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Cooligomerization of Phosphaalkynes and Alkynes in the Coordination Sphere of Rhodium Complexes.

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'J(PH) = 586.2 Hz); '3C{1H}NMR: 6 = 110.1 (dd, 'J(PC) = 52.7. 38.4 Hz.
Cl).
7-(BF4),: 30 min after the preparation of a solution of 2.50 g (3.4 mmol) 3-Br
and 1.01 g (6.8 mmol)Me,OBF, in 10 mL CH,CI,, the volume was reduced to
half. A colorless, very moisture-sensitive powder (1.75 g, 61 %) precipitated on
addition of 10 mL Et,O and was recrystallized from CH,CI,/Et,O. 31PNMR
(AB, spin system): 6(A) = 69.3, d(B) = 22.4 (J(AB) = 11.O Hz, ,J(PH) =
12.8 Hz; "C('H)NMR: 6 = 116.9 (dd, 'J(PC) = 49.0. 36.4 Hz, Cl), 43.0 (d.
'J(PC) = 97.5 Hz, CH,).
Received: August 2. 1990 [Z 41 12 IE]
German version: Angew. Chem. 103 (1991) 333
monophosphacyclobutadiene complex, formed from 1,2bis(trimethylsily1)acetyleneand 1a has been described.[']
We now report the cooligomerizations of tert-butylphosphaacetylene (1 a) [31 and of N-isopropyl-N-trimethylsilyl-2aminophosphaacetylene (1 b)[41with tolane or acetylene in
the coordination sphere of rhodium(1) complexes. The starting point for the syntheses described here was provided by
the rhodium(1) complexes of tolane, 2 and 3, first synthesized
by H. Werner et al.J5] as well as of the vinylidene 6.L6I
[l] E Mathey, Chem. Rev. 88 (1988) 429.
M. H. Palmer, R. H. Findlay, J. Chem. SOC.Perkin Trans. 2 1975. 974.
W. Egan, R. Tang, G. Zon, K. Mislow. J. Am. Chem. SOC.93 (1971) 6205.
C. E. Griffin, K. R. Martin. B. E. Douglas, J. Org. Chem. 27 (1962) 1627.
[2]
[3]
[4]
[S]
For reactions of phosphonium ylides with chlorophosphances see: K.
Issleib, M. Lischewski, J. Prukr. Chem. 311 (1969) 857; ibid. 312 (1970)
135; H. Schmidbaur. W. Tronich, Chem. Ber. 101 (1968) 3545; G. Mirkl,
W. Bauer, Angew. Chem. 101 (1989) 1698; Angew. Chem. Int. Ed. Engl. 28
(1989) 1695; H. Grutzmacher, Z. Naturforsch. B 45 (1990) 170.
[6] 3'P NMR (ABC spin system): &A) = 170.6 (-PC12),6(B) = S(C) = 22.6
(-PPh3'), J(AB) = 219.0 Hz.
171 a) H. H. Karsch, H.-U. Reisacher, G. Muller. Angew. Chem. 98 (1986)
467; Angew. Chem. Int. Ed. Engl. 25 (1986) 454; b) H. Grutzmacher, H.
Pritzkow, ibid. 10f (1989) 768 and 28 (1989) 740.
[S] a)S. Lochschmidt. A. Schmidpeter, Phosphorus Sulfur 29 (1986) 73;
b) A. H. Cowley, R. A. Kemp. Chem. Rev. 85 (1985) 367.
[9] K. Karaghiosoff. A. Schmidpeter, Phosphorus Sulfur 36 (1988) 217.
[lo] "P NMR (AB, spin systems ): 4 (X = OMe) 6(A) = 83.2, 6(B) = 11.9
(J(AB) = 50.8 Hz); 5: 6(A) = 27.6, S(B) = 12.6 (J(AB) = 48.5 Hz.
'J(PH) = 504.9 Hz).
1111 a) R. Appel in M. Regitz, 0.J. Scherer (Eds.): Multiple Bonds and Low
Coordination in Phosphorus Chemistrj', Thieme, Stuttgart, 1990. p. 157;
b) A. R. Barron, A. H. Cowley, J. Chem. Soc. Chem. Commun. 1987,1092.
[12] A. Schmidpeter, K. Karaghiosoffin H. W. Roesky (Ed.): Rings, Clusters
and Polymers o j Main Group and Transirion Elements, Elsevier, Amsterdam 1989, p. 308.
[13] L. D. Qum, S. G. Borleske, R. C. Stocks, Org. Magn. Reson. 5(1973) 161;
G. A. Gray, J. H. Nelson, ibid. 14 (1980) 14.
(141 R. Appel, T. Gaitzsch, F. Knoch, G. Lenz, Chem. Ber. f19(1986) 1977; E.
Niecke, Bonn, personal communication.
[15] L. D. Quin, The Heteroryclic Chemisrry ojPhosphorus, Wiley. New York
1981, p. 90.
Cooligomerization of Phosphaalkynes and
Alkynes in the Coordination Sphere
of Rhodium Complexes **
By Paul Binger,* Josef Haas, Albert 7: Herrmann,
Franz Langhauser, and Carl Kruger
Dedicated to Professor Rolf Appel on the occasion
of his 70th birthday
Cyclizations of phosphaalkynes,['' especially of the kinetically stable, readily accessible terr-butylphosphaacetylene
(1 a), in the coordination sphere of transition-metal complexes have attracted increasing interest in recent years. For example, long-sought phosphorus heterocycles such as 1,3diphosphacyclobutadiene and 1,3,5-triphospha-Dewar-benzene are now accessible via this route.[ll Cooligomerizations
between phosphaalkynes and other unsaturated systems
(e.g., alkynes), however, are very rare. So far only one
[*] Prof. Dr. P. Binger, Dipl.-Chem. J. Haas, DipLChem. A. T. Herrmann,
DipLChem. F. Langhauser, Prof. Dr. C. Kruger
I**]
3 10
Max-Planck-Institut fur Kohlenforschung,
Kaiser-Wilhelm-Platz 1, D-4330 Mulheim a.d. Ruhr (FRG)
This work was supported by the Volkswagen-Stiftung.
0 VCH
Verlagsgesellschafl mbH. W-6940 Weinheim, 1991
t
PECR
0
1 a,b
90 %
'Ph
Ph
3
a. R = tBu;
b, R
=
5
NiPr(SiMe,)
The rhodium tolane complex 2 reacts at - 20 "C with two
equivalents of 1 a to give the cotrimer 4 (yield 76 %), in which
a monophosphacyclobutenyl group, formed from one molecule of 1a and the tolane ligand, is bonded as q 3 ligand to
rhodium. The second molecule of 1 a is bonded to the P atom
of the phosphacyclobutenyl ligand and to the rhodium center in a (r fashion.[71On the other hand, the rhodium (q5-cyclopentadieny1)tolane complex 3 reacts with the two phosphaalkynes 1 a and 1 b in refluxing THF to give the two
rhodium q4-monophosphacyclobutadiene complexes 5a
and 5 b, respectively, in 90 YOyield; that is, complex 3 undergoes codimerization with only one molecule of the phosphaalkyne.
Complex 7, the first l-phospha-2-rhodacyclobutene,is
formed upon reaction of the rhodium vinylidene complex 6
with 1a in a [2+2] cycloaddition as yellow needles (79%).r71
The regiochemistry of this cycloaddition indicates that the
carbene carbon of 6 has electrophilic character.['' Replacement of the chloro ligand in 7 by a cyclopentadienyl ligand
results in smooth formation of the l-phospha-2-rhoda-3methylenecyclobutene 8.
The crystal structure analyses of the rhodium complexes 4
and 7 reveal several structural features.tg1The rhodium atom
in 4 is coordinated in a distorted tetrahedral fashion; the
corners of the tetrahedron are occupied by CI, P2, P3,and
+
0570-0833/9lj0303-0310 $3.50 ,2510
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 3
'2'
A
C316
v
c21c
c
A
(J
kre
,CllA
c45
Fig. 1. Molecular structure of 4 (crystallographic numbering). Selected distances [A] and angles I"]: PI-Cl 1.860(3), Pl-C5 1.875(2), C1-C4 1.434(4).
C4-C5 1.443(4), Rh-P1 2.745(1), Rh-P2 2.226(1), Rh-P3 2.364(1), Rh-C1
2.235(3) Rh-C4 2.276(3). Rh-C5 2.152(3), Rh-CI 2.409(1), P1-C2 1.813(3), P2C2 1.657(3);C4-C5-P1 89.0(2), C5-C4-C1 100.7(2), C4-Cl-Pl 89.8(2), C5-PlC1 72.8(1). P2-C2-P1 108.4(2).
the q3-bonded ally1 part of the phosphacyclobutenyl ligand
(Fig. 1). The phosphacyclobutenyl ring is folded; the angle
between the planes Cl/Pl/CS and Cl/C4/C5 is 29.7". The
q3-allyl partial structure of this ring is characterized by the
nearly equal C1-C4 and C 4 C 5 distances (1.434(4) and
1.443(4) A, respectively) and the corresponding Rh-C distances (see caption to Figure I), which correlate with those
of known Rh-q3-allyl compounds.["] The P1-C1 and P1C5 distances (1.860(3) and 1.875(3) A) are consistent with
P-C single bonds, whereas the Pl-C2 distance is slightly
shortened (1.813(3) A); there is no bonding interaction between PI and rhodium (2.745(1) A). The P2-C2 distance in
the phosphaethylene bridge (1.657(3) A) corresponds to a
P-C double bond, and the P2-Rh distance (2.226(1) A) is
typical of a Rh-P single bond.
The rhodium coordination in 7 consists of a slightly distorted tetragonal bipyramid (Fig. 2) with the two triisopropylphosphane ligands in axial positions and P2, C1, and
CI, together with a free coordination site, in equatorial positions. The heterocycle is planar and, along with C31 and the
CI atom, lies in the crystallographic mirror plane of the molecule. The P2-C2 and C1-C11 distances (1.699(9) and
1.32(1) A, respectively) are in the range of P-C and C-C
double bond lengths, respectively; the CI-C2 single bond
(1.48(1) A) is slightly shortened. The Rh-P2 and Rh-C1 distances (2.241(2) and 2.057(9) A, respectively), as well as the
C1-Rh-P2 angle (68.0(2)"), are as expected. The latter agrees
with the values found in rhodacyclobutanes.["'
The structures of the rhodium complexes 5 and 8 were
derived from their spectroscopic data (mass spectrum, 31P
and I3C NMR spectra). The monophosphacyclobutadiene
complexes 5a, b exhibit the molecular-ion peak as most intense peak; the 31P NMR spectrum contains a doublet at
6 = - 48.75 (JPR,,
= 37.3 Hz) for 5 a and - 26.45 (JPRh
=
36.5 Hz) for 5b. In the I3C NMR spectrum, the characteristic signals for the C atoms of the four-membered ring of 5 a
lie (see formula for numbering) at 6 = 85.1 (CI, Jclp= 42.3,
JClRh
= 13.3 Hz), 103.9 (C2, JCZp
= 3.9, JCZRh
= 9.4 Hz), and
105.2 (C3, Jcjp= 45.7, JC3Rh
= 13.5 Hz). The structure has
meanwhile been confirmed by a crystal structure analysis.[t21
The values for 5 b are similar to those for 5a.
In the 31P NMR spectrum of the rhodium complex 8 (see
formula for numbering), the signal for the Rh-P single bond
(6 = 344.71, JPIRh
= 35.1 Hz, Jplp2
= 12.1 Hz) shows the
characteristic low-field shift. The 13C NMR spectrum con= 55 Hz) and 124.4 (C2,
tains signals at 6 = 235.1 (C3,
Jczp,and JCZRh
= 24.4, 11.2 Hz) for the C atoms of the fourmembered ring; the C atom of the terminal methylene group
gives rise to a signal at 6 = 104.4 (Cl, JCH= 150.5/160.1,
Jclpl= 23.7, JCIRh
= 1.9 Hz). Overall, the structure of 8 corresponds to that of known compounds of type 9.I1']
We are currently exploring the use of other alkynes and
phosphaalkynes in the syntheses describe here and are investigating the properties of the metal-free phosphorus heterocycles released from the complexes.
Experimental Procedure
4: Compound 1 a (2.5 g, 25 mmol) was added to 2 (0.55 g, 0.86 mmol) in 50 mL
of diethyl ether at - 30°C. The resultingdark red solution was stirred for 12 h
at 20°C and then concentrated to 10 mL. After cooling for 2 d at -78''C, the
solution afforded 4 as dark red, nearly black crystals; 0.44 g (76%) of 4 was
obtained after filtration and drying at 0.5 Torr; m.p. = 155°C (dec.).
5 a : Compound l a (0.08 g, 0.8 mmol) was added to a solution of 3 (0.35 g,
0.69 mmol) in 40 mL of THF and the reaction mixture was refluxed for 3 d. The
TH F was then removed by distillation at 0.5 Torr, the residue was dissolved in
5 mL of pentane, and the resulting solution was cooled to -78°C. The yellow
crystals formed after 3 d were freed of mother liquor and dried at 0.5 Torr;
0.28 g (90%) 5a, m.p. 95°C.
7: Compound 6 (0.65 g, 1.3 mmol) was dissolved in 40 mL of THF at 0 C and
1a (0.18 g, 1.8 mmol) was then added, resulting in an immediate change in color
from yellow to red. The reaction mixture was stirred for 12 h at 20 'C, the
volatiles were then removed at 0.5 Torr, and the oily residue was dissolved in
25 mL of diethyl ether; 7 precipitated at -78 "C a s a microcrystalline yellow
solid. A single recrystallization gave 0.63 g (79%) of yellow needles (m.p.
111 T ) .
-
c51'
Received: October 1. 1990 [Z 4219 IE]
German version: Angew. Chem. 103 (1991) 316
Publication delayed at authors' request
qc41
Y
Fig. 2. Molecular structure of 7 (crystallographic numbering). Selected bond
Rh-CI 2.436(2), Rh-P1 2.399(1), Rh-P2 2.241(2),
distances [A] and angles
Rh-Cl 2.057(9). P2-C2 1.699(9), C1-C2 1.48(1) Ct-Cil 1.32(1); Pl-Rh-Pl*
172.1(1), Cl-Rh-CI 174.7(2), Cl-Rh-PZ 68.0(2). C2-PZ-Rh 89.8(3), Cl-C2-P2
98.3(6), C2-Cl-Rh 103.9(6).
r]:
Angew. Chem. I n t . Ed. Engl. 30 (1991) No. 3
0 VCH
CAS Registry numbers:
l a , 78129-68-7; Ib, 118375-89-6: 2, 131564-13-1; 3, 81423-53-2; 4, 13145848-5; 5a, 131458-49-6; 5b, 131458-52-1; 6, 95935-81-2; 7, 131458-50-9;
7 'C 4 H i o 0 , 131458-53-2;8, 131458-51-0.
Verlagsgeselischafr mbH, W-6940 Weinheim. 1991
0570-0833/91/0303-031l 8 3.50-k.2Sj0
31 1
[I] Reviews: a) M. Regitz, P. Binger, Angew. Chem. lOO(1988) 1541; Angew.
Chem. Int. Ed. Engl. 27 (1988) 1484; b) J. F. Nixon. Chem. Rev. 88 (1988)
1327.
[2] P. Binger, R. Milczarek, R. Mynott, M. Regitz, J. Orgunomet. Chem. 323
(1987) C35.
[3] a) G. Becker, G. Grosser, W. Uhl, 2. Naturforsch. B36 (1981) 16; b) W
Rosch, U. Mees, M. Regitz, Chem. Ber. I20 (1987) 1645.
[4] R. Appel. M. Poppe, Angew. Chem. I01 (1989) 70; Angew. Chem. Int. Ed.
Engl. 28 (1989) 53.
[5] H. Werner. J. Wolf, U. Schubert, K. Ackermann, J. Organomer. Chem. 317
(1986) 327.
[6] H. Werner, F. J. G. Alonso, H. Otto, J. Wolf, Z. Naturforsch, 5 4 3 (1988)
722.
(71 Spectroscopic data for 4 and 7 (for numbering see Figs. 1 and 2): 4: 31P
NMR (81 MHz, (DJTHF, 25°C. H,PO,): 6 = - 142.46 (Pl, J(Pl,P2) =
37.3. J(Pl,P3) = J(P1,Rh) = 3.4 Hz), 422.75 (P2. J(P2.P3) = 30.6,
J(P2,Rh) = 30.6 Hz), 46.7 (P3, J(P3,Rh) = 174.5 Hz). 13C NMR
(75.5 MHz, [DJTHF, 3 0 T , TMS): 6 = 195.1 (C2, J(C2,P2) = 87.5,
J(C2,PI) ~ 7 2 . 2Hz), 157.3 (CI, J(CI,P2) = 24.3, J(C1.Pl) = 36.1 Hz),
136.1 (C4, J(C4,P2)=4.7, J(C4,PI)=22,0Hz), 96.7 (C5, J(CS,Pl)=
J(C5,P2) = 12.6, J(C5,Rh) = 2.0Hz). 7: 31P NMR (81 MHz, C,D,,
25”C, H,PO,): 6 = 35.82 (Pl, J(P1,PZ) = 18.3, J(P1,Rh) = 114.4Hz),
379.59 (P2, J(P2,Rh) = 34.3 Hz). 13C NMR (75.5 MHz, [DJTHF, 30‘C.
TMS): 6 = 129.0 (CI, J(C1,PI) = 8.1, J(C1,PZ) = 21.4, J(C1,Rh) =
3.0 Hz), 219.8 (C2, J(C2,Pl) = 5.0, J(C2,PZ) = 52.5, J(C2,Rh) = 4.9 Hz),
99.1 (C11. J(C,H) = 152/160, J(ClI,P2) = 26.5. J(C11,Rh) = 3.1 Hz).
[8] A [2+2] cycloaddition of l a to the Ti-C double bond of (viny1carbene)derivatives (P. Binger,
titanocenes affords 1-phospha-3-titanocyclobutene
B. Biedenbach, P. Miiller, R. Mynott, unpublished results). The same
regioselectivityis observed in the cycloaddition of 1a to chromium cdrbene
complexes (K. H. Dotz, A. Tiriliomis, K. Harms, M. Regitz, U. Annen.
Angew. Chem. fOO(1988) 725; Angew. Chem. Int. Ed. Engl. 27(1988) 713;
K. H. Dotz, A. Tiriliomis, K. Harms, J. Chem. Sor. Chem. Commun. 1989,
788).
[9] a) Crystal structure analysis of 4 at 20°C; C,,H,,CIP,Rh. space group
P2,/n, a = 9.660(1), b = 19.087(2). c = 19.027(2)A, p = 95.75(1)”. Z = 4,
ecSlcd
= 1.29 g
fl(Mo,.) =7.13 cm-I, Enraf-Nonius diffractometer
CAD4: 10042 measured reflections, averaged to 9409, 6807 observed
( I > 20(1)), R = 0.042, R , = 0.042 (w = l/u2(Fo))for 343 parameters [9c];
b) crystal structure analysis of 7 at - 173°C: C,,H,,CIP,Rh
C,HlOO.
space group P2,/m, a = 10.999(4), b = 12.894(3), c = 12.164(2)A,
fl = 97.99(2)”, 2 = 2, eCalcd
= 1.28 gcm-’. p(MoKI)~ 7 . 2 cm-’.
8
EnrafNonius diffractometer CAD4: 4253 measured reflections. averaged to
4061,3183 observed ( I > 20(I)), R = 0.065, R , = 0.073 (M. = 1/u2(F,)) for
172 parameters [Sc]; c) Further details of the crystal structure investigations may be obtained from the Fachinformationszentrum Karlsruhe,
Gesellschaft fur wissenschaftlich-technischeInformation mbH. D-7514
Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number
CSD-54968, the names of the authors, and the journal citation.
[lo] a) M. McPantlein, R. Mason, Chem. Commun. f967.16; b) H. Pasternack.
T. Glowiak, F. Pruchnik, Inorg. Chim. ACIQ19 (1976) 11.
[ l l ] a) R. A. Periana, R. G. Bergmann, J. Am. Chem. Soc. 106 (1984) 7272;
b) L. Andreucci. P. Diverso, G. Ingrosso, A. Lucherini, F. Marchetti. V.
Adovasio, M. Nardelli, J. Chem. Soc. Dalton Trans. 1986, 477.
[12] C. Kriiger, A. T. Herrmann, F. Langhauser, unpublished.
and other main-group elements. However, nothing is known
about the relevance of this class of compounds to coordination chemistry and organometallic synthesis. The related
bis(irnino)phosphorane~,~~~
on the other hand, have found
applications in catalysis.[41We report here the synthesis of
the first metallobis(methylene)phosphorane as well as the
products of its cyclization.
Reaction of the reactive potassium metalate
obtainable from q3-allyl(tricarbonyI)iodoiron and K/Hg, with the
chlorobis(methy1ene)phosphorane 1 led to substitution of
chlorine and formation of 3, as the main product,t6] together
(4), which rewith bis(methylene)propenyIphosph~rane~~~
sults from extrusion of the carbonyl fragment.’’]
2
-KCI
4
R = SiMe,
3
Recently, a transition-metal-substituted bis(methy1ene)phosphorane was also assumed to be the product obtained
from the reaction of K[(q5-C,H,)Fe(CO),] (5) with l.t9]
However, the 31PNMR signal (6 = - 81.6), which is found
at unusually high field for a 03h5-phosphorus atom, especially compared with the signal for 3 (6 = 331.8), indicates
that, instead of the postulated “open” form of a metallobis(methylene)phosphorane, a cyclic isomer was obtained.
By varying the reaction conditions,[”] we have now succeeded in synthesizing the metallobis(methy1ene)phosphorane 6 and its rearrangement product, the phosphaferrocene
7, from 1 and 5. Both isomers were separated by column
chromatography and isolated as pure compounds. The isomerization of 6 and 7 can be regarded as a coupling of the
phosphorane fragment with the two carbonyl groups of the
Fe fragment. Thus, the rearrangement does not lead to the
isomeric metallo- h3-phosphirane S,[‘ as so often observed
The First Metallobis(methy1ene)phosphoranesUnexpected Isomerization to a Phosphaferrocene
Fe
By Hans Jurgen Metternich and Edgar Niecke*
Dedicated to Professor Rolf Appel on the occasion
of his 70th birthday
w
5
K@
co
i
The synthesis of bis[bis(trimethylsilyl)methylene]chlorophosphorane (I), the first P-functionalized 03h5-phosphorane, by Appelet al.[’’ led to an intensive investigation of this
class of compounds.[2]The focus of this work has been the
preparation of compounds with bonds between phosphorus
[*] Prof. Dr. E. Niecke, Dipl.-Chem. H. J. Metternich
Anorganisch-chemisches Institut der Universitlt
Gerhard-Domagk-Strasse 1, W-5300 Bonn (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
3 12
0 VCH
Verlagsgeseilsehaji mbH, W-6940 Weinheim, 1991
0570-0833/9l/0303-0312$3.50+ .2S/O
6
49
7
Angew. Chem. Inr.
8
Ed. Engl. 30 (1991) No. 3
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