Strong evidence for a transient phosphinidenoid complex

Article abstract of DOI:10.1002/anie.200701962

(Figure Presented) Caught in the trap: Two different routes to the thermally unstable phosphinidenoid complex I are described, and chemical evidence for this novel intermediate is provided through selective reactions. For example, methyl iodide, dimethylcyanamide, or butyraldehyde furnished complexes II, III, and IV (see scheme) under very mild conditions.

Full text of DOI:10.1002/anie.200701962

Angewandte
Chemie
DOI: 10.1002/anie.200701962
Phosphinidenoid Complexes
Strong Evidence for a Transient Phosphinidenoid Complex**
Aysel Özbolat, Gerd von Frantzius, Janaina Marinas PØrez, Martin Nieger, and Rainer Streubel*
Dedicated to Professor Gottfried Huttner on the occasion of his 70th birthday
Carbenoids (I, Scheme 1) are versatile reactive intermediates
in organic synthesis.[1] This situation does not hold for related
phosphinidenoids (II) and mononuclear transition-metal
complexes thereof (III). Their potential 1,1-elimination
products however—terminal phosphinidene complexes
(IV)—are important and well-established building blocks in
organophosphorus chemistry, and these complexes are acces-
sible from a variety of precursors.[2–4]
phirane complexhowever (that could have formed from
reaction of a transient phosphinidene complexwith the
solvent, THF) suggested the existence of [LnM{RP(M’)X)}] as
an intermediate.[8]
For the CuI-catalyzed reaction of 7-phosphanorborna-
diene complexes with alkenes, a reaction discovered by
Mathey and Marinetti in 1984,[9], Lammertsma et al.[10]
proposed that the phosphinidenoid [W(CO)5{PhP(Cu)Cl}]
was the intermediate on the basis of calculations. In turn,
Mathey and Compain generated the short-lived phosphanide
complex[W(CO) {PhP(F)}]À which acts as a strong anionic
5
nucleophile; [Cs([18]crown-6)]+ was most probably the
counterion.[11] We gained access to [W(CO)5{RP-
(CNLi)([12]crown-4)}][12] (R = CH(SiMe3)2), the first struc-
tural isomer of a phosphinidenoid complex( III). Herein, we
present a method to generate phosphinidenoid–transition-
metal complexes under very mild conditions that can undergo
selective substitution reactions and behave like a terminal
phosphinidene complex.
Scheme 1. Carbenoids (I), phosphinidenoids (II) and complexes there-
of (III), and phosphinidene complexes (IV). R=ubiquitous organic
substitutents; M’=main-group metal; X=halogen; MLn =transition
metal complex fragment.
First attempts to generate mononuclear phosphinidenoid
complexes (III) as precursors of terminal phosphinidene
complexes (IV) date back to 1975, when Huttner et al.
attempted chlorine/lithium exchange on RPLi2 (R = Ph)
transition-metal complexes, which led to trigonal-planar
dinuclear m2-phosphinidene complexes instead.[5] Although
in subsequent studies chlorine/lithium exchange on RPCl2
(R = alkyl) complexes could be controlled to yield diphos-
phene and diphosphane complexes,[6,7] strong evidence for
transient formation of phosphinidenoid complexes
[LnM{RP(M’)X)}] was not obtained. Formation of a phos-
Deprotonation of chloro(organo)phosphane complex 1[13]
with lithium diisopropylamide (LDA) in the presence of
[12]crown-4 selectively generated complex 2 (Scheme 2).
[*] Dipl.-Chem. A. Özbolat, Magister G. von Frantzius,
M.Sc. J. M. PØrez, Dr. M. Nieger, Prof. Dr. R. Streubel
Institut für Anorganische Chemie
Scheme 2. Generation and reactions of complex 2.
Rheinische Friedrich-Wilhelms-Universität Bonn
Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany)
Fax: (+49)228-739-616
E-mail: r.streubel@uni-bonn.de
Homepage: http://anorganik.chemie.uni-bonn.de/akstreubel/
Streubel_Home.html
Warming up the reaction mixture to ambient temperature in
the absence of any trapping reagents led to E-diphosphene
complex 3[14] and a product that is unstable at room temper-
ature and which has a signal in the 31P NMR spectrum at d =
347.7 ppm (Et2O, product ratio 4:1) with small phosphorus–
tungsten coupling constants of 143.7 and 103.0 Hz. These
NMR data are similar to those of the dinuclear Z diphos-
Dr. M. Nieger
Laboratory of Inorganic Chemistry
Department of Chemistry
University of Helsinki
P.O. Box 55 (A. I. Virtasen aukio 1), 00014 Helsinki (Finland)
=
phene complex[L nW(Mes)P P(Mes)WLn] (Mes = 2,4,6-tri-
methylphenyl, Ln = (CO)5; d = 313.6 ppm, CDCl3, J(W,P) =
116 Hz).[14] Similar NMR spectroscopic data for a dinuclear
Z diphosphene–tungsten complexwere also reported by
Yoshifuji et al. (d = 332.0 ppm; CDCl3, J(W,P) = 145.0 and
116.0 Hz).[15] In contrast, the E diphosphene complex
[**] We thank the Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie for financial support by and the John
von Neumann Institute for Computing (Jülich) for computing time
(HBN12).
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
=
[LnW(R)P P(R)WLn] (R = CH(SiMe3)2, Ln = (CO)5) has a
Angew. Chem. Int. Ed. 2007, 46, 9327 –9330
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9327
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Communications
signal at d = 342.2 ppm with a coupling constant of 1J(W,P) =
268 Hz (CDCl3).[14]
To show that the phosphinidenoid complex 2 had formed,
we examined its generation in the presence of methyl iodide
and thus obtained P-methyl-substituted chlorophosphane
complex 4 (Scheme 2) as the sole phosphorus-containing
product, which showed without doubt the existence of
intermediate complex 2.
To investigate alternative routes to 2H-azaphosphirene
complexes,[16] we reacted complex 2 with dimethylcyanamide,
ꢀ
[17]
Scheme 4. Reaction of complex 2 with Ph(H)CO or PhC CH.
which gave 2H-azaphosphirene complex 6 selectively
if
diluted solutions of 2 were used. At higher concentrations, a
mixture of 6 and N-iminophosphane complex 7a was
obtained (ratio 1:1; Scheme 3). Complex 7a is not a follow-
up product of complex 6, as reaction of isolated complex 6
Scheme 5. Simpler access to complex 2.
trometry, and elemental analysis. In addition, complexes 6
and 7a were investigated by single-crystal diffraction studies,
but the data shall not be discussed herein (see Supporting
Information).
To gain some insight into the bonding of intermediate
complex 2, density-functional theory (DFT)[20] calculations
were carried out on 2 and, for comparison, also on 2’, for
which the crown ether is absent. The gas-phase DFT structure
of complex 2’ (Figure 1) has a lithium atom at phosphorus
with a short Li···O contact (2.005 Š) to the oxygen atom of a
carbonyl ligand, which is distorted by this interaction. The
distance between the lithium and chlorine atoms is 3.774 Š,
which is larger than the sum of covalent radii (2.33 Š) but
below the sum of van der Waals radii taken from the solid
state (4.00 Š).[21] The positive charge at lithium (and to a
small extent at phosphorus) is counterbalanced by the
negative charge at chlorine and the interacting oxygen of
the carbonyl ligand. The structure of 2’ can be compared to
Scheme 3. Reaction of complex 2 with nitriles.
with diisopropylamine at ambient temperature did not yield
complex 7a. Although complex 6 might stem from a formal
[2+1] cycloaddition, the formation of complex 7a hints at
nitrilium phosphane-ylid 5a as intermediate precursor for all
final products. Complex 5a can undergo valence isomer-
ization to give 6 and/or regioselective 1,2-addition of diiso-
propylamine, formed during deprotonation of 1, to yield 7a.
This was further supported by the reaction with benzonitrile,
as in this case complex 7b was obtained as the major product;
the corresponding 2H-azaphosphirene complexwas not
observed.
the
DFT-calculated
structure
of
the
fluoro-
The formation of phosphinidenoid complex 2 in the
presence of benzaldehyde and phenylacetylene lead to
heterocyclic complexes 8[18] and 9,[18] respectively
(Scheme 4). When phenylacetylene was used as reagent,
another product 10 was observed which could not be isolated
(products 9/10 in a ratio of 5:1) and had a signal in the
31P NMR spectrum at d = À78.3 ppm and coupling constants
of 1J(W,P) = 235.2 Hz and 1J(P,H) = 354.8 Hz.
Figure 1. DFT gas-phase structure of 2’ (without [12]crown-4; B3LYP/6-
311g(d,p), LanL2DZ at W); ball-and-stick model (left) and space-filling
model (right). Selected bond lengths [Š] and angles [8]: W-P 2.631, P-Cl
2.160, P-Li 2.416, Cl-Li 3.774, P-C3 1.890, W-C1 2.024, W-C2 1.987, C1-
O1 1.149, C2-O2 1.181; W-C2-O2 164.71, Cl-P-W 112.31, Cl-P-C3
103.65, W-P-C3 122.21, ꢀaP 338.178. Charges from a natural popula-
tion analysis (Mulliken charges in brackets) of Hartree–Fock orbitals:
P +0.201 (+0.203), W À0.933 (+0.773), Cl À0.401 (À0.358), C3
À1.502 (À1.198), C1 +0.688 (À0.028), O1 À0.578 (À0.288), C2
+0.680 (+0.064), O2 À0.743 (À0.429), Li +0.906 (+0.599).
Chlorine/lithium exchange of dichloro(organo)phosphane
complex 11[19] using tert-butyllithium at low temperature in
the presence of [12]crown-4 along with benzaldehyde or
butyraldehyde gave easier access to the phosphinidenoid
complex 2, yielding selectively oxaphosphirane complexes
8
[18] and 12, respectively (Scheme 5).
All complexes were purified by column chromatography
and fully characterized by NMR spectroscopy, mass spec-
9328
www.angewandte.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 9327 –9330
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Angewandte
Chemie
(methyl)phosphanide complex[(OC) 5Cr{PF(Me)}]À, for
which Mathey and Compain also found a significant bending
of the equatorial CO ligands towards phosphorus; the
HOMO was ascribed to the pronounced phosphorus lone
pair.[11]
Büchi apparatus, with samples sealed in capillaries under argon.
Selected NMR and MS data are given below.
4: Compound 1 (300 mg, 0.545 mmol), [12]crown-4 (0.089 mL,
0.545 mmol), and MeI (0.034 mL, 0.55 mmol) were dissolved in Et2O
(11 mL) in a cooled (À358C) dropping funnel. This solution was then
added dropwise to a cooled (À808C) suspension of freshly prepared
LDA (58.9 mg, 0.55 mmol) in Et2O (5.5 mL) and the reaction mixture
was stirred for 20 h. The suspension was allowed to stand, LiI was
removed by filtration, and the solvent removed under reduced
pressure (ca. 0.01 bar). The residue was dissolved in petroleum ether/
diethyl ether 1:1 (2 mL) and subjected to column chromatography
(neutral SiO2, À208C, petroleum ether). Complex 4 was obtained as a
colorless solid upon evaporation of the fourth fraction. Yield: 24 mg
(78%); m.p. 808C (decomp); 1H NMR: d = 2.47 (d, 3H, 2J(P,H) =
3.78 Hz, CH3), 1.77 (d, 1H, 2J(P,H) = 8,97 Hz, PCH(SiMe3)2),
0.38 ppm (s, 18H, SiMe3); 13C{1H} NMR: d = 198.4 (2J(P,C) =
30.1 Hz, COtrans), 196.2 (2J(P,C) = 7.4 Hz, COcis), 31.1 (1J(P,C) =
13.6 Hz, PCH) 30.8 (1J(P,C) = 18.4 Hz, CH3), 2.5 (3J(P,C) = 2.9 Hz,
SiMe3), 2.0 ppm (3J(P,C) = 3.6 Hz, SiMe3); 31P{1H} NMR: d =
Coordination of the [12]crown-4 moiety to lithium in 2’
significantly increases the distance between phosphorus and
À
lithium atoms from 2.416 (in 2’) to 2.652 Š (in 2) and the P Cl
bond from 2.160 (2’) to 2.217 Š (2), whereas the distortion of
the equatorial carbonyl ligand vanishes (Figure 2). The
1
105.4 ppm (ssat, J(P,W) = 273.4 Hz); MS: m/z (%): 564.0 (28) [M+].
6 and 7a: Compound 1 (550 mg, 1 mmol), [12]crown-4 (0.179 mL,
1.1 mmol), and dimethylcyanamide (0.407 mL, 5 mmol ) were dis-
solved in Et2O (3 mL) and added to a cooled (À308C) dropping
funnel. This solution was then added dropwise to a cooled (À808C)
solution of freshly prepared LDA (117.8 mg, 1.1 mmol) in Et2O
(7 mL) and the reaction mixture was stirred for 3 h until the reaction
bath had warmed to 08C. The orange solution was filtered to remove
LiCl and the solvent was removed under reduced pressure (ca.
0.01 bar). The residue was dissolved in 2 ” 2mL diethyl ether and
subjected to column chromatography (neutral Al2O3, À208C, petro-
leum ether). Complex 7a was obtained as the first fraction using
80 mL of eluent (petroleum ether/diethyl ether 95:5). Complex 6 was
obtained as the second fraction using 40 mL of eluent (petroleum
ether/diethyl ether 95:5) and the third fraction using 50 mL of eluent
(petroleum ether/diethyl ether 50:50). The second and third fraction
were combined. Compounds 6 and 7a were obtained as off-white and
colourless solids, respectively, after evaporation of solvent. 6: Yield:
169 mg (29%); m.p. 788C (decomp); 1H NMR: d = 3.31 (br s, 3H,
NCH3), 3.15 (br s, 3H, NCH3), 0.73 (d, 1H, 2J(P,H) = 2.90 Hz, PCH),
0.32 (s, 9H, SiMe3), 0.20 ppm (s, 9H, SiMe3); 13C{1H} NMR: d = 197.6
(d, 2J(P,C) = 34.3 Hz; COtrans), 195.4 (d, 2J(P,C) = 9.1; COcis), 176.1 (d,
2J(P,C) = 12.3 Hz; PNC), 39.9 (s, NCH3), 35.8 (s, NCH3), 29.6 (d,
Figure 2. Gas-phase DFT structure of complex 2; ball-and-stick model
(left) and space-filling model (right). Selected bond lengths [Š] and
angles [8]: W-P 2.652, P-Cl 2.217, P-Li 2.652, P-C2 1.905, Cl-Li 3.465, W-
C1 2.011, C1-O1 1.154; Cl-P-W 110.43, Cl-P-C2 101.45, W-P-C2 112.03,
ꢀaP 323.918. Charges from a natural population analysis (Mulliken
charges in brackets) of Hartree–Fock orbitals: P +0.248 (+0.162), W
À0.963 (+0.733), Cl À0.462 (À0.460), C2 À1.515 (À1.227), C1
+0.678 (À0.039), O1 À0.606 (À0.314), Li +0.853 (+0.816).
combination of a decreased W-P-C angle (122.218 vs.
112.038 in 2) and a decreased sum of bond angles at P (from
338.17 (2’) to 323.918) can be interpreted as the formation of a
pronounced, stereochemically active electron lone pair at
phosphorus. The natural population analysis showed that the
positive charge at phosphorus is somewhat larger in 2 than in
À
2’. As the Cl P bond length increases, the Cl–Li distance
decreases accordingly (from 3.774 (2’) to 3.465 Š), which can
be understood as the beginnings of the generation and
expulsion of lithium chloride.
3
1J(P,C) = 26.5 Hz, PCH), 1.08 (d, J(P,C) = 3.6 Hz, SiMe3), 0.10 ppm
(d, 3J(P,C) = 2.9 Hz, SiMe3); 31P{1H} NMR: d = À65.7 ppm (ssat
,
1J(P,W) = 293.7 Hz). MS: m/z (%): 584 (10) [M+]. 7a: Yield:
180 mg (26%); m.p. 838C (decomp); 1H NMR: d = 7.60 (dd, 1H,
1J(P,H) = 306.7 Hz, 3J(H,H) = 2.55 Hz, PH), 3.88 (mc, 2H,
N(C(H)Me2)2)), 2.88 (s, 6H, CN(CH3)2), 1.29 (d, 6H, 3J(H,H) =
We have shown that a transient phosphinidenoid complex
can be formed selectively by deprotonation or chlorine/
lithium exchange reactions under very mild conditions, and
reactivity was illustrated by the synthesis of heterocyclic
three-membered rings. DFT calculations showed that addi-
tional binding of the phosphinidenoid complexto [12]crown-4
leads to a more positively charged and more pyramidal
phosphorus, which has a weaker contact to lithium and
chlorine than without the crown ether.
3
6.99 Hz, N(C(H)(CH3)2)), 1.26 (d, 6H, J(H,H) = 6.89 Hz, N(C(H)-
(CH3)2), 0.80 (dd, 1H, 2J(P,H) = 4.34 Hz, 3J(H,H) = 2.55 Hz, PCH),
0.30 (s, 9H, SiMe3), 0.21 ppm (s, 9H, SiMe3); 13C{1H} NMR: d = 199.7
(d, 2J(P,C) = 20.7 Hz; COtrans), 197.5 (d, 2J(P,C) = 7.4 Hz; COcis), 160.1
(d, 2J(P,C) = 8.7 Hz; PNC), 48.7 (s, N(CHMe2)2), 40.0 (d, 2J(P,C) =
1.9 Hz; N(CH3)2), 22.6 (s, N(C(H)(CH3)2)), 20.9 (s, N(C(H)(CH3)2)),
20.1 (d, 1J(P,C) = 23.0 Hz, CH(SiMe3)2), 1.7 (d, 3J(P,C) = 2.6 Hz,
SiMe3), 0.0 ppm (d, 3J(P,C) = 2.6 Hz, SiMe3); 31P{1H} NMR: d =
1
À3.4 ppm (ssat, J(W,P) = 246.7 Hz). MS: m/z (%): 685 (5) [M+].
7b: Yellow solid; yield: 532 mg (74%); m.p. 898C (decomp);
1H NMR: d = 7.46 (m, 3H, Ph), 7.28 (m, 1H, Ph), 7.11 (m, 1H, Ph),
Experimental Section
1
3
6.33 (dd, 1H, J(P,H) = 315.3 Hz, J(H,H) = 5.00 Hz, PH), 4.45 (br s,
1H, N(C(H)Me2)2), 3.69 (mc, 1H, N(C(H)Me2)2), 1.52 (d, 3H,
All the reactions were carried out under an atmosphere of purified
and dried argon using standard Schlenk techniques. Solvents were
dried over sodium wire and distilled under argon. NMR data were
recorded on a Bruker DMX 300 spectrometer at 308C using CDCl3 as
solvent and internal standard; shifts are given relative to tetrame-
thylsilane (13C: 75.5 MHz, 29Si: 59.6 MHz) and 85% H3PO4 (31P:
3
3J(H,H) = 6.70 Hz, N(C(H)(CH3)2)), 1.43 (d, 3H, J(H,H) = 6.80 Hz,
N(C(H)(CH3)2)), 1.07 (d, 6H, 3J(H,H) = 6.70 Hz, N(C(H)(CH3)2)),
0.97 (dd, 1H, 2J(P,H) = 8.12 Hz, 3J(H,H) = 5.00 Hz, PCH), 0.28 (s, 9H,
SiMe3), 0.05 ppm (s, 9H, SiMe3); 13C{1H} NMR: d = 200.3 (d,
2J(P,C) = 13.6 Hz; COtrans), 197.6 (d, 2J(P,C) = 7.8 Hz; COcis), 160.5
(d, 2J(P,C) = 9.1 Hz; PNC), 134.1 (d, 3J(P,C) = 12.9 Hz; i-Ph-C), 128.2
121.5 MHz). Mass spectra were recorded on
a Kratos MS 50
spectrometer (EI, 70 eV). Melting points were determined using a
Angew. Chem. Int. Ed. 2007, 46, 9327 –9330
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org 9329
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Communications
(s, Ph-C), 128.0 (s, Ph-C), 127.7 (s, Ph-C), 125.5 (d, J(P,C) = 25.9 Hz;
[8] J. Borm, G. Huttner, O. Orama, J. Organomet. Chem. 1986, 306,
29 – 38.
[9] F. Mathey, A. Marinetti, Organometallics 1984, 3, 456 – 461.
[10] K. Lammertsma, A. W. Ehlers, M. L. McKee, J. Am. Chem. Soc.
2003, 125, 14750 – 14759.
1
Ph-C), 21.4 (br d, iPr-CH3), 20.3 (d, J(P,C) = 12.9 Hz, CH(SiMe3)2),
20.2 (s, iPr-CH3), 20.0 (s, iPr-CH3) 1.9 (d, 3J(P,C) = 1.9 Hz, SiMe3),
0.0 ppm (d, 3J(P,C) = 2.9 Hz, SiMe3); 31P{1H} NMR: d = 8.9 ppm (ssat
,
1J(W,P) = 256.9 Hz). MS: m/z (%): 718 (24) [M+].
8
and 12:
A
solution of tert-butyllithium (0.3 mL, 1.5m,
[11] C. Compain, F. Mathey, Z. Anorg. Allg. Chem. 2006, 632, 421 –
424.
0.46 mmol) was added dropwise to a solution of 11 (200 mg,
0.31 mmol) in diethyl ether (10 mL), [12]crown-4 (0.051 mL,
0.31 mmol) and benzaldehyde (0.032 mL, 0.31 mmol) or butyralde-
hyde (0.027 mL, 0.31 mmol) at À808C with stirring. The solution was
stirred for 90 minutes while gently warming to 08C. The solvents were
then removed in vacuo (ca. 10À2 bar) and the residues extracted with
n-pentane (20 mL). The product was purified by column chromatog-
raphy (Al2O3, À308C, petroleum ether). After evaporation, the raw
product was washed with a small amount of n-pentane at À208C. 8:
Yield: 102 mg (0.18 mmol, 44%); for further data see Ref. [18]. 12:
Yield: 106 mg (53%); m.p. 868C (decomp); 1H NMR: d = 2.75 (d,
1H, 2J(P,H) = 9.8 Hz, POCH), 1.60 (m, 1H, CH(CH3)2), 1.21 (d, 3H,
2J(H,H) = 6.7 Hz, CH3O), 1.17 (d, 3H ,2J(H,H) = 6.5 Hz, CH3), 1.05
(m, 1H, CH(SiMe3)2), 0.30 (s, 9H, SiMe3), 0.25 ppm (s, 9H, SiMe3);
13C{1H} NMR: d = 195 (d, 2J(P,C) = 33.6 Hz, COtrans), 193.4 (d,
2J(P,C) = 8.4, COcis), 62.9 (d, J(P,C) = 28.7 Hz, PCO), 28.7 (d, CH-
(SiMe3)2, J(P,C) = 17.1 Hz), 29.0 (d, CHCH3, J(P,C) = 3.3 Hz), 17.4 (d,
J(P,C) = 11.6 Hz, CHCH3), 17.2 (s, CHCH3), 0.0 (d, J(P,C) = 2.6 Hz,
SiMe3), À0.4 ppm (d, J(P,C) = 4.5 Hz, SiMe3); 31P{1H} NMR: d =
[12] A. Özbolat, E. Ionescu, S. Schneider, G. von Frantzius, M.
Nieger, P. G. Jones, R. Streubel, Organometallics 2007, in press.
[13] R. Streubel, S. Priemer, F. Ruthe, P. G. Jones, Eur. J. Inorg.
Chem. 2000, 1253 – 1259.
[14] H. Lang, O. Orama, G. Huttner, J. Organomet. Chem. 1985, 291,
293 – 309.
[15] M. Yoshifuji, N. Shinohara, K. Toyota, Tetrahedron Lett. 1996,
37, 7815 – 7818.
[16] R. Streubel, Coord. Chem. Rev. 2002, 227, 175 – 192.
[17] H. Wilkens, F. Ruthe, P. G. Jones, R. Streubel, Chem. Eur. J.
1998, 4, 1542 – 1553.
[18] R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem.
1994, 106, 2564 – 2566; Angew. Chem. Int. Ed. Engl. 1994, 33,
2427 – 2428.
[19] A. A. Khan, C. Wismach, P. G. Jones, R. Streubel, Dalton Trans.
2003, 2483 – 2487.
[20] GAUSSIAN03, RevB.02, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A.
Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M.
Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M.
Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida,
T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E.
Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J.
Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J.
Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K.
Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G.
Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas,
D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman,
J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L.
Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A.
Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc.,
Wallingford CT, 2003. B3LYP: A. D. Becke, J. Chem. Phys. 1993,
98, 5648. Valence triple zeta + polarization basis 6-311g(d,p): R.
Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys.
1980, 72, 650; A. D. McLean, G. S. Chandler, J. Chem. Phys.
1980, 72, 5639; Tungsten is described by the effective core
potential of Hay and Wadt: P. J. Hay, W. R. Wadt, J. Chem. Phys.
1985, 82, 270; Structures 2 and 2’ are minima, as confirmed by a
frequency calculation.
1
31.9 ppm (ssat, J(W,P) = 298.8 Hz); MS: m/z (%): 586 (10) [M+].
Received: May 3, 2007
Revised: August 7, 2007
Published online: November 5, 2007
Keywords: phosphinidenes · phosphinidenoids · P ligands ·
.
reactive intermediates · tungsten
[1] a) G. Köbrich, Angew. Chem. 1967, 79, 15 – 27; Angew. Chem.
Int. Ed. Engl. 1967, 6, 41 – 52; b) W. Kirmse, Angew. Chem. 1965,
77, 1 – 10; Angew. Chem. Int. Ed. Engl. 1965, 4, 1 – 10; c) G.
Boche, J. W. Lohrenz, Chem. Rev. 2001, 101, 697 – 756.
[2] F. Mathey, Angew. Chem. 2003, 115, 1616 – 1643; Angew. Chem.
Int. Ed. 2003, 42, 1578 – 1604.
[3] K. Lammertsma, Top. Curr. Chem. 2003, 229, 95 – 119.
[4] F. Mathey, N. H. Tran Huy, A. Marinetti, Helvet. Chim. Acta
2001, 84, 2938 – 2957.
[5] G. Huttner, H.-D. Müller, A. Frank, H. Lorenz, Angew. Chem.
1975, 87, 714 – 715; Angew. Chem. Int. Ed. Engl. 1975, 14, 705 –
706.
[6] G. Huttner, Acc. Chem. Res. 1986, 19, 406 – 413.
[7] H. Lang, G. Huttner, I. Jibril, Z. Naturforsch. B 1986, 41, 473 –
485.
[21] S. S. Batsanov, Russ. Chem. Bull. 1995, 44, 2245 – 2250; S. S.
Batsanov, Inorg. Mater. 2001, 37, 871 – 885.
9330
www.angewandte.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 9327 –9330
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&
&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
&
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&
Take advantage of blue reference links
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&