P-OR functional phosphanido and/or Li/OR phosphinidenoid complexes?

Article abstract of DOI:10.1002/ejic.201200368

P-H,P-OR-substituted phosphane complexes 3a-e have been synthesized by two methods: (1) the thermal reaction of 2H-azaphosphirene complex 1 with methanol, n-butanol, or ethylene glycol monomethyl ether (3b,c,e) or (2) the reaction of P-chlorophosphane complex 2 with appropriate sodium phenolate salts (3a,d). All the complexes 3a-e were obtained in good yields and fully characterized by NMR, IR, MS, and elemental analysis. Furthermore, the structures of 3a, 3d and 3e were confirmed unambiguously by X-ray analysis. The deprotonation of complexes 3a-e by using lithium diisopropylamide in the presence of 12-crown-4 led to phosphinidenoid complexes 4a-e, which exhibit downfield ³¹P resonances and small tungsten-phosphorus coupling constants. Studies on the reactivity of complexes 4a-c,e revealed a phosphanido-type reactivity, and only for complex 4d, a thermally labile complex, was evidence found for a phosphinidene-type reactivity. Bifunctional phosphane complexes 3a-e have been synthesized and deprotonated with lithium diisopropylamide as base to provide Li/OR phosphinidenoid complexes 4a-e. Solutions of 4a-e display relatively high thermal stability, except for complex 4d. Whereas the NMR signatures of 4a-e correlate with a phosphinidenoid- type bonding, a phosphanido-type reactivity was revealed by reactions of 4a with electrophiles and C-C and C-O π-systems. Copyright

Full text of DOI:10.1002/ejic.201200368

FULL PAPER
DOI: 10.1002/ejic.201200368
P-OR Functional Phosphanido and/or Li/OR Phosphinidenoid Complexes?
Lili Duan,[a] Gregor Schnakenburg,[a] Jörg Daniels,[a] and Rainer Streubel*[a]
Dedicated to Professor K. Tamao[‡]
Keywords: Phosphanes / P ligands / Lithium / Phosphinidenoids / Tungsten / Structure elucidation
P-H,P-OR-substituted phosphane complexes 3a–e have been
synthesized by two methods: (1) the thermal reaction of 2H-
azaphosphirene complex 1 with methanol, n-butanol, or eth-
ylene glycol monomethyl ether (3b,c,e) or (2) the reaction of
protonation of complexes 3a–e by using lithium diisoprop-
ylamide in the presence of 12-crown-4 led to phosphinid-
enoid complexes 4a–e, which exhibit downfield 31P reso-
nances and small tungsten–phosphorus coupling constants.
P-chlorophosphane complex 2 with appropriate sodium phen- Studies on the reactivity of complexes 4a–c,e revealed a
olate salts (3a,d). All the complexes 3a–e were obtained in “phosphanido-type” reactivity, and only for complex 4d, a
good yields and fully characterized by NMR, IR, MS, and ele- thermally labile complex, was evidence found for a “phos-
mental analysis. Furthermore, the structures of 3a, 3d and 3e
phinidene-type” reactivity.
were confirmed unambiguously by X-ray analysis. The de-
vide [(CO)5W(RPH2)]; the bonding situation of lithium re-
mained unclear. In 2005, Westerhausen et al. reported the
phosphanido complex [Li(thf)4][(CO)5W{P(SiiPr3)2}], re-
vealing a solvent-separated ion-pair structure[2b] and an un-
usually upfield-shifted 31P resonance (δ = –409.2 ppm, 1JW,P
= 136.1 Hz). In addition to such examples of ill- and well-
defined bonding situations of P–Li compounds are exam-
ples in which the lithium ion coordinates within the mole-
cule but not to the phosphorus atom. One recent example
Introduction
Alkali phosphanides[1]
I
and their complexes[2] II
(Scheme 1) are classes of compounds in which an alkali
metal is (most often) bound directly to the phosphorus
atom. They can be considered as key reagents in main-
group-element and transition-metal chemistry as they are
valuable synthons for the formation of P–E bond systems.
may be the phosphanido complex [(CO)5W(RP{CNLi(12-
1
crown-4)})][2c] [R = CH(SiMe3)2; δ = –152.9, JW,P
=
100 Hz], in which the lithium ion is bound to the nitrogen
atom; this phosphanido complex reacts with electrophiles
such as MeI or MeOSO2CF3 exclusively to give the P-meth-
ylated phosphane complex. Note also that, despite the pres-
ence of the cyano functionality, no decomposition to yield
LiCN was observed at ambient temperature.
Given this background and the formal similarities be-
tween phosphinidenoids[3] III and their complexes IV on
the one hand, and carbenoids[4] V and silylenoids[5] VI
(Scheme 1) on the other, one might wonder why it took so
long to establish phosphinidenoid complexes IV[6] or why
phosphinidenoids III have not yet even been fully
achieved.[7] This is even more strange given the versatile use
of V and VI in organic synthesis, that is, enabling a plethora
of reactions such as electrophilic, nucleophilic, carbene-like,
and, to some extent, redox reactions. The chemistry of
Ph2Si(Li)OtBu[5b] might be a good case in point for silyl-
enoids VI, which have been developed by Tamao et al. It
is remarkable that all the Li/X or Li/OR carbenoids and
silylenoids known to date show 13C or 29Si NMR chemical
Scheme 1. Phosphanides I and their complexes II, phosphinidenoids
III and their complexes IV, carbenoids V, and silylenoids VI (R, RЈ
= organic substituent; M = alkali metal, such as Li, Na, K; X =
halogen; MLn = transition-metal fragment).
In 1987, Mathey and co-workers reported the synthesis
of the first monometalated terminal (phosphanido)transi-
tion-metal complex (II) [(CO)5W(LiPH2)],[2a] which was ob-
tained by treating the (phosphane)tungsten complex with
nBuLi at low temperature. The complex, identified by 31P
1
1
NMR spectroscopy (δ = –273 ppm, JW,P = 68 Hz, JP,H
=
320 Hz), reacted as a nucleophile with alkyl halides to pro-
[a] Institut für Anorganische Chemie
Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
Fax: +49-228-739616
E-mail: r.streubel@uni-bonn.de
[‡] For his inspiring work on silylenoid chemistry.
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P-OR Phosphanido and/or Li/OR Phosphinidenoid Complexes?
shifts downfield of their non-lithiated precursors. In ad-
dition to this important NMR feature, they show markedly
elongated C–E or Si–E bonds (E = Cl, O) in solid-state
structures compared with their corresponding non-lithiated
derivatives.[4g,5h]
Recently, Li/X (phosphinidenoid)tungsten complexes (X
= F,[8a] Cl[8b,8c]) were firmly established, and their thf solu-
tions displayed markedly downfield-shifted 31P NMR reso-
nances and small tungsten–phosphorus coupling constants;
information on the solid-state structures of such derivatives
is still lacking. Reactivity studies on Li/Cl (phosphinid-
enoid)tungsten complexes [R = CH(SiMe3)2, C5Me5] re-
vealed nucleophilic reactivity towards organic iodides[9] and
acyl chlorides,[10] and phosphinidene-like reactivity towards
π-systems such as nitriles, alkynes, and aldehydes.[8b] The
high negative charge density at the phosphorus atom also
enabled redox reactions, as the initial studies revealed: SET
oxidation occurs with tritylium salts, thus leading to tran-
sient P-X functional phosphanyl complexes that were de-
tected by EPR spectroscopy.[11] The latter not only possess
high electron-spin density at the phosphorus atom (70–
85%) but also underwent phosphorus-centered reactions
thereby providing new perspectives in synthesis[11] as well
as new insights into systems possessing very weak P–C
bonds.[12]
Recently, we gained further insight into these systems.
The use of strong and sterically demanding organic bases
enabled the synthesis of P-X and P-OR (phosphinidenoid)
tungsten complexes possessing enhanced thermal stabilities.
The first single-crystal structure of a P-OPh complex deriv-
ative revealed a solvent-separated ion pair by virtue of
weakly coordinating cations.[13] In contrast, the first
attempts to synthesize Li/OAc (phosphinidenoid)tungsten
complexes (OAc = CH3CO2) resulted only in decomposi-
tion upon warming to ambient temperature,[14] whereas an
Li/OPh (phosphinidenoid)tungsten complex was success-
fully used in P–C bond-forming reactions with acyl chlor-
ides.[10]
Scheme 2. Synthesis of 1,1Ј-bifunctional phosphane complexes 3a–e.
fully characterized by multinuclear NMR, IR, MS, and ele-
mental analysis. Moreover, the structures of 3a, 3d, and 3e
were unambiguously confirmed by single-crystal X-ray
analysis.
The 31P NMR resonances of complexes 3a–e appear in
the narrow range of δ = 99.0–109.7 ppm (1JW,P = 265–
1
275 Hz, JP,H = 320–330 Hz), in quite good agreement with
the values reported earlier by Mathey and co-workers for
1,1Ј-bifunctional phosphane complexes, although they
demonstrated that the chemical shifts are strongly influ-
enced by the R group on the phosphorus atom. For exam-
ple, [(CO)5W{ClH2CP(H)OMe}][17] displays a resonance at
1
δ = 104.8 ppm (1JW,P = 283.2 Hz, JP,H = 352 Hz), whereas
[(CO)5W{EtO2CP(H)OMe}][18] exhibits a resonance at δ =
1
78.3 ppm (1JW,P = 278 Hz, JP,H = 365.5 Hz). Selected
NMR spectroscopic data for the new complexes 3a–e are
given in Table 1.
Table 1. Selected NMR spectroscopic data (in CDCl3) for complexes
3a–e.
Complex
δ [ppm]/J [Hz]
δ(1H)[a]/1JP, H
δ(31P)/1JW,P
δ(13C)[b]/1JP,C
3a
3b
3c
3d
3e
106.8/275.9
109.7/267.0
107.3/267.0
99.0/274.7
102.5/267.0
8.41/325.2
7.80/320.7
7.86/324.1
8.47/336.3
7.83/319.7
22.6/13.7
21.4/13.6
23.5/13.6
24.2/9.7
30.2/8.4
Herein we report the first extensive study on the synthe-
sis and reactions of Li/OR (phosphinidenoid)tungsten com-
plexes.
[a] Hydrogen atom directly bound to the phosphorus atom. [b] Car-
bon atom directly bound to the phosphorus atom.
Results and Discussion
Potential precursors for Li/OR phosphinidenoid com-
The 13C{1H} NMR data shown in Table 1 reveal 13C res-
1
plexes, that is, bifunctional phosphane complexes 3a–e, onances in the range δ = 21.4–30.2 ppm with JP,C values
were conveniently prepared according to the two routes of 8.4–13.7 Hz; these have been assigned to the carbon
shown in Scheme 2: (1) by thermal reaction of 2H-azaphos- atom of the CH(SiMe3)2 group directly bound to the phos-
phirene complex 1[15] with methanol, ethylene glycol mono- phorus atom and are similar to the data of related P-X
methyl ether, or n-butanol in toluene at 75 °C (3b,c,e) or organophosphane complexes [R = CH(SiMe3)2], such as
(2) by reaction of P-chlorophosphane complex 2[16] and so- [(CO)5W{RP(H)F}][8a] (δC = 28.0 ppm, JP,C = 18.8 Hz)
1
dium phenolate salts in diethyl ether at –40 °C with NaCl and [(CO)5W{RP(H)Cl}][16] (δC = 24.6 ppm, JP,C
=
1
elimination (3a,d).
4.8 Hz).
All reactions led selectively and in good yields (51–66%)
The IR spectra of the complexes 3a–e display a ν(P–H)
to the 1,1Ј-bifunctional phosphane complexes 3a–e, which absorption band at 2367 (3a), 2264 (3b), 2260 (3c), 2257
were isolated by column chromatography or by washing (3d), and 2290 (3e), which are in the normal range found
with n-pentane at low temperature. Complexes 3a–e were for P–H absorptions (2200–2400 cm–1).[19,20] Typically very
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L. Duan, G. Schnakenburg, J. Daniels, R. Streubel
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intense absorptions due to CO stretching vibrations of the
W(CO)5 group in complexes 3a–e can be observed in the
range 1910–2010 cm–1.
The molecular structures of 3a, 3d, and 3e in the solid
state were determined by single-crystal X-ray diffraction
studies (Figures 1, 2 and 3). The crystal system/space group
of 3e is orthorhombic P212121, whereas those of 3a and 3d
¯
are triclinic P1. These complexes show common molecular
structural features; for example, all the phosphorus centers
have a trigonal geometry [sum of the bond angles at the
phosphorus atom (includes the W(CO)5 moiety but not the
P–H group): 342.3 (3a), 338.4 (3d), 341.1° (3e)]. Although
measured carefully, the P–H bond lengths of 3a, 3d, and 3e
vary significantly: 1.40 (3a), 1.27 (3d), and 1.34 Å (3e).
Figure 3. Molecular structure of complex 3e in the crystal form (ellip-
soids drawn at the 50% probability level; except for H1 hydrogen
atoms have been omitted for clarity). Selected bond lengths [Å] and
angles [°]: P–H1 1.34(3), P–O1 1.621(2), P–W 2.4750(8), P–C5
1.807(3); H1–P–O1 95.9(13), H1–P–C5 105.2(13), H1–P–W
111.0(12), O1–P–C5 99.33(13), O1–P–W 121.39(9), C5–P–W
120.38(11).
4a–e were observed at low field (δ = 200–220 ppm) with
small tungsten–phosphorus coupling constants of about
76 Hz (Table 2). This matches the data obtained for the re-
1
lated Li/F (δ = 305.9 ppm, JW,P = 71.3 Hz)[8a] and Li/Cl
1
phosphinidenoid complexes (δ = 212.9 ppm, JW,P
=
67.4 Hz) with the same substituent on the phosphorus
atom.[8b] In particular, the latter set of data are strikingly
similar to the NMR spectroscopic data of 4a–e, which in
turn means that the Li/X phosphinidenoid complexes are
largely determined by the specific bonding situation of the
phosphorus center and to a minor extent by the nature of
the substituent X. Even more important is the observation
that these data are also almost identical to those reported
Figure 1. Molecular structure of complex 3a in the crystal form (ellip-
soids drawn at the 50% probability level; except for H1, hydrogen
atoms have been omitted for clarity). Selected bond lengths [Å] and
angles [°]: P1–H1 1.40(3), P1–C1 1.811(2), P1–W 2.4791(6), P1–O1
1.6522(17), O1–C8 1.397(3); H1–P1–C1 102.4(12), H1–P1–O1
97.9(12), H1–P1–W1 110.4(11), C1–P1–W1 123.40(8), C1–P1–O1
100.43(10), W1–P1–O1 118.47(7).
for the solvent-separated ion pairs [cation: N,N-di-tert-
1
butylimidazolium, X = OPh: δ = 208.6 ppm, JW,P
=
75.5 Hz; cation: tBu-P4-phosphazene, X = OPh: δ =
Scheme 3. Synthesis of Li/OR organophosphinidenoid complexes 4a–
e.
Figure 2. Molecular structure of complex 3d in the crystal form (ellip-
soids drawn at the 50% probability level; except for H16, hydrogen
atoms have been omitted for clarity). Selected bond lengths [Å] and
angles [°]: P–H16 1.27(3), P–W 2.4918(6), P–C1 1.810(3), P–O1
1.6571(18), O1–C8 1.404(3); H16–P–W 114.9(16), H16–P–C1
103.3(16), H16–P–O1 97.2(16), C1–P–W 117.04(8), C1–P–O1
102.37(10), O1–P–W 119.03(7).
Table 2. Selected NMR spectroscopic data (in [D8]thf) for complexes
4a–e.
Complex
δ [ppm]/J [Hz]
δ(13C)[a]/1JP,C
δ(31P)/1JW,P
4a
4b
4c
4d
4e
209.1/76.2
209.6/68.7
208.8/69.0
220.7/78.5
201.3/68.6
25.4/75.0
25.8/66.6
24.3/68.5
22.7/78.8
–/–[b]
The 1,1Ј-bifunctional organophosphane complexes 3a–e
were then subjected to deprotonation by using lithium di-
isopropylamide (LDA) in diethyl ether at –78 °C in the
presence of 12-crown-4 (Scheme 3). The 31P NMR reso-
[a] Carbon atom directly bound to the phosphorus atom. [b] Could
nances of the resulting Li/OR phosphinidenoid complexes not be clearly assigned.
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P-OR Phosphanido and/or Li/OR Phosphinidenoid Complexes?
209.7 ppm, 1JW,P = 76.3 Hz], which led us to the conclusion
All the products 5a–d, 6, 7a–c,[10] 8, and 9 were fully
that complexes 4a–e have separated ion pairs as well; phos- characterized by multinuclear NMR, IR, MS, and elemen-
phorus–lithium coupling was not observed.[13]
tal analysis. In addition, the structures of 5a (Figure 4) and
In contrast to the former report on Li/OAc phosphinid- 6 (Figure 5) were established unequivocally by X-ray crystal
enoid complexes,[14] the Li/OR complexes 4a–c,e (not 4d) analysis.
are stable at ambient temperature and could be fully charac-
From the reactions with typical electrophiles such as
terized by multinuclear NMR spectroscopy in [D8]thf. The MeI, CDCl3, and PhC(O)Cl, the nucleophilic reactivity of
13C{1H} NMR spectra of complexes 4a–e display reso- complexes 4a–d came to the fore. It is noteworthy that the
nances for the carbon atom of the CH(SiMe3)2 group di- reaction of 4a with CDCl3 led to the P-chlorophosphane
rectly bound to the phosphorus atom at δ ≈ 23–25 ppm. complex 6, most probably via an intermediate P-CDCl2
The increase in the phosphorus–carbon coupling constants complex by a CǞP chlorine shift; related decompositions
is remarkable relative to the precursors 3a–d [75.0 (4a), 66.0 have been observed previously.[22]
(4b), 68.5 (4c), and 78.8 Hz (4d)] and parallel the finding for
the Li/F and Li/Cl phosphinidenoid complexes (87.4 and PhCCH and PhCHO differed from those of the corre-
80.5 Hz). sponding Li/Cl phosphinidenoid complex. Here, the P-vin-
In addition to the already noted significantly enhanced ylphosphane complex (from 4a) and P-(α-meth-
The outcomes of the reactions of complexes 4a,b with
8
thermal stabilities of the Li/OR phosphinidenoid complexes oxybenzyl)phosphane complex 9 (from 4b) were obtained
compared with their halogen analogues, one more aspect as the final products after methylation with TfOMe, clearly
deserves mention: None of the derivatives underwent de- showing the nucleophilic reactivity of the Li/OR derivatives
composition to give diphosphene complexes; however, in in the first reaction step. The 31P NMR signal for complex
the case of complex 4d, the presence of cyclotriphos- 8 appears at δ = 154.1 ppm (1JW,P = 269.6 Hz), which is
phane[21] was observed in the NMR spectra (after ca. 1 h). downfield of the P-vinylphosphane complexes [(CO)5W(Ph)-
1
Although the pathway for its formation is unclear at this P(OMe)(ClC=CH2)][23] (δ = 125.6 ppm, JW,P = 289.0 Hz)
point, the latter provides some evidence of decomposition and [(CO)5W(Ph)P(OMe)(PhC=CHPh)] (δ = 129.3 ppm,
by a phosphinidene-like pathway. Having now accessed Li/ 1JW,P = 278.0 Hz).[24] Comparison of the 31P NMR spectro-
1
OR phosphinidenoid complexes and given the increased la- scopic data of complex 9 (δ = 161.8 ppm, JW,P = 275.9 Hz)
bility of 4d, the reactivities of 4a–d towards different sub- with those of [(CO)5WP(R)(F){CH(OH)Ph}] [R
=
1
strates, such as methyl iodide, deuteriated chloroform (4a), CH(SiMe3)2; δ = 198.1 ppm, JW,P = 296 Hz][25] lend further
benzoyl chloride (4a–c), phenylacetylene (4a,b), and benzal- support to this assignment. It is also remarkable that the for-
dehyde (4a,b), were studied; the results are shown in mation of complex 9 was only observed in the case of the
Scheme 4.
methoxy derivative 4b and not in the case of the phenoxy
analogue 4a, which may be explained by either the higher
steric demand of the phenyl group in 4a and/or by assuming
a higher nucleophilicity of complex 4b compared with 4a.
The molecular structure of P-methylphosphane complex
5a was confirmed by X-ray analysis (Figure 4); comparison
with its precursor 3a and [(CO)5W{RP(Me)(CN)}] [R =
CH(SiMe3)2][3] showed no differences of particular interest.
Figure 4. Molecular structure of complex 5a in the crystal form (ellip-
soids are shown at the 50% probability level, hydrogen atoms have
been omitted for clarity). Selected bond lengths [Å] and angles [°]:
P–O1 1.649(2), P–W 2.5045(7), P–C8 1.819(3), P–C1 1.814(3), O1–
C2 1.398(3); C1–P–O1 100.28(12), C1–P–C8 106.89(13), C1–P–W
Scheme 4. Reactions of Li/OR phosphinidenoid complexes 4 with 115.28(10), O1–P–C8 97.66(12), O1–P–W 114.80(8), C8–P–W
different reagents.
119.05(9), P–O1–C2 124.68(17).
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P-Chlorophosphane complex 6 showed a resonance at δ = col.[26] The NMR spectroscopic data of complex 13 (δ =
1
1
186.7 ppm in the 31P NMR spectrum with a large coupling 33.2 ppm, JW,P = 227.6 Hz, JP,H = 300.1 Hz) are similar to
constant (1JW,P = 335.7 Hz). The crystallographic parameters those of the known complex [Li(12-crown-4)][(CO)5WRP(H)
of 6 (Figure 5) are in the normal range as also observed for O] (δ = 46.0 ppm, 1JW,P = 244.1 Hz, 1JP,H = 302.6 Hz),[14] but
complex 5a.
has a solvent-separated ion-pair structure.
To examine this surprising result further, the reaction of
pure [(CO)5WP(R)H{OLi(12-crown-4)}] (14)[14] with tetra-n-
butylammonium fluoride was performed (Scheme 6), but
yielded the same result.
Scheme 6. Selective transformation of complex 14 into complex 13.
Conclusions
Figure 5. Molecular structure of complex 6 in the crystal form (ellip-
soids are shown at the 50% probability level, hydrogen atoms have
been omitted for clarity). Selected bond lengths [Å] and bond angles
[°]: P–O1 1.6187(16), P–C1 1.799(2), P–W 2.4731(6), P–Cl 2.0918(9),
O1–C8 1.411(3); W–P–O1 117.48(7), W–P–C1 120.18(8), W–P–Cl
114.08(3), C1–P–O1 99.58(10), Cl–P–O1 99.00(7), P–O1–C8
124.35(16).
In this first systematic study on the synthesis, properties,
and reactions of Li/OR (phosphinidenoid)tungsten com-
plexes the following results were obtained. P-Bifunctional
phosphane complexes 3a–e, synthesized by two different
routes, are excellent precursors for Li/OR phosphinidenoid
complexes 4a–e, which were obtained by the reactions of 3a–
e with lithium diisopropylamide (LDA) and 12-crown-4. The
31P NMR analyses of complexes 4a–e revealed resonances at
low field (ca. 200–220 ppm) and small tungsten–phosphorus
coupling constants (ca. 68–75 Hz), which is the typical NMR
signature.
Complexes 4a–c,e showed a significantly increased thermal
stability and hence a more pronounced phosphanido-type re-
activity. However, derivative 4d showed a tendency to decom-
pose to a cyclotriphosphane, but not to a diphosphene com-
plex, as has been observed previously for chloro Li/Cl phos-
phinidenoid complex.
The nucleophilic reactivity of complexes 4 was examined
in reactions with MeI, CDCl3, and PhC(O)Cl, and also with
π-systems such as PhCHO and PhCCH. In the last two cases,
quenching with TfOMe allowed the isolation of complexes 8
and 9 and hence confirmed that nucleophilic attack of com-
plex 4 at C–C (4a) and C–O double bonds (4b) is effective.
Cation exchange in complex 4a failed, and instead salt 13
was obtained, which shows that a complicated decomposi-
tion, including a desilylation of the phosphorus ligand, had
taken place.
Encouraged by our initial success in using NHC and phos-
phazene derivatives and creating a cation in the process,[13]
we carried out a preliminary study on the possibility of re-
placing the lithium ion by an organic cation by using an al-
ready formed Li/OR phosphinidenoid complex. As the reac-
tion of complex 4a with tetra-n-butylammonium fluor-
ide (10) with a 1:1 stoichiometry was unselective, we em-
ployed an excess of the ammonium fluoride, which led to a
selective, albeit surprising outcome. We assume that the an-
ionic phosphane complex 12 is initially formed, which decom-
poses to give complex 13 as the final product (Scheme 5). One
byproduct, compound 11, was isolated and unambiguously
confirmed. As complex 13 possesses a P-CH3 substituent in-
stead of the P-CH(SiMe3)2, it must have been formed by a
desilylation pathway, which is still unknown. Recently, a selec-
tive desilylation of this particular substituent was achieved in
the case of a diazaphosphole complex by a different proto-
Experimental Section
General: All operations were performed under purified and dried ar-
gon. Solvents were distilled from sodium wire/benzophenone. NMR
spectroscopic data were recorded with a Bruker Avance 300 spec-
trometer at 25 °C. Shifts are given relative to tetramethylsilane (1H:
300.1 MHz; 13C: 75.5 MHz) and 85% H3PO4 (31P: 121.5 MHz) in
ppm. MS data were recorded with a Kratos MS 50 spectrometer
(EI, 70 eV). IR spectra were recorded with an FT-IR Nicolet 380
spectrometer. Melting points were obtained with a Büchi 535 capil-
Scheme 5. Proposed mechanism for the reaction of complex 4a with
tetra-n-butylammonium fluoride.
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P-OR Phosphanido and/or Li/OR Phosphinidenoid Complexes?
lary apparatus. Elemental analyses were performed by using an Ele- [s, ν(CO)], 2072 [s, ν(CO)], 2260 [w, ν(PH)] cm–1. MS: m/z (%) =
menta (Vario EL) analytical gas chromatograph.
589.9 (40) [M]+, 562.0 (30) [M – CO]+, 534.0 (37) [M – 2 CO]+, 506.0
(85) [M – 3 CO]+, 73.0 (100) [SiMe3]+. C16H29O6PSi2W (588.40):
calcd. C 30.52, H 4.61; found C 30.79, H 4.24.
Synthesis of 3a: Phosphane complex 2 (551 mg, 1 mmol) in Et2O
(10 mL) was added to a solution of sodium phenolate (150 mg,
1.2 mmol) in Et2O (10 mL) at low temperature. Then the reaction Synthesis of 3d: Complex 2 (551 mg, 1 mmol) in Et2O (10 mL) was
mixture was stirred overnight, while gently warming to ambient tem- added to a solution of sodium 2,6-dimethylphenolate (106 mg,
perature. The mixture was filtered, the solvent removed in vacuo
1.1 mmol) in Et2O (10 mL) at low temperature. Then the reaction
mixture was stirred overnight, while gently warming to ambient tem-
(10–2 mbar), and the raw product was purified by washing with n-
pentane at low temperature (ca. –50 °C); yellow crystals were ob- perature. It was then filtered, and all the volatiles were removed in
tained from n-pentane. Yield: 378 mg (0.62 mmol), 62%; m.p. 78 °C
vacuo (10–2 mbar). The raw product was purified by washing with n-
(decomp.). 1H NMR (CDCl3): δ = 0.28 [d, JH,H = 0.6 Hz, 9 H, pentane at low temperature (ca. –50 °C); pale-yellow crystals were
4
Si(CH3)3], 0.38 [s, 9 H, Si(CH3)3], 1.10 [dd, 3JP,H = 1.9, 2JP,H = 2.8 Hz,
obtained from n-pentane. Yield: 420 mg (0.66 mmol), 66%; m.p. 88–
3
3
2
1 H, PCH], 7.08 (d, JH,H = 7.6 Hz, 2 H, o-Ph-H), 7.17 (t, JH,H
=
90 °C. 1H NMR (CDCl3): δ = 0.35 [d, JH,H = 11.1 Hz, 18 H,
3
2
3
7.6 Hz, 1 H, p-Ph-H), 7.36 (t, JH,H = 7.5 Hz, 2 H, m-Ph-H), 8.41
Si(CH3)3], 1.36 (dd, JP,H = 5.1, JH,H = 3.1 Hz, 1 H, PCH), 2.39 [s,
3
1
(d, 1JP, H = 325.2, JP,H = 1.7 Hz, 1 H, P-H) ppm. 13C{1H} NMR: δ
6 H, 2,6-(CH3)2C6H3], 7.01 (s, 3 H, 2,6-Me2C6H3), 8.47 (dd, JP,H =
3
3
3
= 0.3 [d, JP,C = 2.6 Hz, Si(CH3)3], 2.2 [d, JP,C = 2.6 Hz, Si(CH3)3],
336.3, JH,H = 4.5 Hz, 1 H, P-H) ppm. 13C{1H} NMR: δ = 1.2 [d,
1
4
3
22.9 (d, JP,C = 13.7 Hz, PCH), 120.2 (d, JP,C = 6.5 Hz, m-PhC),
3JP,C = 3.2 Hz, Si(CH3)3], 3.0 [d, JP,C = 2.6 Hz, Si(CH3)3], 24.2 (d,
5
2
124.1 (d, JP, C = 1.3 Hz, p-PhC), 129.7 (s, o-PhC), 153.7 (d, JP,C
=
=
=
1JP,C = 9.7 Hz, PCH), 124.9 (d, 5JP,C = 1.9 Hz, p-PhC), 130.0 (d, 4JP,C
2
2
6.5 Hz, POC), 195.8 (d, JP,C = 7.8 Hz, cis-CO), 198.3 (d, JP,C
= 1.9 Hz, m-PhC), 130.6 (d, 3JP,C = 4.5 Hz, o-PhC), 150.4 (d, 2JP, C
=
=
27.2 Hz, trans-CO) ppm. 31P{1H} NMR: δ = 106.8 (ssat
,
1JW,P
7.8 Hz, POC), 196.3 (d, JP,C = 6.5 Hz, cis-CO), 198.4 (d, JP,C
2
2
275.9, JP,H = 325.5 Hz) ppm. IR (KBr): ν = 1910 [vs, v(CO)], 1920 27.2 Hz, trans-CO) ppm. 31P{1H} NMR: δ = 99.0 (ssat, 1JW,P = 274.7,
1
˜
[vs, ν(CO)], 1957 [s, ν(CO)], 1979 [m, ν(CO)], 2073 [m, ν(CO)], 2290
[w, ν(PH)] cm–1. MS: m/z (%) = 608.0 (51) [M]+·, 524.0 (80) [M – 3
CO]+, 496.0 (45) [M – 4 CO]+, 468.0 (40) [M – 5 CO]+, 73.0 (100)
1JP,H = 335.7 Hz) ppm. IR (KBr): ν = 1915 [s, ν(CO)], 1985 [s,
˜
ν(CO)], 2072 [m, ν(CO)], 2367 [w, ν(PH)] cm–1. MS: m/z (%) = 636.1
(41) [M]+, 552.1 (55) [M – 3 CO]+, 524.1 (28) [M – 4 CO]+, 515.0
[SiMe3]+. C18H25O6PSi2W (608.39): calcd. C 35.54, H 4.14; found C (60) [M – 2,6-Me2C6H3O]+, 487.0 (49) [M – 5 CO – 2,6-Me2C6H3O]
35.57, H 4.27.
+, 73.0 (100) [SiMe3]+. C18H25O6PSi2W (608.39): calcd. C 37.74, H
4.59; found C 37.76, H 4.65.
Synthesis of 3b: Methanol (41 μL, 1 mmol) was added to a solution
of 2H-azaphosphirene complex 1 (1 mmol, 617 mg) in toluene Synthesis of 3e: n-Butanol (90 μL, 1 mmol) was added to a solution
(30 mL), and the solution was stirred at 75 °C for 3 h. All volatiles of 2H-azaphosphirene complex 1 (1 mmol, 617 mg) in toluene
were then removed in vacuo (ca. 0.01 mbar), and the product was (30 mL) and then stirred at 75 °C for 3 h. The solvents were then
purified by column chromatography (SiO2, –20 °C, eluent: petroleum removed in vacuo (ca. 0.01 mbar), and the product was purified by
ether) and obtained as the first fraction. Yield: 290 mg (0.53 mmol), column chromatography (SiO2, –20 °C, eluent: petroleum ether) and
1
53%; m.p. 64 °C. H NMR (CDCl3): δ = 0.12 (s, 9 H, SiMe3), 0.18
obtained in the first fraction. Yellow single crystals were obtained
(s, 9 H, SiMe3), 0.86 (d, 3JH,H = 1.5 Hz, 1 H, PCH), 3.43 (d, 3JP,H
=
from n-pentane solutions. Yield: 300 mg (0.51 mmol), 51%; m.p.
1
3
1
14.7 Hz, 3 H, POCH3), 7.8 (d, JP,H = 320.7, JH,H = 1.5 Hz, 1 H,
62 °C. H NMR (CDCl3): δ = 0.21 [s, 9 H, Si(CH3)3], 0.27 [s, 9 H,
POCH3) ppm. 13C{1H} NMR: δ = –1.9 [d, JP,C = 2.6 Hz, Si(CH3)
Si(CH3)3], 0.91 (d, JH,H = 1.3 Hz, 1 H, PCH), 0.94 (t, JH,H
=
H,
3
3
2
3
1
2
3], 0.0 [d, JP,C = 3.2 Hz, Si(CH3)3], 21.4 [d, JP,C = 13.6 Hz,
7.4 Hz,
3
H, OC3H6CH3), 1.42 (m, JH,H
OC2H4CH2CH3), 1.66 (m, JH,H = 6.4 Hz, 2 H, OCH2CH2C2H4),
=
7.4 Hz,
2
CH(SiMe3)2], 54.1 (d, JP,C = 3.9 Hz, POCH3), 194.6 (d, 2JP,C = 7.1,
2
2
1JW,C = 125.4 Hz, cis-CO), 197.3 (d, 2JP,C = 24.6 Hz, trans-CO) ppm. 3.66 (m, 2JH,H = 6.5 Hz, 2 H, OCH2C3H6), 7.83 (d, 1JP, H = 319.7 Hz,
31P{1H} NMR: δ = 109.7 (ssat, 1JW,P = 267.0, 1JP,H = 320.4 Hz) ppm.
1 H, P-H) ppm. 13C{1H} NMR: δ = –1.8 [d, 3JP,C = 1.9 Hz, Si(CH3)
3
IR (KBr): ν = 1917 [s, ν(CO)], 1941 [s, ν(CO)], 1994 [m, ν(CO)], 2071
3], 0.0 [d, JP,C = 2.6 Hz, Si(CH3)3], 11.5 (s, OC3H6CH3), 17.1 (s,
˜
[m, ν(CO)], 2257 [w, ν(PH)] cm–1. MS: m/z (%) = 546.0 (64) [M]+,
518.0 (42) [M – CO]+, 490.0 (72) [M – 2 CO]+, 462.0 (41) [M – 3
CO]+, 406.0 (65) [M – 5 CO]+, 73.0 (100) [SiMe3]+. C13H23O6PSi2W
(546.32): calcd. C 28.58, H 4.24; found C 28.74, H 4.31.
OC2H4CH2CH3), 21.3 (d, 3JP,C = 13.6 Hz, OCH2CH2C2H4), 30.4 (d,
1JP,C = 8.4 Hz, PCH), 67.3 (d, 2JP, C = 4.5 Hz, OCH2C3H7), 195.6 (d,
1
2
2JP,C = 7.8, JW,C = 125.4 Hz, cis-CO), 197.3 (d, JP,C = 24.6 Hz,
trans-CO) ppm. 31P{1H} NMR: δ = 102.5 (ssat, JW,P = 267.0, JP,H
1
1
= 320.4 Hz) ppm. IR (KBr): ν = 1921 [s, ν(CO)], 1980 [s, ν(CO)],
˜
Synthesis of 3c: Ethylene glycol monomethyl ether (85 μL, 1 mmol)
was added to a solution of 2H-azaphosphirene complex 1 (1 mmol,
617 mg) in toluene (30 mL) and then stirred at 75 °C for 3 h. The
solvent was then removed in vacuo (ca. 0.01 mbar) and the product
purified by column chromatography (SiO2, –20 °C, eluent: petroleum
ether) and obtained in the second fraction as a yellow viscous oil
2070 [s, ν(CO)], 2264 [w, ν(PH)] cm–1. MS: m/z (%) = 588.0 (75) [M]
+, 560.0 (34) [M – CO]+, 448.0 (41) [M – 5 CO]+, 73.0 (100) [SiMe3]
+. C16H29O6PSi2W (588.40): calcd. C 32.66, H 4.97; found C 32.79,
H 5.14.
Synthesis of 4a: A solution of 3a (122 mg, 0.2 mmol) and 12-crown-
after concentration. Yield: 366 mg (0.62 mmol), 62%. 1H NMR 4 (32 μL, 0.2 mmol) in diethyl ether (2 mL) was added dropwise to a
(CDCl3): δ = 0.21 [s, 9 H, Si(CH3)3], 0.27 [s, 9 H, Si(CH3)3], 0.93 (d,
solution of lithium diisopropylamide (LDA; 0.22 mmol), freshly pre-
pared from n-butyllithium (1.6 m, 0.14 mL, 0.22 mmol) and diisopro-
pylamine (30 μL, 0.2 mmol) in diethyl ether (2 mL), cooled to –78 °C,
2
2JP,H = 1.8 Hz, 1 H, PCH), 3.35 (s, 3 H, OCH3), 3.57 (t, JH,H
=
4.3 Hz, 2 H, CH2OCH3), 3.78 (m, 2JH,H = 4.8 Hz, 2 H, OCH2CH2),
1
4
7.90 (dd, JP, H = 324.1, JH,H = 1.3 Hz, 1 H, P-H) ppm. 13C{1H} and the reaction mixture was stirred for 2 h. The solvent was then
3
3
NMR: δ = 0.2 [d, JP,C = 2.6 Hz, Si(CH3)3], 2.0 [d, JP,C = 3.2 Hz,
evaporated in vacuo and the residue washed with n-pentane at low
1
Si(CH3)3], 23.4 (d, JP,C = 13.6 Hz, PCH), 58.7 (s, OCH3), 68.0 (d,
temperature (ca. –50 °C). Yield: 400 mg (0.51 mmol), 50.6%; m.p.
3JP,C = 3.9 Hz, CH2OCH3), 71.6 (d, JP,C = 7.8 Hz, OCH2CH2O),
75 °C. 1H NMR ([D8]THF): δ = 0.08 [d, JH,H = 1.7 Hz, 9 H,
2
2
2
1
2
196.6 (dd, JP,C = 7.1, JW,C = 125.4 Hz, cis-CO), 199.4 (d, JP,C
=
=
Si(CH3)3], 0.17 [s, 9 H, Si(CH3)3], 2.28 (d, 2JP,H = 1.7 Hz, 1 H, PCH),
24.6 Hz, trans-CO) ppm. 31P{1H} NMR: δ = 107.3 (ssat
,
1JW,P
3.76 (s, 16 H, 12-crown-4), 7.01 (m, 5 H, Ph) ppm. 13C{1H} NMR:
1
3
3
267.0, JP,H = 324.2 Hz) ppm. IR (KBr): ν = 1935 [s, ν(CO)], 1980
δ = 1.7 [d, JP, C = 4.5 Hz, Si(CH3)3], 4.0 [d, JP,C = 1.3 Hz, Si(CH3)
˜
Eur. J. Inorg. Chem. 2012, 3490–3499
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3495

L. Duan, G. Schnakenburg, J. Daniels, R. Streubel
FULL PAPER
3], 25.4 (d, 1JP,C = 75.0 Hz, PCH), 68.6 (s, 12-crown-4), 118.1 (d, 4JP,C solution was characterized by 31P NMR spectroscopy. 31P{1H}
3
5
1
= 1.9 Hz, m-Ph), 119.4 (d, JP,C = 15.5 Hz, o-Ph), 128.8 (d, JP,C
=
NMR: δ = 201.1 (ssat, JW,P = 68.7 Hz) ppm.
1.9 Hz, p-Ph), 162.2 (d, 2JP,C = 9.1 Hz, i-Ph), 206.4 (d, 2JP,C = 5.2 Hz,
Synthesis of 5a: Methyl iodide (12 μL) was added through a syringe
to a solution of freshly prepared complex 4a that had been stirred
for 0.5 h. Then the reaction mixture was stirred for another 2 h, the
solution filtered, the solvent removed in vacuo (ca. 0.01 mbar), and
the raw product purified by column chromatography (SiO2, –20 °C;
eluent: petroleum ether) after which yellow crystals were obtained.
Yield: 470 mg (0.86 mmol), 43%; m.p. 127–130 °C. 1H NMR
cis-CO), 210.3 (d, JP,C = 14.9 Hz, trans-CO) ppm. 31P{1H} NMR:
2
δ = 209.1 (ssat, 1JW,P = 76.2 Hz) ppm. MS (ESI+): m/z = 788.0 [M –
2 H]+.
Synthesis of 4b: A solution of 3b (109 mg, 0.2 mmol) and 12-crown-
4 (32 μL, 0.2 mmol) in diethyl ether (2 mL) was added dropwise to a
solution of lithium diisopropylamide (0.22 mmol), freshly prepared
from n-butyllithium (1.6 m, 0.14 mL, 0.22 mmol) and diisopropyl-
amine (30 μL, 0.2 mmol) in diethyl ether (2 mL), cooled to –78 °C,
and the reaction mixture was stirred for 2 h. The resulting orange-
red solution was characterized by NMR spectroscopy. 1H NMR ([D8]
THF): δ = 0.04 (s, 9 H, SiMe3), 0.11 (d, 4JP,H = 1.5 Hz, 9 H, SiMe3),
(CDCl3):
δ
=
0.27 [s,
9
H, Si(CH3)3], 0.29 [s,
9
H,
=
2
2
Si(CH3)3], 1.79 (d, JP,H = 10.3 Hz, 1 H, PCH), 2.20 (d, JP,H
4.7 Hz, 3 H, PCH3), 7.02 (d, JH,H = 8.7 Hz, 2 H, o-Ph), 7.16 (3JH,H
3
3
= 7.3 Hz, 1 H, p-Ph), 7.27 (t, JH,H = 8.1 Hz, 2 H, m-Ph) ppm.
13C{1H} NMR: δ = 1.9 [d, JP,C = 3.2 Hz, Si(CH3)3], 2.5 [d, JP, C
=
=
=
=
=
=
3
3
3
1
1
2.09 (s, 1 H, PCH), 3.13 (d, JP,H = 14.9 Hz, 3 H, POCH3), 3.77 (s,
2.0 Hz, Si(CH3)3], 26.4 (d, JP,C = 18.1 Hz, PCH3), 30.0 (d, JP, C
11.1 Hz, PCH), 121.7 (d, JP,C = 3.6 Hz, Ph-o), 124.0 (d, JP,C
1.9 Hz, Ph-p), 129.0 (d, JP,C = 1.0 Hz, Ph-m), 151.9 (d, JP,C
12 H, 12-crown-4) ppm. 13C{1H} NMR: δ = 1.4 [d, 3JP,C = 12.3 Hz,
3
5
1
4
2
Si(CH3)3], 4.0 [s, Si(CH3)3], 25.8 (d, JP,C = 66.6 Hz, PCH), 58.0 (d,
2JP,C = 29.1 Hz, POCH3), 69.1 (s, 12-crown-4), 208.1 (d, JP,C
=
2
2
2
6.6 Hz, POC), 196.2 (d, JP,C = 7.5 Hz, cis-CO), 198.1 (d, JP,C
5.7 Hz, cis-CO), 212.1 (d, JP,C = 14.2 Hz, trans-CO) ppm. 31P{1H}
2
25.7 Hz, trans-CO) ppm. 31P{1H} NMR: δ = 142.4 (ssat 1JW,P
,
1
NMR: δ = 209.6 (ssat, JW,P = 68.7 Hz) ppm.
279.2 Hz) ppm. IR (KBr): ν = 1920 [vs, ν(CO)], 1984 [m, ν(CO)],
˜
2068 [s, ν(CO)], 2961 [w, ν(CH/CH3)], 3440 [br, ν(aromatic-H)] cm–1.
MS: m/z = 622.0 [M]+·. C19H27O6PSi2W (622.41): calcd. C 36.67, H
4.37; found C 36.58, H 4.64.
Synthesis of 4c: A solution of 3c (118 mg, 0.2 mmol) and 12-crown-
4 (32 μL, 0.2 mmol) in diethyl ether (2 mL) was added dropwise to a
solution of lithium diisopropylamide (0.22 mmol), freshly prepared
from n-butyllithium (1.6 m, 0.14 mL, 0.22 mmol) and diisopropyl-
amine (30 μL, 0.2 mmol) in diethyl ether (2 mL), cooled to –78 °C,
and the reaction mixture was stirred for 2 h. Then the volatiles were
removed in vacuo (ca. 10–2 mbar), and the residue was characterized.
Synthesis of 5b: Methyl iodide (12 μL) was added through a syringe
to a solution of freshly prepared complex 4b that had been stirred
for 0.5 h. Then the reaction mixture was stirred for another 2 h, the
solution then filtered, and the solvent removed in vacuo (ca.
0.01 mbar). The raw product was further purified by column
chromatography (SiO2, –20 °C, eluent: petroleum ether). Yield: 34 mg
(0.06 mmol), 30%; m.p. 125 °C. 1H NMR (CDCl3): δ = 0.24 [s, 9 H,
1H NMR (300.13 MHz, [D8]THF): δ = 0.00 [d, JP,H = 1.5 Hz, 9 H,
Si(CH3)3], 0.10 [s, 9 H, Si(CH3)3], 1.86 (br., 1 H, PCH), 3.18 (s, 3 H,
POC2H4OCH3), 3.45 (m, 2 H, POCH2CH2OCH3), 3.50 (m, 2 H,
POCH2CH2OCH3), 3.69 (s, 16 H, 12-c-4) ppm. 13C{1H} NMR
4
2
Si(CH3)3], 0.28 [s, 9 H, Si(CH3)3], 1.61 (d, JP,H = 10.8 Hz, 1 H,
3
(75.5 MHz, [D8]THF): δ = –0.1 [d, JP,C = 4.5 Hz, Si(CH3)3], 2.4 [s,
PCH), 1.94 (d, 2JP,H = 4.9 Hz, 3 H, PCH3), 3.46 (d, 3JP,H = 13.0 Hz,
1
Si(CH3)3], 24.3 (d, JP,C = 68.5 Hz, PCH), 57.2 (s, POC2H4OCH3),
3 H, POCH3) ppm. 13C{1H} NMR: δ = 2.8 [d, JP,C = 3.2 Hz,
3
67.0 (s, 12-c-4), 68.1 (d, 2JP,C = 23.9 Hz, POCH2CH2OCH3), 72.3 (d,
Si(CH3)3], 3.4 [d, 3JP, C = 1.9 Hz, Si(CH3)3], 24.2 (d, JP,C = 18.7 Hz,
1
3JP,C = 9.7 Hz, POCH2CH2OCH3), 206.3 (d, 2JP, C = 5.2 Hz, cis-CO),
1
2
PCH3), 29.8 (d, JP,C = 11.6 Hz, PCH), 52.9 (d, JP,C = 3.2 Hz,
2
210.2 (d, JP, C
=
14.2 Hz, trans-CO) ppm. 31P{1H} NMR
POCH3), 197.7 (d, 2JP,C = 7.1 Hz, cis-CO), 199.6 (d, 2JP,C = 23.9 Hz,
1
(121.5 MHz, [D8]THF): δ = 208.8 (ssat, JW,P = 69.0 Hz) ppm.
trans-CO) ppm. 31P{1H} NMR:
δ = 130.4 (ssat, =
1JW,P
269.6 Hz) ppm. IR (KBr): ν = 1933 [s, ν(CO)], 2069 [m, ν(CO)], 2963
˜
Synthesis of 4d: A solution of 3d (127 mg, 0.2 mmol) and 12-crown-
4 (32 μL, 0.2 mmol) in diethyl ether (2 mL) was added dropwise to a
solution of lithium diisopropylamide (0.22 mmol), freshly prepared
from n-butyllithium (1.6 m, 0.14 mL, 0.22 mmol) and diisopropyl-
amine (30 μL, 0.2 mmol) in diethyl ether (2 mL), cooled to –78 °C,
and the reaction mixture was stirred for 2 h. Then the resulting
orange-red solution was characterized by NMR spectroscopy (–
40 °C). 1H NMR ([D8]THF): δ = –0.08 (s, 9 H, SiMe3), 0.10 (s, 9 H,
[m, ν(CH3)] cm–1. MS: m/z (%) = 560.1 (22) [M]+·, 532.1 (20) [M –
CO]+·, 504.1 (30) [M – 2 CO]+·, 476.0 (28) [M – 3 CO]+·, 420.1 (50)
[M – 5 CO]+·, 374.0 (32) [M – 5 CO – (CH3)2O]+·, 223.1 (50) [M –
W(CO)5 – CH3]+·, 73.0 (100) [SiMe3]+·. C14H25O6PSi2W (560.34):
calcd. C 30.01, H 4.50; found C 30.42, H 4.65.
Synthesis of 5c: Methyl iodide (12 μL) was added through a syringe
to a solution of freshly prepared complex 4c that had been stirred
for 0.5 h. Then the reaction mixture was stirred for another 2 h, the
solution filtered, and the solvent then removed in vacuo (ca.
0.01 mbar). The raw product was further purified by column
chromatography (SiO2, –20 °C, eluent: petroleum ether). Yield: 43 mg
(0.07 mmol), 35%. 1H NMR (300.13 MHz, CDCl3): δ = 0.26 [s, 9 H,
2
2
SiMe3), 0.95 (d, JH,H = 6.0 Hz, 12 H, HNiPr2-H), 2.08 (d, JH,H
=
13.0 Hz, 3 H, PO-2,6-Me2C6H3), 2.17 (s, 3 H, PO-2,6-Me2C6H3),
2.32 (br. s, 1 H, PCH), 2.85 {oct, 3JH,H = 6.2 Hz, 2 H, NH[CH(CH3)
3
2]2}, 3.74 (s, 16 H, 12-c-4-H), 6.75 (m, JH,H = 7.3 Hz, 2 H, m-Ph-
H), 6.93 (d, 3JH,H = 7.4 Hz, 1 H, p-Ph-H) ppm. 13C{1H} NMR: δ =
3
1.3 [d, JP,C = 10.3 Hz, Si(CH3)3], 2.9 [s, Si(CH3)3], 20.8 (s, 2,6-
2
Si(CH3)3], 0.28 [s, 9 H, Si(CH3)3], 1.61 (d, JP,H = 10.2 Hz, 1 H,
Me2C6H3), 22.7 (d, 1JP,C = 78.8 Hz, PCH), 68.7 (s, 12-c-4), 126.2 (d,
2
PCH), 1.97 (d, JP,H = 4.9 Hz, 3 H, PCH3), 3.32 (s, 3 H, POC2H4-
5JP,C = 1.9 Hz, p-Ph), 131.1 (d, 4JP,C = 1.9 Hz, m-Ph), 131.5 (d, 3JP,C
OCH3), 3.56 (m, 2 H, POCH2CH2OCH3), 3.78 (m, 2 H, POCH2CH2-
2
2
= 3.9 Hz, o-Ph), 153.5 (d, JP,C = 8.4 Hz, P-O-C), 219.7 (d, JP,C
=
OCH3) ppm. 13C{1H} NMR (75.5 MHz, CDCl3): δ = 1.8 [d, 3JP,C
=
=
12.9 Hz, cis-CO), 223.4 (d, 2JP, C = 21.3 Hz, trans-CO) ppm. 31P{1H}
NMR: δ = 215.3 (ssat, JW,P = 69.9 Hz) ppm.
3
1
3.1 Hz, Si(CH3)3], 2.3 [d, JP,C = 2.1 Hz, Si(CH3)3], 23.8 (d, JP,C
1
1
18.9 Hz, PCH), 28.9 (d, JP,C = 12.4 Hz, PCH3), 57.6 (s, POC2H4-
3
2
Synthesis of 4e: A solution of 3e (118 mg, 0.2 mmol) and 12-crown-
OCH3), 64.8 (d, JP,C = 3.2 Hz, POCH2CH2OCH3), 70.7 (d, JP,C =
2
1
4 (32 μL, 0.2 mmol) in diethyl ether (2 mL) was slowly added to a 8.1 Hz, POCH2CH2OCH3), 197.2 (d, JP,C = 8.0, JW,C = 125.5 Hz,
2
solution of lithium diisopropylamide (0.22 mmol), freshly prepared
from n-butyllithium (1.6 m, 0.14 mL, 0.22 mmol) and diisopropyl- (121.5 MHz, CDCl3): δ = 130.2 (ssat
cis-CO), 199.1 (d, JP,C = 23.2 Hz, trans-CO) ppm. 31P{1H} NMR
,
1JW,P = 269.6 Hz) ppm. IR
amine (30 μL, 0.2 mmol) in diethyl ether (2 mL), cooled to –78 °C. (KBr): ν = 2959 [w, ν(CH/CH )], 2069 [s, ν(CO)], 1921 [vs, ν(CO)]
˜
3
Then the reaction mixture was stirred for 2 h, and the resulting yellow cm–1. MS (EI, 70 eV, 184W): m/z (%) = 604.0 (16) [M]+·, 576.0 (16)
3496
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 3490–3499

P-OR Phosphanido and/or Li/OR Phosphinidenoid Complexes?
1
4
[M – CO]+·, 548.0 (40) [M – 2 CO]+·, 520.0 (65) [M – 3 CO]+·, 464.1
C=CCH3), 25.8 (d, JP,C = 11.0 Hz, PCH), 123.1 (d, JP, C = 3.9 Hz,
5
3
(25)
[M
–
5
CO]+·,
73.1
(100)
Ph), 125.3 (d, JP,C = 1.9 Hz, Ph), 127.3 (d, JP,C = 18.8 Hz, Ph),
[SiMe3]+·. C16H29O7PSi2W (604.40): calcd. C 31.80, H 4.84; found C 129.3 (s, Ph), 130.2 (d, 5JP,C = 1.9 Hz, Ph), 135.9 (d, 3JP, C = 16.2 Hz,
2
2
32.51, H 5.05.
Ph), 150.9 (d, JP,C = 18.7 Hz, i-Ph), 154.0 (d, JP, C = 5.8 Hz, i-Ph),
1
2
175.7 (d, JP, C = 26.5 Hz, PC=C), 205.2 (d, JP,C = 5.2 Hz, cis-CO),
Synthesis of 5d: Methyl iodide (12 μL) was added through a syringe
to a solution of freshly prepared complex 4d that had been stirred
for 0.5 h. Then the reaction mixture was stirred for another 1 h. The
solution was then filtered and the solvent removed in vacuo (ca.
0.01 mbar). The raw product was then purified further by column
2
208.8 (d, JP, C
=
30.1 Hz, trans-CO) ppm. 31P{1H} NMR
(121.5 MHz, CD2Cl2): δ = 154.1 (ssat
,
1JW,P = 269.6 Hz) ppm.
29Si{1H} NMR (59.6 MHz, CD2Cl2): δ = 0.1 [d, JP, Si = 10.1 Hz,
2
2
PCHSi(CH3)3], 0.3 [d, J(P,Si) = 3.4 Hz, PCHSi(CH3)3] ppm. IR
(KBr): ν = 2960 [s, ν(CH/CH )], 2070 [s, ν(CO)], 2019 [vs, ν(CO)],
˜
3
1
chromatography (SiO2, –20 °C). Yield: 196 mg (0.3 mmol), 15%. H
1932 [vs, ν(CO)], 1592 [w, ν(trans C=C)] cm–1. MS (EI, 70 eV, 184W):
m/z (%) = 724.1 (10) [M]+·, 696.1 (19) [M – CO]+·, 640.1 (50) [M – 3
CO]+·, 612.1 (23) [M – 4 CO]+·, 597.1 (24) [M – 4 CO – Me]+·, 367.1
2
NMR (CDCl3): δ = 0.27 (d, JH,H = 8.4 Hz, 18 H, SiMe3), 1.28 (d,
2
2JP,H = 10.4 Hz, PCH), 2.21 (d, JP,H = 6.0 Hz, 3 H, PCH3), 2.26 (s,
2
6 H, 2,6-Me2C6H3), 6.80 (d, JH,H = 7.5 Hz, 1 H, p-Ph), 6.93 (d,
(39)
[M
–
W(CO)5
–
P]+·,
73.0
(100)
2JH,H = 7.5 Hz, 2 H, m-Ph) ppm. 13C{1H} NMR: δ = –0.1 (s, SiMe3),
[SiMe3]+·.
3
1.9 (d, JP,C
=
2.5 Hz, SiMe3), 17.1 [s, PO-2,6-(CH3)2-
1
1
C6H3], 28.6 (d, JP,C = 16.8 Hz, PCH3), 30.2 (d, JP, C = 25.4 Hz,
Synthesis of 9: MeLi (0.25 mL, 1.6 m in hexane, 0.4 mmol) was added
dropwise to a solution of P-methoxyphosphane complex 3b (221 mg,
0.4 mmol) and 12-crown-4 (67 μL, 0.42 mmol) in thf (3 mL), cooled
to –78 °C. After stirring of the reaction mixture for 0.5 h, a solution
of benzaldehyde (40 μL, 0.4 mmol) in THF (3 mL) was added (by
syringe) to freshly prepared complex 4b at –78 °C without any color
change. After stirring for another 0.5 h, MeOTf (44 μL, or 24 μL of
MeI) was added to quench the reaction. All the volatiles were then
removed in vacuo (ca. 0.01 mbar), and the raw product was purified
by column chromatography (SiO2, –20 °C, 2ϫ5 cm, eluent: petro-
leum ether). The second fraction contained products 9 and another
byproduct in a 3:1 ratio. Column-chromatographic separation was
3
PCH), 120.3 (s, p-Ph), 127.4 (s, m-Ph), 128.5 (d, JP,C = 2.3 Hz, o-
Ph), 151.5 (d, 2JP,C = 9.3 Hz, POC), 195.3 (d, 2JP,C = 6.8 Hz, cis-CO),
198.1 (d, 2JP, C = 25.0 Hz, trans-CO) ppm. 31P{1H} NMR: δ = 134.0
1
(ssat, JW,P = 273.4 Hz) ppm.
Synthesis of 6: A solution of phosphane complex 3a (61 mg,
0.1 mmol) and 12-crown-4 (20 μL, 0.1 mmol) in diethyl ether
(0.5 mL) was added dropwise to a solution of freshly prepared lith-
ium diisopropylamide at –78 °C. The reaction solution was stirred
for 0.5 h. Evaporation of the solvent in vacuo (ca. 0.01 mbar) led to
a yellow compound, which upon dissolving in CDCl3 immediately
changed color to dark red. Evaporation of all volatiles, washing of
the residue with n-pentane at low temperature (ca. –60 °C), and dry-
ing gave complex 6 as an orange powder, which crystallized from
Et2O at ambient temperature as light-orange crystals. Yield: 58 mg
performed on the second fraction, but the ratio did not change. 31P
3
NMR (121.5 MHz, THF): δ = 161.8 (ssat
,
1JW,P = 275.9, JP,H
=
15.3 Hz) ppm. MS (EI, 70 eV, 184W): m/z (%) = 666.1 (10) [M]+·,
582.1 (39) [M – 3 CO]+·, 526.1 (21) [M – 5 CO]+·, 179.0 (100) [M –
W(CO)5 – CH(SiMe3)2]+·, 73.0 (48) [SiMe3]+·.
1
(0.09 mmol), 90%; m.p. 100 °C. H NMR (300.13 MHz, CDCl3): δ
= 0.30 [s, 9 H, Si(CH3)3], 0.34 [s, 9 H, Si(CH3)3], 1.72 [s, 18 H,
2
NC(CH3)3], 1.98 (d, JP,H = 7.0 Hz, 1 H, PCH), 7.27 (m, 5 H, Ph), Synthesis of 13: A solution of phosphane complex 3a (61 mg,
0.1 mmol) and 12-crown-4 (20 μL, 0.1 mmol) in diethyl ether
1.7 [d, JP,C = 3.6 Hz, Si(CH3)3], 2.0 [d, JP,C = 2.4 Hz, Si(CH3)3], (0.5 mL) was added dropwise to a solution of freshly prepared lith-
7.68 (s, 2 H, NCH) ppm. 13C{1H} NMR (75.5 MHz, CDCl3): δ =
3
3
29.3 [s, NC(CH3)3], 59.7 [s, NC(CH3)3], 118.9 (s, NCCN), 121.1 (d,
ium diisopropylamide at –78 °C, and the mixture was stirred for
0.5 h. Tetra-n-butylammonium fluoride (0.5 mL, 1 m in thf) was then
3JP,C = 5.3 Hz, o-Ph), 125.1 (d, 4JP,C = 2.2 Hz, m-Ph), 129.1 (d, 5JP,C
= 1.0 Hz, p-Ph), 151.5 (d, 2JP,C = 7.2 Hz, POC), 195.0 (d, 2JP,C = 7.9, added. The solution changed color immediately from orange to pale
1JW,C = 126.9 Hz, cis-CO), 197.2 (d, 2JP,C = 39.8 Hz, trans-CO) ppm. yellow. After stirring for another 1 h, the solvent was removed in
1
31P{1H} NMR (121.5 MHz, CDCl3): δ = 186.7 (ssat, JW,P = 335.7,
vacuo (ca. 0.01 mbar), and the residue was washed with n-pentane at
2JP,H = 6.4 Hz) ppm. IR (KBr): ν = 2970 [w, ν(CH/CH )], 2078 [m, low temperature (ca. –50 °C). Yield: 43 mg (0.068 mmol), 68%. H
1
˜
3
ν(CO)], 1999 [m, ν(CO)], 1942 [vs, ν(CO)], 1915 [s, ν(CO)] cm–1. MS
(EI, 70 eV, 184W): m/z (%) = 641.9 (30) [M]+·, 544.8 (50) [M – OPh]
+·, 501.9 (17) [M – 5 CO]+·, 283.1 (100) [M – 5 CO – Cl]+·, 73.0 (60)
[SiMe3]+·. C18H24ClO6PSi2W (642.83): calcd. C 33.63, H 3.76; found
C 33.97, H 3.79.
NMR (300.13 MHz, [D8]THF): δ = 0.92 [t, JH,H = 7.4 Hz, 24 H,
2
2
CH3(CH2)3N], 1.33 [m, JH,H = 7.4 Hz, 16 H, CH3CH2(CH2)2N+],
2
2
1.57 (m, JH,H = 7.4 Hz, 16 H, C2H5CH2CH2N+), 1.73 (dd, JP,H
=
5.3 Hz, 3 H, PCH3), 3.31 (m, JH,H = 7.2 Hz, 16 H, C3H5CH2N+),
6.33 (t, JH,H = 7.4 Hz, 1 H, Ph), 6.67 (d, JH,H = 7.4 Hz, 2 H, m-
Ph), 6.87 (d, JH,H = 7.6 Hz, 2 H, Ph), 8.11 (qd, JP,H = 300.6, JP,H
= 5.3 Hz, PH) ppm. 13C{1H} NMR (75.5 MHz, [D8]THF): δ = 14.2
(s, NC3H7CH3), 20.8 (s, NC2H5CH2CH3), 24.9 (s, NCH2CH2C2H5),
28.1 (d, 1JP,C = 22.6 Hz, PCH3), 59.4 (s, NCH2C3H7), 200.0 (d, 2JP,C
= 9.7 Hz, cis-CO), 204.0 (d, 2JP, C = 10.5 Hz, trans-CO) ppm. 31P{1H}
2
2
2
2
1
2
Synthesis of 8: A solution of phenylacetylene (0.1 mL, 1.0 mmol) was
added to freshly prepared complex 4a in THF (5 mL) at –78 °C; the
color immediately changed to red. After 0.5 h of stirring, phenyl-
acetylene (0.1 mL) was added and the mixture heated at reflux for
2 h, which was accompanied of a color change to dark red. After
cooling to ambient temperature, MeOTf was added to quench the
reaction. After evaporation of all volatiles in vacuo (ca. 0.01 mbar),
1
1
NMR (121.5 MHz, [D8]THF): δ = 33.2 (ssat, JW,P = 227.6, JP,H
=
300.1 Hz) ppm.
the raw product was purified by column chromatography (SiO2, X-ray Crystallographic Analysis of 3a,d,e, 5a, and 6: Data were col-
–20 °C, 2ϫ11 cm, eluent: petroleum ether/Et2O, 10:1). Complex 8 lected with a Nonius–KappaCCD diffractometer at 123 K by using
was obtained from the second fraction as a brownish yellow solid
after evaporation. Yield: 449 mg (0.62 mmol), 62%. 1H NMR
(300.13 MHz, CD2Cl2): δ = 0.36 [s, 9 H, Si(CH3)3], 0.43 [s, 9 H,
Mo-Kα radiation (λ = 0.71073 Å). The structures were refined by full-
matrix least squares on F2 (SHELXL-97[27]). All non-hydrogen atoms
were refined anisotropically. The hydrogen atoms were included in
Si(CH3)3], 1.23 (s, 1 H, PCH), 1.31 (br., 3 H, Me), 7.22 (m, 5 H, Ph), calculated positions by using a riding model. CCDC-867925 (for
3
2
7.41 (t, JH,H = 3.9 Hz, 5 H, Ph), 7.64 (d, JP,H = 4.6 Hz, 1 H,
3a), -867926 (for 3d), -867927 (for 3e), -867928 (for 5a), and -867929
6) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
PCH=C) ppm. 13C{1H} NMR (75.5 MHz, CD2Cl2): δ = 2.8 [d, 3JP,C (for
= 3.9 Hz, Si(CH3)3], 3.6 [d, JP,C = 1.9 Hz, Si(CH3)3], 22.7 (s,
3
Eur. J. Inorg. Chem. 2012, 3490–3499
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3497

L. Duan, G. Schnakenburg, J. Daniels, R. Streubel
FULL PAPER
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4024.
from The Cambridge Crystallographic Data Centre via www.ccdc.ca-
m.ac.uk/data_request/cif.
Crystal Data for Complex 3a: Yellow single crystals of 3a were grown
from n-pentane solution at –30 °C. C18H25O6PSi2W, crystal size
¯
0.24ϫ0.23ϫ0.08 mm, triclinic, P1, a = 12.8195(2), b = 13.38630(10),
c = 14.26660(10) Å, α = 103.8230(2), β = 92.7380(10), γ =
90.3910(10)°, V = 2374.19(4) Å3, Z = 4, 2θmax = 55°, collected (inde-
pendent) reflections 78053 (10860), Rint = 0.0464, μ = 5.062 mm–1,
525 refined parameters, 0 restraints, R1 [for IϾ2σ(I)] = 0.0226, wR2
(for all data) = 0.0535, max./min. residue electron density = 2.549/–
1.650 eÅ–3.
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1996, 35, 1518–1520; k) G. Boche, J. C. W. Lohrenz, Chem. Rev.
2001, 101, 697–756.
Crystal Data for Complex 3d: Pale-yellow single crystals of 3d were
grown from n-pentane solution at –30 °C. C20H29O6PSi2W, crystal
¯
size 0.60ϫ0.59ϫ0.40 mm, triclinic, P1, a = 9.4714(2), b = 9.9051(3),
15.0145(3) Å, 96.4330(10), 103.0160(10),
c
=
α
=
β
=
γ =
111.9870(10)°, V = 1242.16(5) Å3, Z = 2, 2θmax = 56°, collected (inde-
pendent) reflections 16042 (5921), Rint = 0.0513, μ = 4.842 mm–1, 284
refined parameters, 0 restraints, R1 [for IϾ2σ(I)] = 0.0245, wR2 (for
all data) = 0.0640, max./min. residue electron density = 2.244/–
1.767 eÅ–3.
Crystal Data for Complex 3e: Yellow single crystals of 3e were grown
from n-pentane solution at –30 °C. C16H29O6PSi2W, crystal size
0.33ϫ0.24ϫ0.22 mm, orthorhombic, P212121, a = 11.1201(3), b =
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11.9397(3), c = 17.9401(4) Å, V = 2381.92(10) Å3, Z = 4, 2θmax
=
55°, collected (independent) reflections 17207 (5328), Rint = 0.0359,
μ = 5.043 mm–1, 351 refined parameters, 0 restraints, R1 [for
IϾ2σ(I)] = 0.0214, wR2 (for all data) = 0.0385, max./min. residue
electron density = 1.217/–0.962 eÅ–3.
Crystal Data for Complex 5a: Yellow single crystals of 5a were grown
from concentrated diethyl ether solution at –30 °C. C19H27O6PSi2W,
crystal size 0.60ϫ0.40ϫ0.12 mm, monoclinic, P21, a = 9.7329(6), b
= 12.5170(7), c = 11.2360(7) Å, β = 115.163(2)°, V = 1238.94(13) Å3,
Z = 2, 2θmax = 56°, collected (independent) reflections 11600 (5293),
Rint = 0.0337, μ = 4.853 mm–1, 270 refined parameters, 1 restraint,
R1 [for IϾ2σ(I)] = 0.0162, wR2 (for all data) = 0.0414, max./min.
residue electron density = 0.965/–1.511 eÅ–3.
[6]
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The first attempts were described by: G. Huttner, H. D. Mueller,
A. Frank, H. Lorenz, Angew. Chem. 1975, 87, 714–715; Angew.
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Crystal Data for Complex 6: Colorless single crystals of 6 were grown
from concentrated diethyl ether solution at room temperature.
C18H24ClO6PSi2W, crystal size 0.56ϫ0.40ϫ0.32 mm, monoclinic,
P21/c, a = 14.9583(2), b = 14.2798(4), c = 11.6683(3) Å, β =
97.233(2)°, V = 2472.53(10) Å3, Z = 4, 2θmax = 56°, collected (inde-
pendent) reflections 34586 (5961), Rint = 0.0587, μ = 4.971 mm–1, 269
refined parameters, 1 restraint, R1 [for IϾ2σ(I)] = 0.0221, wR2 (for
all data) = 0.0486, max./min. residue electron density = 1.593/–
0.995 eÅ–3.
R. Streubel, E. Niecke, Chem. Ber. 1990, 123, 1245–1251.
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Acknowledgments
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van Gastel, F. Neese, R. Streubel, Angew. Chem. Int. Ed. 2010,
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2000, 1253–1259.
We thank the Deutsche Forschungsgemeinschaft (STR 411/26-1) and
the COST action cm0802 “PhoSciNet” for financial support. G. S.
thanks Prof. A. C. Filippou for support.
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3498
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 3490–3499

P-OR Phosphanido and/or Li/OR Phosphinidenoid Complexes?
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Received: April 13, 2012
Published Online: June 13, 2012
Eur. J. Inorg. Chem. 2012, 3490–3499
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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