New access to and reactions of P-Functional acylphosphane complexes

Article abstract of DOI:10.1002/ejic.201001122

P-Functional (acylphosphane)tungsten complexes 4a-f have been prepared in good yields by the reaction of phosphinidenoid complexes 2a-d with acyl chlorides 3a,b. The reactions of acyl(chloro)phosphane complex 4a at -80 °C with organolithium reagents selec

Full text of DOI:10.1002/ejic.201001122

FULL PAPER
DOI: 10.1002/ejic.201001122
New Access to and Reactions of P-Functional Acylphosphane Complexes
Vitaly Nesterov,[a] Lili Duan,[a] Gregor Schnakenburg,[a] and Rainer Streubel*[a]
Dedicated to Professor O. I. Kolodiazhnyi
Keywords: Phosphanides / Phosphane ligands / Phosphaalkenes / Tungsten
P-Functional (acylphosphane)tungsten complexes 4a–f have
been prepared in good yields by the reaction of phosphinid-
enoid complexes 2a–d with acyl chlorides 3a,b. The reactions
of acyl(chloro)phosphane complex 4a at –80 °C with organo-
lithium reagents selectively led to the formation of lithiated
phospha-enolate complex 5b. The ambident reactivity of this
compound was demonstrated in reactions with electrophiles
such as PhC(O)Cl, MeI, and Me3SiCl, which yielded O-sub-
stituted complexes 6a,b and 8a,b and P-substituted complex
7.
of phosphanes with metal complexes,[5] the migration of an
acyl moiety from a transition-metal center to a phosphan-
ido ligand,[3b,6] and the conversions of phosphanes ligated
to transition-metal centers.[3a]
Introduction
Of the organophosphorus compounds containing a car-
bonyl group directly attached to a phosphorus atom the
most important examples are mono- and bis(acyl)phos-
phane oxides I (Scheme 1), which have proved to be effec-
tive photoinitiators and have therefore raised great interest
from industry and academia.[1] Although acylphosphane
derivatives II[2] have been known for a long time, acylphos-
phanes coordinated to a transition-metal center (III) are
less studied, and their synthetic potential is largely unex-
plored.[3]
The first synthesis and reactions of (Li/X-phosphinid-
enoid)transition-metal complexes have recently been de-
scribed;[7] it was shown that they can behave similarly to
carbenoids[8] and silylenoids[9] as the corresponding phos-
phinidene complex behavior was observed.[7a,10] It was dem-
onstrated that such species can react with electrophiles such
as methyl iodide[7a] or iodoacetylene derivatives,[11] and thus
they display nucleophilic behavior. As part of our ongoing
research into M/X-phosphinidenoid complex chemistry we
would like to report here on their reactions with acyl chlo-
rides opening a general access to P-functional (acylphos-
phane)transition-metal complexes. Furthermore, we de-
scribe the reactivity of the latter towards organolithium
compounds.
Scheme 1. Functional acylphosphanes I and II and their complexes
III {[M] = MLn, R = organic substituent, X = RC(O) or group 16
or 18 element}.
Results and Discussion
Because of the known stabilizing ability of transition-
metal complexes on otherwise highly reactive compounds,
the increased stability of III could be safely assumed, and
therefore they could mimic the chemical behavior of the
corresponding carbon analogues, as expected from the diag-
onal relationship between carbon and phosphorus.[4] The
main methods of preparation of mononuclear (acylphos-
phane)transition-metal complexes III include the reactions
(Li/X-phosphinidenoid)metal complexes 2a,b and Li/
RO-phosphanide complexes 2c,d were generated by lithi-
ation of the corresponding P-H bifunctional phosphane
complexes 1a,[12] 1b,[7b] and 1c,d[13] with LDA in the pres-
ence of 12-crown-4 at –80 °C and allowed to react in situ
with acyl chlorides 3a,b to give selectively the (acylphos-
phane)tungsten complexes 4a–f (Scheme 2). The reactivity
of the complexes 2a–d depended largely on the nature of
the substituent X bonded to the phosphorus atom and, in
general, complexes 2c,d bearing alkoxy substituents at the
phosphorus atom appeared to be less reactive than the
halogen-substituted complexes 2a,b.
[a] Institut für Anorganische Chemie, Rheinische Friedrich-
Wilhelms-Universität Bonn,
Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
Fax: +49-228-73-9616
E-mail: r.streubel@uni-bonn.de
Eur. J. Inorg. Chem. 2011, 567–572
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V. Nesterov, L. Duan, G. Schnakenburg, R. Streubel
FULL PAPER
atom in 4a as ligand has a trigonal-pyramidal geometry [in
the ligand the sum of the bond angles at P(1) is 301.8°] with
a P–C(1) distance of 1.912(5) Å. The tendency towards P–
C bond elongation in α-carbonyl derivatives of organophos-
phorus compounds (the sum of the covalent radii of P and
C atoms is 1.83 Å) has been observed before for transition-
metal-free acylphosphanes,[2,14] bis(acyl)phosphane ox-
ides,[15] and nonfunctional (acylphosphane)transition-metal
complexes.[3b,6a]
As a case in point, the reactions of complex 4a with
organolithium nucleophiles were studied to investigate the
use of P-functional acylphosphane complexes in organo-
phosphorus and coordination chemistry. It was found that
the reactions of complex 4a with RLi (R = Me, nBu, or
Scheme 2. Preparation of the P-functional (acylphosphane)tung- tBu) in THF at –80 °C led to the selective formation of
sten complexes 4a–f.
phospha-enolate complex 5b without any evidence of nucle-
ophilic attack on the P- and/or W-bonded carbonyl groups
(Scheme 3).[3b]
Complexes 4a–f were obtained in good yields (70–85%)
after silica gel column chromatography and/or after
crystallization from n-pentane at low temperatures and were
fully characterized; pure 4a–f are stable under inert-gas
conditions.
The signals of the carbonyl carbon atoms directly
bonded to the phosphorus atom in the 13C NMR spectra
of complexes 4a–f appeared at δ = 202.3–216.6 ppm. Inter-
estingly, in the case of the P-chloro-substituted acylphos-
phane complexes 4a,b these signals displayed surprisingly
small P,C coupling constants (4a: J = 1.3 Hz; 4b: J =
1.9 Hz) compared with the other complexes (4c–f: J = 7.1–
19.6 Hz).
The IR spectra exhibit absorption bands of the carbonyl
group of the acyl moieties in 4a–f in the range 1648–
Scheme 3. Reactions of complex 4a with various organolithium
1702 cm–1. Maxima are observed in the UV spectra of the
compounds.
acylphosphane complexes 4a–f in the range 229.5–235 nm.
The molecular structure of 4a was confirmed by single-
We propose that the first step is a chlorine/lithium ex-
crystal X-ray diffraction studies (Figure 1). The phosphorus
change reaction that yields complex 5a as a transient spe-
cies, which rearranges to give complex 5b [δP = –19.0 ppm,
1J(P,W) = 179.2 Hz] as the thermodynamically more fa-
vored isomer. All the reactions were accompanied by a
change in color from yellow to red. If the reactions were
carried out in the presence of 12-crown-4, complex 5bЈ was
isolated in high yield with the lithium ion coordinated to
12-crown-4 (without THF). Complex 5bЈ is characterized
1
by a signal at δ = –23.8 ppm with a J(P,W) coupling con-
stant of 167.8 Hz (31P NMR spectrum, THF, 25 °C). The
13C{H} NMR spectrum displayed a signal for the α-carbon
atom of 5bЈ that was more downfield-shifted and had a
1
larger C,P coupling constant [δC = 227.5 ppm, J(C,P) =
18.1 Hz] than the starting material, complex 4a [δC
=
1
202.3 ppm, J(C,P) = 1.3 Hz]. As no Li,P coupling was ob-
served in the NMR spectra, we assume that the lithium cat-
ion is bonded to the oxygen atom in 5bЈ. This is further
supported by our reactivity studies (see below) and by re-
sults reported before for nonligated lithium acyl- and bis-
(acyl)phosphanides[16,17] in which the lithium ion is bound
to the more electronegative oxygen atom and, additionally,
to the solvent donor molecules.
Figure 1. Crystal structure of complex 4a (50% probability level,
hydrogen atoms have been omitted for clarity). Selected bond
lengths [Å] and angles [°]: W–P 2.506(1), P–C(1) 1.912(5), P–C(8)
1.809(4), P–Cl 2.903(2), C(1)–O(1) 1.219(6), C(1)–C(2) 1.481(7);
C(8)–P–C(1) 101.4(2), C(8)–P–Cl 107.30(15), C(1)–P–Cl(15)
93.13(16), C(2)–C(1)–P 123.4(4), O(1)–C(1)–P 114.7(3).
568
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Eur. J. Inorg. Chem. 2011, 567–572

P-Functional Acylphosphane Complexes
The O-lithiated alkylidenephosphane complexes 5b and typical range of P–C bond lengths in phosphaalkenes and
5bЈ can be considered as phosphorus analogues of metal (η1-phosphaalkene)transition-metal complexes.[20]
enolates derived from ketones.[18] To examine the reactivity
When complex 5bЈ was treated with methyl iodide, the
of complex 5bЈ, that is, the ratio of O- versus P-substitution, P-methyl-substituted complex 7 was obtained selectively
it was treated with various electrophiles (Schemes 4 and 5). (Scheme 4); complex 7 showed a doublet of doublets in its
The reaction of complex 5bЈ with benzoyl chloride led to 31P NMR spectrum at δ = 7.03 ppm [1J(P,W) = 223.8 Hz,
2
1
the selective formation of phosphaalkene complexes 6a,b, 2J(P,H) = 6.3 Hz, J(P,H) = 5.0 Hz]. In the H NMR spec-
which were obtained as a mixture of (Z)/(E) isomers (ratio trum the P-methyl protons appeared as a doublet at δ =
ca. 2:1). Complexes 6a,b displayed two resonances in the 2.15 ppm [2J(P,H) = 6.2 Hz].
31P NMR spectrum at δ = 163.5 and 165.8 ppm, respec-
The reactions of nonligated lithium acylphosphanides
tively, with a W,P coupling constant of 267.0 Hz (in both with trimethylsilyl chloride have previously been reported
cases) but different P,H coupling constants for the CH pro- to give O-[16a] and P-substituted products.[16b] To examine
ton of the P-substituent [2J(P,H) = 8.9 Hz for 6a (Z) and the influence of the transition metal on the reactivity, com-
2J(P,H) = 17.8 Hz for 6b (E)].
plex 5bЈ was treated with trimethylsilyl chloride at low tem-
peratures (Scheme 5). In this case a mixture of three prod-
ucts was formed: two major products (ratio of 2:1) with 31
P
NMR resonances similar to those of 6a,b [δP = 106.9 ppm,
1J(P,W) = 256.8 Hz, 2J(P,H) = 17.8 Hz and δP = 101.9 ppm,
2
1J(P,W) = 258.1 Hz, J(P,H) = 8.9 Hz] and thus were as-
signed to the O-silylated alkylidenephosphane complexes
8a,b. A minor product 9 (ca. 15%) with δP = 120.7 ppm
2
[1J(P,W) = 251.7 Hz, J(P,H) = 19.0 Hz] could not be iden-
tified. If this solution of 8a,b and 9 was treated with small
amounts of water, the selective formation of complex 10
was observed; the final product 10 was isolated by column
chromatography and fully characterized.
Scheme 4. Reactivity of 5bЈ towards PhCOCl and MeI.
The molecular structure of the (Z)-phosphaalkene com-
plex 6a[19] was confirmed by single-crystal X-ray diffraction
studies (Figure 2); suitable crystals were obtained from n-
pentane solutions of the (Z)/(E) mixture at 24 °C.
Scheme 5. Reaction of 5bЈ with Me3SiCl.
The existence of a P–H bond in 10 was revealed by its
large coupling constant [δP = –39.8 ppm, 1J(P,W) =
1
2
212.3 Hz, J(P,H) = 319.5 Hz, J(P,H) = 7.6 Hz].
Figure 2. Crystal structure of complex 6a (50% probability level,
hydrogen atoms have been omitted for clarity). Selected bond
lengths [Å] and angles [°]: W–P(1) 2.473(8), P(1)–C(1) 1.676(4),
P(1)–C(15) 1.811(3), C(1)–C(2) 1.474(5), C(1)–O(1) 1.410(4), C(8)–
O(2) 1.203(4); C(1)–P(1)–W 127.25(12), C(1)–P(1)–C(15)
111.89(16), C(15)–P(1)–W 119.97(11).
Conclusions
It has been shown that the in situ reactions of phosphini-
denoid complexes 2a,b and phosphanide complexes 2c,d
with acyl chlorides represent a new method for the prepara-
tion of P-functional (acylphosphane)tungsten complexes.
The structure of complex 6a contains all the features As illustrated for acyl(chloro)phosphane complex 4a, reac-
characteristic of (phosphaalkene)transition-metal com- tions with various organolithium compounds do not lead
plexes: The phosphorus and carbon centers of the P=C to nucleophilic attack at the P- and W-bonded carbonyl
moiety have trigonal-planar environments [sum of the bond groups but to the selective formation of O-lithiated deriva-
angles at P(1) and C(1) are 359.1 and 359.7°, respectively], tives 5b and 5bЈ as the final products. Complex 5bЈ pos-
the P(1)–C(1) bond length is 1.676(4) Å, which is in the sesses ambident nucleophilic character, thus giving rise to
Eur. J. Inorg. Chem. 2011, 567–572
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V. Nesterov, L. Duan, G. Schnakenburg, R. Streubel
FULL PAPER
(CDCl3): δ = 115.4 [sSat, 1J(P,W) = 260.6 Hz] ppm. MS (EI, 70 eV):
P- and O-substituted products depending on the nature of
the electrophile employed. The chemistry of the transition-
metal complexes of α-carbonyl-substituted phosphanes and
their derivatives is currently under investigation.
m/z (%) = 592.0 (8) [M]+. IR (KBr): ν = 543 (s), 567 (s), 597 (s),
˜
682 (m), 859 (s), 1003 (m), 1119 (m), 1254 (s) 1347 (s), 1702 (s),
1949 (s), 2075 (s) cm–1. UV/Vis (n-pentane): λ (abs.) = 230.0 (1.5),
305.0 (0.153), 346.5 (0.100) nm. C14H22ClO6PSi2W (592.76): calcd.
C 28.37, H 3.74; found C 28.58, H 3.90.
Complex 4c: Yellow solid; yield: 378 mg (0.59 mmol, 74%); m.p.
Experimental Section
4
58 °C (dec.). 1H NMR (CDCl3): δ = 0.21 [d, J(P,H) = 1.9 Hz, 9
2
General Procedures: All the reactions were carried out under puri-
fied argon by using standard vacuum, Schlenk, and glove-box tech-
niques. Solvents were dried and degassed by standard procedures.
NMR spectroscopic data were recorded at 25 °C with a Bruker
H, Si(CH3)3], 0.38 [s, 9 H, Si(CH3)3], 1.90 [d, J(H,P) = 10.3 Hz, 1
H, PCH], 7.53 (m, 2 H, Ph), 7.65 (m, 1 H, Ph), 8.08 (m, 2 H, Ph)
3
3
ppm. 13C{1H} NMR (CDCl3): δ = 2.56 [dd, J(C,P) = 2.9, J(C,F)
3
= 1.8 Hz, Si(CH3)3], 3.44 [d, J(C,P) = 2.3 Hz, Si(CH3)3], 32.6 [dd,
DMX 300 spectrometer (1H: 300.13 MHz; 13C: 75.5 MHz; 31P: 1J(C,P) = 11.3, 2J(C,F) = 4.1 Hz, PCH], 128.98 [d, 4J(C,P) =
3
121.5 MHz) by using CDCl3 or [D8]THF (complex 5bЈ) as solvent
and internal secondary standard; chemical shifts are referenced to
tetramethylsilane (1H, 13C: Ξ = 19.867187 MHz) and 85% H3PO4
(31P: Ξ = 40.480742 MHz). Mass spectra were recorded with a
MAT 95 XL Finnigan (EI, 70 eV, 184W) spectrometer (selected data
given). UV/Vis spectra were recorded with a Shimadzu UV-1650
PC spectrometer. Infrared spectra were recorded with a Thermo
Nicolet 380 FT-IR spectrometer (selected data given). Elemental
analyses were performed by using an Elementar VarioEL instru-
ment. Melting points were determined with a Büchi apparatus, with
samples sealed in capillaries under argon.
1.1 Hz, Ph], 129.36 [d, J(C,P) = 6.5 Hz, Ph], 134.3 (s, Ph), 135.8
[dd, 2J(C,P) = 40.5, 3J(C,F) = 2.3 Hz, Ph], 196.31 [ddSat, 2J(C,P) =
3
1
2
7.1, J(C,F) = 2.9, J(C,W) = 128.5 Hz, cis-CO], 198.0 [d, J(C,P)
= 29.2 Hz, trans-CO], 207.3 [d, 1J(C,P) = 13.1 Hz, C(O)P] ppm.
31P{1H} NMR (CDCl3): δ = 193.27 [dSat, J(P,W) = 281.0, J(P,F)
1
1
= 858.3 Hz] ppm. 19F{1H} NMR (CDCl3): δ = –113.4 [dSat
,
2J(F,W) = 11.2, J(F,P) = 858.3 Hz] ppm. IR (KBr): ν = 568 (s),
1
˜
596 (s), 778 (s), 847 (s), 1115 (s), 1209 (s), 1256 (s), 1648 (s), 1950
(s), 2075 (s) cm–1. UV/Vis (n-pentane): λ (abs) = 232.5 (1.553),
393.5 (0.042) nm. MS (EI, 70 eV): m/z (%) = 638.0 (10) [M]+.
C19H24FO6PSi2W (638.37): calcd. C 35.75, H 3.79; found C 36.00,
H 3.62.
General Procedure for the Synthesis of Complexes 4a–f: A cooled
solution (–50 °C) of the appropriate phosphane complex 1a
(440 mg, 0.8 mmol), 1b (427 mg, 0.8 mmol), 1c (437 mg, 0.8 mmol),
Complex 4d: White solid; yield: 364 mg (0.63 mmol, 79%); m.p.
1
4
49 °C (dec.). H NMR (CDCl3): δ = 0.21 [d, J(H,P) = 1.7 Hz, 9
2
or 1d (472 mg, 0.8 mmol) and 12-crown-4 (0.13 mL, 0.84 mmol) in H, Si(CH3)3], 0.31 [s, 9 H, Si(CH3)3], 1.92 [d, J(H,P) = 12.1 Hz, 1
THF (4 mL) was added dropwise to a stirred solution of freshly
prepared LDA (0.84 mmol) in THF (9 mL) at –80 °C. After 15 min
at –80 °C, the acyl chloride 3a (0.98 mL, 0.84 mmol) or 3b (0.6 mL,
0.84 mmol) was added, and the reaction mixture was warmed up
to 10 °C (ca. 2 h) in a cooling bath. The volatiles were evaporated
in vacuo, n-pentane (15 mL) was added, and the precipitate was
filtered off. The solvent was then removed and the residue subjected
to column chromatography (–20 °C, petroleum ether, petroleum
ether/diethyl ether = 10:0.5). Elution of the second band yielded
complexes 4a–d, which were crystallized from n-pentane at –80 °C.
H, PCH], 2.61 [dd, 3J(H,P) = 3.6, 4J(H,F) = 2.6 Hz, 3 H, CH3]
ppm. 13C{1H} NMR (CDCl3): δ = 2.35 [dd, J(C,P) = 2.6, J(C,F)
3
4
= 2.6 Hz, Si(CH3)3], 2.97 [d, 3J(C,P) = 1.9 Hz, Si(CH3)3], 28.03 [dd,
1J(C,P) = 42.0, J(C,F) = 1.9 Hz, PCH], 31.56 [dd, J(C,P) = 11.6,
2J(C,F) = 7.7 Hz, CH3], 195.47 [ddSat, 2J(C,P) = 7.1, 3J(C,F) = 3.2,
1J(C,W) = 128.5 Hz, cis-CO], 197.8 [d, 2J(C,P) = 27.8 Hz, trans-
CO], 216.6 [dd, 1J(C,P) = 19.6, 2J(C,F) = 13.5 Hz, C(O)P] ppm.
2
1
31P{1H} NMR (CDCl3): δ = 189.4 [dSat, J(P,W) = 275.9, J(P,F)
1
1
= 841.8 Hz] ppm. 19F{1H} NMR (CDCl3): δ = –121.8 [dSat
,
1J(F,W) = 11.2, J(P,F) = 841.8 Hz] ppm. IR (KBr): ν = 567 (m),
1
˜
596 (s), 846 (s), 1012 (s), 1121 (s), 1252 (s), 1698 (s), 1942 (s), 2078
(s) cm–1. UV/Vis (n-pentane): λ (abs.) = 229.5 (1.430), 298.0 (0.144),
340.0 (0.070) nm. MS (EI, 70 eV): m/z (%) = 575.9 (17) [M]+.
C14H22FO6PSi2W (576.3): calcd. C 29.18, H 3.85; found C 29.51,
H 3.97.
Complex 4a: Yellow solid; yield: 445 mg (0.68 mmol, 85%); m.p.
105 °C (dec.). H NMR (CDCl3): δ = 0.34 [s, 9 H, Si(CH3)3], 0.35
1
4
2
[d, J(H,P) = 0.5 Hz, 9 H, Si(CH3)3], 1.98 [d, J(H,P) = 4.1 Hz, 1
H, PCH], 7.53 (m, 2 H, Ph), 7.62 (m, 1 H, Ph), 8.17 (m, 2 H, Ph)
ppm. 13C{1H} NMR (CDCl3): δ = 3.4 [d, 3J(C,P) = 2.5 Hz,
3
1
Si(CH3)3], 3.62 [d, J(C,P) = 3.2 Hz, Si(CH3)3], 30.5 [d, J(C,P) =
Complex 4e: Yellow viscous liquid; yield: 338 mg (0.52 mmol,
1
14.2 Hz, PCH], 129.0 (s, Ph), 129.8 (s, Ph), 134.1 (s, Ph), 135.1 [d, 65%). H NMR (CDCl3): δ = 0.21 [s, 9 H, Si(CH3)3], 0.32 [s, 9 H,
2J(C,P) = 46.5 Hz, Ph], 196.6 [dSat
,
2J(C,P) = 6.4, 1J(C,W) = Si(CH3)3], 2.06 [d, J(H,P) = 11.7 Hz, 1 H, PCH], 3.60 [d, J(H,P)
2
3
127.4 Hz, cis-CO], 198.2 [d, 2J(C,P) = 31.6 Hz, trans-CO], 202.3 [d,
= 13.0 Hz, 3 H, POCH3], 7.51 [t, J(H,H) = 7.7 Hz, 2 H, Ph], 7.62
3
1J(C,P) = 1.3 Hz, C(O)P] ppm. 31P{1H} NMR (CDCl3): δ = 113.8 [t, 3J(H,H) = 7.7 Hz, 1 H, Ph], 8.05 [d, J(H,H) = 7.4 Hz, 2 H, Ph]
3
1
[sSat, J(P,W) = 267.0 Hz] ppm. IR (KBr): ν = 574 (s), 593 (s), 772
ppm. 13C{1H} NMR (CDCl3): δ = 2.9 [d, 3J(C,P) = 3.1 Hz,
˜
(s), 859 (s), 1663 (s), 1909 (s), 2075 (s) cm–1. UV/Vis (n-pentane): λ Si(CH3)3], 3.4 [d, 3J(C,P) = 2.8 Hz, Si(CH3)3], 27.3 [d, 1J(C,P) =
(abs.) = 235.0 (1.54) nm. MS (EI, 70 eV): m/z (%) = 653.9 (1.5)
[M]+. C19H24ClO6PSi2W (654.83): calcd. C 34.85, H 3.69; found C
34.89, H 3.87.
3.6 Hz, PCH], 56.3 [d, 2J(C,P) = 3.3 Hz, POCH3], 128.9 (s, Ph),
2
129.0 (s, Ph), 133.6 (s, Ph), 135.3 [d, J(C,P) = 36.5 Hz, Ph], 196.9
[dSat, 2J(C,P) = 7.1, 1J(C,W) = 118.2 Hz, cis-CO], 198.0 [d, 2J(C,P)
= 26.8 Hz, trans-CO], 208.8 [d, 1J(C,P) = 12.1 Hz, C(O)P] ppm.
Complex 4b: Yellow-green solid; yield: 334 mg (0.56 mmol, 70%);
1
31P{1H} NMR (CDCl3): δ = 154.1 [sSat, J(P,W) = 273.4 Hz] ppm.
1
m.p. 59 °C (dec.). H NMR (CDCl3): δ = 0.29 [s, 9 H, Si(CH3)3],
IR (KBr): ν = 505 (w), 574 (s), 599 (s), 694 (w), 844 (w), 1100 (w),
˜
0.34 [d, 4J(H,P) = 0.5 Hz, 9 H, Si(CH3)3], 1.89 [d, 2J(H,P) = 9.2 Hz,
1 H, PCH], 2.75 [d, 3J(H,P) = 5.1 Hz, 3 H, CH3] ppm. 13C{1H}
1256 (s), 1670 (s), 1929 (s), 2072 (s) cm–1. UV/Vis (n-pentane): λ
(abs) = 231.5 (1.703) nm. MS (EI, 70 eV): m/z (%) = 650.1 (16)
[M]+. C20H27O7PSi2W (650.41): calcd. C 36.93, H 4.18; found C
37.93, H 5.05.
3
NMR (CDCl3): δ = 3.14 [d, J(C,P) = 3.2 Hz, Si(CH3)3], 3.34 [d,
3J(C,P) = 3.2 Hz, Si(CH3)3], 26.71 [d, 1J(C,P) = 49.7 Hz, PCH],
28.38 [d, 2J(C,P) = 18.7 Hz, CH3], 196.46 [dSat 2J(C,P) = 6.4,
,
1J(C,W) = 126.8 Hz, cis-CO], 197.9 [d, 2J(C,P) = 30.4 Hz, trans- Complex 4f: Yellow viscous liquid; yield: 344 mg (0.50 mmol, 62%).
CO], 209.9 [d, 1J(C,P) = 1.9 Hz, C(O)P] ppm. 31P{1H} NMR 1H NMR (CDCl3): δ = 0.17 [s, 9 H, Si(CH3)3], 0.30 [s, 9 H, Si-
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Eur. J. Inorg. Chem. 2011, 567–572

P-Functional Acylphosphane Complexes
2
1
(CH3)3], 2.16 [d, 2J(H,P) = 12.7 Hz, 1 H, PCH], 3.26 (s, 3 H,
(CDCl3): δ = 163.5 [dSat, J(P,H) = 8.9, J(P,W) = 267.0 Hz] ppm.
OCH3), 3.59 (m, 2 H, CH2OCH3), 3.91 (m, 2 H, POCH2), 7.52 [t, 6b: 1H NMR (CDCl3): δ = 0.28 [s, 18 H, 2 Si(CH3)3], 2.64 [d,
3J(H,H) = 7.9 Hz, 2 H, Ph], 7.61 [t, 3J(H,H) = 7.7 Hz, 1 H, Ph],
2J(H,P) = 18.3 Hz, 1 H, PCH], 7.35 (m, 3 H, PhЈ), 7.47 (m, 2 H,
Ph), 7.56 (m, 1 H, Ph), 7.61 (m, 2 H, Ph), 8.08 (m, 2 H, PhЈ) ppm.
3
8.17 [d, J(H,H) = 8.1 Hz, 2 H, Ph] ppm. 13C{1H} NMR (CDCl3):
δ = 2.8 [d, 3J(C,P) = 3.1 Hz, Si(CH3)3], 3.4 [d, 3J(C,P) = 2.8 Hz, 13C{1H} NMR (CDCl3): δ = 1.67 [d, Si(CH3)3], 1.71 [s, Si(CH3)3],
1
1
4
Si(CH3)3], 27.5 [d, J(C,P) = 5.2 Hz, PCH], 58.3 (s, POCH3), 68.1
22.4 [d, J(C,P) = 31.0 Hz, PCH], 128.6 [d, J(C,P) = 1.9 Hz, Ph],
[d, 3J(C,P) = 3.2 Hz, CH2OCH3], 71.3 [d, 2J(C,P) = 8.4 Hz, 129.1 (s, PhЈ), 129.5 (s, PhЈ), 129.9 [d, J(C,P) = 2.6 Hz, Ph], 130.3
3
POCH2], 128.8 (s, Ph), 129.4 (s, Ph), 133.6 (s, Ph), 135.8 [d, 2J(C,P)
= 35.5 Hz, Ph], 197.1 [d, 2J(C,P) = 7.1 Hz, cis-CO], 198.0 [d,
2J(C,P) = 27.2 Hz, trans-CO], 208.4 [d, 1J(C,P) = 7.1 Hz, C(O)P]
(s, Ph), 130.5 (s, PhЈ), 134.1 (s, PhЈ), 137.4 [d, J(C,P) = 14.2 Hz,
2
Ph], 163.5 [d, 3J(C,P) = 11.6 Hz, PhC(O)O], 181.4 [d, 1J(C,P) =
21.9 Hz, (Ph)(O)C=P], 195.5 [dSat,
2J(C,P) = 5.2, 1J(C,W) =
ppm. 31P{1H} NMR (CDCl3): δ = 153.5 [sSat, 1J(P,W) = 278.5 Hz] 126.1 Hz, cis-CO], 197.3 [d, 2J(C,P) = 31.6 Hz, trans-CO] ppm. 31
P
ppm. IR (KBr): ν = 575 (s), 599 (s), 695 (s), 801 (m), 843 (m), 1096 NMR (CDCl3): δ = 165.8 [dSat, 2J(P,H) = 17.8, 1J(P,W) = 267.0 Hz]
˜
(m), 1260 (s), 1447 (s), 1647 (s), 1931 (s), 2072 (s) cm–1. UV/Vis (n- ppm.
pentane): λ (abs.) = 232.0 (1.314) nm. MS (EI, 70 eV): m/z (%) =
Complex 7: Methyl iodide (26 μL, 0.42 mmol) was added dropwise
to a stirred solution of complex 5bЈ (0.3 mmol) in THF (prepared
as described above) at –60 °C. The mixture was left to warm up
694.1 (16) [M]+. C22H31O8PSi2W (694.46): calcd. C 38.05, H 4.50;
found C 38.17, H 5.28.
Reaction of Complex 4a with Alkyllithium Reagents. Representative
Protocol for the Synthesis of 5bЈ by Using nBuLi: A solution of
n-butyllithium in n-hexane (1.6 m, 0.2 mL, 0.32 mmol) was added
dropwise to a stirred solution of complex 4a (196 mg, 0.3 mmol)
and 12-crown-4 (51 μL, 0.32 mmol) in THF (6 mL) at –78 °C to
give a red solution. The mixture was warmed to 0 °C in a cooling
bath. After removing the solvent, the residue was washed with n-
pentane at room temperature to give 5bЈ as a yellow-orange solid.
Yield: 216 mg (0.269 mmol, 90%); m.p. 186 °C (dec.). 1H NMR
([D8]THF): δ = 0.21 [s, 18 H, 2 Si(CH3)3], 0.33 [d, 2J(H,P) = 3.6 Hz,
1 H, PCH], 3.61 (s, 16 H,12-crown-4), 7.16 (m, 3 H, Ph), 7.49 (m,
2 H, Ph) ppm. 13C{1H} NMR ([D8]THF): δ = 2.03 [s, Si(CH3)3],
with stirring in a cooling bath for 1.5 h. The solvent was evaporated
in vacuo, and the residue was subjected to column chromatography
(–20 °C, petroleum ether/diethyl ether = 10:0.5). The product ob-
tained was crystallized from n-pentane at –50 °C to give 7 as a
yellow solid. Yield: 99 mg (0.156 mmol, 52%); m.p. 94 °C. 1H
NMR (CDCl3): δ = 0.15 [s, 9 H, Si(CH3)3], 0.38 [s, 9 H, Si-
2
2
(CH3)3], 1.14 [d, J(H,P) = 10.2 Hz, 1 H, PCH], 2.15 [d, J(H,P) =
6.2 Hz, 3 H, PCH3], 7.52 (m, 2 H, Ar), 7.61 (m, 1 H, Ph), 8.03 (m,
2 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 3.58 [d, 3J(C,P) =
2.6 Hz, Si(CH3)3], 3.65 [d, 3J(C,P) = 2.6 Hz, Si(CH3)3], 16.70 [d,
1
1J(C,P) = 1.3 Hz, PCH], 20.5 [d, J(C,P) = 26.5 Hz, PCH3], 129.3
(s, Ph), 129.38 [d, 3J(C,P) = 1.3 Hz, Ph], 133.86 (s, Ph), 136.1 [d,
1
2J(C,P) = 41.4 Hz, Ph], 197.8 [dSat 2J(C,P) = 5.8, 1J(C,W) =
,
2.07 [s, Si(CH3)3], 17.13 [d, J(C,P) = 24.5 Hz, PCH], 69.08 (s, 12-
126.7 Hz, cis-CO], 198.6 [d, 2J(C,P) = 21.3 Hz, trans-CO], 208.6 [d,
crown-4), 127.76 [d, J(C,P) = 1.2 Hz, Ph], 127.9 [d, J(C,P) =
12.2 Hz, Ph], 128.3 [d, J(C,P) = 1.9 Hz, Ph], 146.8 [d, 2J(C,P) =
1J(C,P) = 7.1 Hz, PhC(O)P] ppm. 31P{1H} NMR (CDCl3): δ = 7.03
,
2J(C,P) = 3.2, 1J(C,W) = 125.4 Hz, cis-
[sSat, 1J(P,W) = 223.8 Hz] ppm. IR (KBr): ν = 576. (s), 598 (s), 772
48.5 Hz, Ph], 200.1 [dSat
CO], 204.3 [d, 2J(C,P) = 19.4 Hz, trans-CO], 227.5 [d, 1J(C,P) =
18.1 Hz, PhCP] ppm. 31P{1H} NMR ([D8]THF): δ = –23.3 [sSat
1J(P,W) = 167.8 Hz] ppm. 7Li{1H} NMR ([D8]THF): δ = –0.24 (s)
˜
(m), 835 (s), 862 (s), 1253 (s), 1652 (s), 1936 (s), 2069 (s) cm–1. UV/
Vis (n-pentane): λ (abs.) = 231.5 (1.461), 249.0 (1.294), 350.5 (0.059)
nm. MS (EI, 70 eV): m/z (%) = 634.0 (4) [M]+. C20H27O6PSi2W
(634.41): calcd. C 37.86, H 4.29; found C 37.78, H 4.60.
,
ppm. IR (Nujol): ν = 581 (s), 766 (s), 843 (m), 1022 (s), 1087 (s),
˜
1136 (s), 1243 (s), 1918 (s), 2056 (s) cm–1. C27H40LiO10PSi2W
(802.53): calcd. C 40.41, H 5.02; found C 40.52, H 5.02.
Complex 10: Trimethylsilyl chloride (77 μL, 0.6 mmol) was added
dropwise to a stirred solution of complex 5bЈ (0.3 mmol) in THF
(prepared as described above) at –60 °C. The mixture was left to
warm up with stirring in a cooling bath for 1.5 h, and then water
(11 μL, 0.6 mmol) was added. The solvent was evaporated in vacuo,
and the residue was subjected to column chromatography (–20 °C,
petroleum ether, petroleum ether/diethyl ether = 10:0.5) to give 10
as yellow oil, which formed a crystalline material at 4 °C in 2 weeks.
Yield: 121 mg (0.195 mmol, 65%); m.p. 41 °C; Rf = 0.37 (petroleum
ether). 1H NMR (CDCl3): δ = 0.20 [s, 9 H, Si(CH3)3], 0.39 [s, 9 H,
Complexes 6a,b: A solution of n-butyllithium in hexane (1.6 m,
0.2 mL, 0.32 mmol) was added dropwise to a stirred solution of
complex 4a (196 mg, 0.3 mmol) and 12-crown-4 (51 μL, 0.32 mmol)
in THF at –78 °C. After warming the reaction mixture to –60 °C
(20 min) in a cooling bath, benzoyl chloride (37.2 μL, 0.32 mmol)
was added dropwise. The mixture was left to warm up in a cooling
bath for 1.5 h. The solvent was evaporated, n-pentane (5 mL) was
added, and the precipitate was filtered off. After evaporation of the
solvent, the residue was crystallized from n-pentane at low tem-
peratures to give a mixture of 6a,b (6a/6b = 2:1) as a yellow solid.
2
1
Si(CH3)3], 0.60 [d, J(H,P) = 7.0 Hz, 1 H, PCH], 6.77 [d, J(H,P)
= 319.5 Hz, 1 H, PH], 7.53 (m, 2 H, Ph), 7.64 (m, 1 H, Ph), 7.89
Yield: 130 mg (0.18 mmol, 60%). IR (KBr): ν = 573 (s), 593 (s),
˜
3
(m, 2 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 0.36 [d, J(C,P) =
705 (m), 854 (m), 1017 (s), 1042 (s), 1162 (s), 1254 (s), 1746 (s),
1942 (s), 2073 (s) cm–1. UV/Vis (n-pentane): λ (abs.) = 235.0 (1.355),
380.50 (0.223) nm. MS (EI, 70 eV): m/z (%) = 724.0 (4) [M]+.
C26H29O7PSi2W (724.49): calcd. C 43.10, H 4.03; found C 43.12,
2.6 Hz, Si(CH3)3], 2.93 [d, 3J(C,P) = 3.2 Hz, Si(CH3)3], 12.2 [d,
1J(C,P) = 7.1 Hz, PCH], 127.9 (s, Ph), 129.3 (s, Ph), 134.6 (s, Ph),
137.0 [d, 2J(C,P) = 40.0 Hz, Ph], 196.5 [dSat, 2J(C,P) = 5.8, 1J(C,W)
2
= 126.1 Hz, cis-CO], 198.5 [d, J(C,P) = 21.9 Hz, trans-CO], 208.0
1
H 4.29. 6a: H NMR (CDCl3): δ = 0.28 [s, 18 H, 2 Si(CH3)3], 1.41
[d, 1J(C,P) = 12.9 Hz, PhC(O)P] ppm. 31P NMR (CDCl3): δ =
2
[d, J(H,P) = 8.9 Hz, 1 H, PCH], 7.31 (m, 3 H, PhЈ), 7.5 (m, 2 H,
–39.8 [ddSat,
1J(P,H) = 319.5, 1J(P,W) = 212.3, 2J(P,H) = 7.6 Hz]
Ph), 7.54 (m, 1 H, Ph), 7.60 (m, 2 H, Ph), 8.0 (m, 2 H, PhЈ) ppm.
13C{1H} NMR (CDCl3): δ = 1.76 [s, Si(CH3)3], 1.80 [s, Si(CH3)3],
32.5 [d, 1J(C,P) = 13.6 Hz, PCH], 128.6 (s, Ph), 128.8 (s, Ph), 129.0
ppm. IR (KBr): ν = 573 (s), 627 (s), 854 (m), 1255 (s), 1652 (s),
˜
1936 (s), 2071 (s) cm–1. UV/Vis (n-pentane): λ (abs.) = 234.0 (1.448),
347.0 (0.053) nm. MS (EI, 70 eV): m/z (%) = 619.9 (17) [M]+.
C19H25O6PSi2W (620.38): calcd. C 36.78, H 4.06; found C 37.22,
H 4.28.
4
3
[d, J(C,P) = 1.3 Hz, Ph], 129.6 [d, J(C,P) = 2.6 Hz, Ph], 130.4 (s,
2
PhЈ), 130.0 (s, Ph), 134.2 (s, PhЈ), 137.6 [d, J(C,P) = 16.1 Hz, Ph],
164.2 [d, 3J(C,P) = 9.0 Hz, PhC(O)O], 182.1 [d, 1J(C,P) = 23.9 Hz,
2
1
(Ph)(O)C=P], 195.4 [dSat, J(C,P) = 5.2, J(C,W) = 126.1 Hz, cis-
Crystallographic Data: Crystal structure data for complex 4a
(C19H24ClO6PSi2W): M = 654.83, orthorhombic, P212121, a =
CO], 198.4 [d, 2J(C,P) = 31.0 Hz, trans-CO] ppm. 31P NMR
Eur. J. Inorg. Chem. 2011, 567–572
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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571

V. Nesterov, L. Duan, G. Schnakenburg, R. Streubel
FULL PAPER
9.5057(2), b = 10.8944(2), c = 24.2214(5) Å, V = 2508.34(9) Å3, Z
= 4, dcalcd. = 1.734 Mg/m3, μ = 4.901 mm–1, T = 123(2) K. A total
of 21607 reflections were measured with a Nonius–KappaCCD dif-
fractometer by using monochromated Mo-Kα radiation (λ =
0.71073 Å), 5981 of which were unique (Rint = 0.0598). A semi-
empirical absorption correction from equivalents was applied
(min./max. transmission 0.1615/0.3087). The structure was solved
by Patterson methods and refined by full-matrix least-squares fit-
ting against F2 for all reflections. Non-hydrogen atoms were refined
anisotropically; hydrogen atoms were refined as rigid groups. R val-
ues [IϾ2σ(I)]: R1 = 0.0293, wR2 = 0.0584. R values (all data): R1
= 0.0369, wR2 = 0.0607, min./max. electron difference –1.360/
1.090 e/Å3. Crystal-structure data for complex 6a (C26H29O7P-
Si2W): M = 724.49, monoclinic, P21/n, a = 10.4754(2), b =
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=
1.582 Mg/m3, μ = 3.968 mm–1, T = 123(2) K. A total of 56829 re-
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tion correction from equivalents was applied (min./max. trans-
mission 0.1993/0.2998). The structure was solved by Patterson
methods and refined with full-matrix least-squares fitting against
F2 for all reflections. Non-hydrogen atoms were refined anisotropi-
cally; hydrogen atoms were refined as rigid groups. R values
[IϾ2σ(I)]: R1 = 0.0311, wR2 = 0.0675. R values (all data): R1
=
0.0431, wR2 = 0.0700, min./max. electron difference –1.454/1.190 e/
Å3. CCDC-785125 (4a) and -785126 (6a) contain the supplemen-
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Acknowledgments
Financial support by the Deutsche Forschungsgemeinschaft (STR
411/26-1) and the COST action cm0802 “PhoSciNet” is gratefully
acknowledged.
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Received: October 20, 2010
Published Online: December 27, 2010
572
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Eur. J. Inorg. Chem. 2011, 567–572