073 A, T ϭ 133 K; yellow
˚
tablet (0,41 x 0,23 x 0,09 mm). Of 25931 reflections collected to
2θmax 52.7°, 6454 were independent (Rint ϭ 0,0299). Number of
parameter: 380. The structure was refined as above to give R1 ϭ
0,0177, wR2 ϭ 0,0473 (all data). Res. electr. dens. 1.3 e/ A . Hydro-
gen atoms were refined using a riding model or rigid methyl groups.
3
˚
[11] F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G.
Orpen, R. Taylor, J. Chem. Soc., Perkin Trans. II 1987, S1.
[12] E. Ionescu, P. G. Jones, R. Streubel, J. Chem. Soc., Chem.
Commun. 2002, 2204.
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publication
no. CCDC-240380 and 240381. Copies of the data can be
[13] P. Müller, N. Pautex, Helv. Chim. Acta 1991, 74, 55.
Z. Anorg. Allg. Chem. 2004, 630, 1215Ϫ1219
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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