Half-sandwich type rhodium(I) complexes with arenes and functionalized arenes C6H5X(CH2)nPR2 (R = iPr, tBu) as nonchelating and chelating ligands

Article abstract of DOI:10.1021/om0004646

A series of arenerhodium(I) complexes [(η⁶-arene)Rh(C₈H₁₄)(PiPr₃)]PF₆ (2-6) were prepared, from the highly reactive starting material cis-[Rh(C₈H₁₄)(PiPr₃)(acetone)₂]PF ₆ (1) and the arene in CH₂Cl₂ in excellent yields. The related ethene compound [(η⁶-C₆H₆)Rh(C₂H₄)(PiPr₃)]P F₆ (7) was obtained by stirring a solution of the corresponding cyclooctene derivative 2 under an ethene atmosphere. Reaction of cis-[Rh(C₈H₁₄)₂(acetone)₂]PF₆ (10) with the new alkyldiisopropylphosphines iPr₂P(CH₂)_nC₆H₅(8, n = 2;9, n = 3), which were prepared from HPiPr₂ and C₆H₅(CH₂)_nBr in the presence of ammonia, in the molar ratio of 1:1 gave the half-sandwich type complexes [{η⁶-C₆H₅(CH₂)_nPiPr₂ -κ-P}Rh (C₈H₁₄)]PF₆ (11,12). They afforded upon treatment with a second equivalent of 8 or 9 the bis(phosphine) compounds [{η⁶-C₆H₅(CH₂)_nPiPr₂- κ-P}{C₆H₅(CH₂)_nPiPr₂ -κ- P}Rh]PF₆ (13, 14). The NMR spectra of 13 and 14 are not temperature-dependent, and therefore a fluxional behavior in solution can be excluded. The cyclooctene ligand of 11 could easily be displaced by ethene, maleicacid anhydride, ethyl propiolate, and triisopropylstibine to generate the substitution products 15-18 in 80-90% yield. Similarly, the ethene complex 19 was obtained from 12 and C₂H₄. The even more bulky alkyldi-tert-butylphosphines tBu₂P(CH₂)_nXC₆H₅ (20, n = 1, X = CH₂; 21, n = 2, X = O) and their respective olefin and alkyne rhodium(I) complexes 22a, 23, and 24 were prepared by using the same methodology as applied for the iPr₂P counterparts. The corresponding triflate [{η⁶-C₆H₅(CH₂)₂PtBu₂- κ-P}Rh(C₈H₁₄)]CF₃SO₃ (22b) was obtained from the dimer 25 and the phosphine 20 as starting materials. The molecular structures of 11, 12, and 19 were determined by X-ray crystallography.

Full text of DOI:10.1021/om0004646

4756
Organometallics 2000, 19, 4756-4766
Ha lf-Sa n d w ich Typ e Rh od iu m (I) Com p lexes w ith Ar en es
a n d F u n ction a lized Ar en es C6H5X(CH2)n P R2 (R ) iP r ,
tBu ) a s Non ch ela tin g a n d Ch ela tin g Liga n d s
Helmut Werner,* Giuseppe Canepa, Kerstin Ilg, and J ustin Wolf
Institut fu¨r Anorganische Chemie, Universita¨t Wu¨rzburg, Am Hubland,
D-97074 Wu¨rzburg, Germany
Received J une 1, 2000
A series of arenerhodium(I) complexes [(η6-arene)Rh(C8H14)(PiPr3)]PF6 (2-6) were prepared
from the highly reactive starting material cis-[Rh(C8H14)(PiPr3)(acetone)2]PF6 (1) and the
arene in CH2Cl2 in excellent yields. The related ethene compound [(η6-C6H6)Rh(C2H4)(PiPr3)]-
PF6 (7) was obtained by stirring a solution of the corresponding cyclooctene derivative 2
under an ethene atmosphere. Reaction of cis-[Rh(C8H14)2(acetone)2]PF6 (10) with the new
alkyldiisopropylphosphines iPr2P(CH2)nC6H5 (8, n ) 2; 9, n ) 3), which were prepared from
HPiPr2 and C6H5(CH2)nBr in the presence of ammonia, in the molar ratio of 1:1 gave the
half-sandwich type complexes [{η6-C6H5(CH2)nPiPr2-κ-P}Rh(C8H14)]PF6 (11, 12). They afforded
upon treatment with a second equivalent of 8 or 9 the bis(phosphine) compounds [{η6-C6H5-
(CH2)nPiPr2-κ-P}{C6H5(CH2)nPiPr2-κ-P}Rh]PF6 (13, 14). The NMR spectra of 13 and 14 are
not temperature-dependent, and therefore a fluxional behavior in solution can be excluded.
The cyclooctene ligand of 11 could easily be displaced by ethene, maleicacid anhydride, ethyl
propiolate, and triisopropylstibine to generate the substitution products 15-18 in 80-90%
yield. Similarly, the ethene complex 19 was obtained from 12 and C2H4. The even more
bulky alkyldi-tert-butylphosphines tBu2P(CH2)nXC6H5 (20, n ) 1, X ) CH2; 21, n ) 2, X )
O) and their respective olefin and alkyne rhodium(I) complexes 22a , 23, and 24 were prepared
by using the same methodology as applied for the iPr2P counterparts. The corresponding
triflate [{η6-C6H5(CH2)2PtBu2-κ-P}Rh(C8H14)]CF3SO3 (22b) was obtained from the dimer 25
and the phosphine 20 as starting materials. The molecular structures of 11, 12, and 19
were determined by X-ray crystallography.
In tr od u ction
ing ligands of the general formula R2P(CH2)nPR′2 (n )
1, 2, 3; R, R′ ) Ph, iPr, Cy, etc.),2,3 we recently observed
that the labile starting material cis-[Rh(C8H14)2(acetone)2]-
PF6 reacts with iPr2PCH2PCy2 in acetone-benzene or
acetone-toluene to give the half-sandwich type com-
plexes [(η6-arene)Rh(κ2-iPr2PCH2PCy2)]PF6 (arene )
C6H6, C6H5Me).2 If instead of cis-[Rh(C8H14)2(acetone)2]-
PF6 the triisopropylphosphine derivative cis-[Rh(C8H14)-
(PiPr3)(acetone)2]PF6 (1)4 is used, the reaction with
The intention to undertake the work reported in this
paper was twofold: First, we were interested to find out
whether cationic arenerhodium(I) compounds of the
general composition [(η6-arene)Rh(L)(PiPr3)]+, where L
is a labile ligand such as acetone, THF, and cyclooctene,
are accessible and, if so, can be used as starting
materials for carbene, vinylidene, and allenylidene
complexes [(η6-arene)Rh{dC(dC)nR2}(PiPr3)]+ (n ) 0,
1, 2). Second, we were tempted to answer the question
whether diisopropylphosphine and di-tert-butylphos-
phine derivatives of the type R′2P(CH2)nXC6H5 (X ) O,
CH2) are able to behave as chelating ligands and thus
generate a (possibly solvated) 16-electron rhodium(I)
fragment [{η6-C6H5X(CH2)nPR′2-κ-P}Rh]+, which might
be more suitable to stabilize a RhdC(dC)nR2 linkage
than the nonchelating [(η6-arene)Rh(PiPr3)]+ moiety. We
were aware of the fact that various cationic rhodium(I)
complexes [(η6-arene)Rh(L)(L′)]+ were known,1 but to
the best of our knowledge none of them contain a
sterically demanding trialkylphosphine such as PiPr3
and iPr2P(CH2)nC6H5.
(1) (a) Schrock, R. R.; Osborn, J . A. J . Am. Chem. Soc. 1971, 93,
3089-3091. (b) Green, M.; Kuc, T. A. J . Chem. Soc., Dalton Trans.
1972, 832-839. (c) Green, M.; Parker, G. J . J . Chem. Soc., Dalton
Trans. 1974, 333-343. (d) Uson, R.; Lahuerta, P.; Reyes, J .; Oro, L.
A. Inorg. Chim. Acta 1980, 42, 75-84. (e) Uson, R.; Oro, L. A.; Foces-
Foces, C.; Cano, F. H.; Vegas, A.; Valderrama, M. J . Organomet. Chem.
1981, 215, 241-253. (f) Uson, R.; Oro, L. A.; Foces-Foces, C.; Cano, F.
H.; Garcia-Blanco, S.; Valderrama, M. J . Organomet. Chem. 1982, 229,
293-304. (g) Valderrama, M.; Oro, L. A. Can. J . Chem. 1982, 60, 1044-
1047. (h) Burch, R. R.; Muetterties, E. L.; Day, V. W. Organometallics
1982, 1, 188-197. (i) Valderrama, M.; Scotti, M.; Ganz, R.; Oro, L. A.;
Lahoz, F. J .; Foces-Foces, C.; Cano, F. H. J . Organomet. Chem. 1985,
288, 97-107. (j) Bittersmann, E.; Hildenbrand, K.; Cervilla, A.;
Lahuerta, P. J . Organomet. Chem. 1985, 287, 255-263. (k) Bleeke, J .
R.; Donaldson, A. J . Organometallics 1988, 7, 1588-1596.
(2) (a) Wolf, J .; Manger, M.; Schmidt, U.; Fries, G.; Barth, D.;
Weberndo¨rfer, B.; Vicic, D. A.; J ones, W. D.; Werner, H. J . Chem. Soc.,
Dalton Trans. 1999, 1867-1875. (b) Manger, M. Dissertation, Uni-
versita¨t Wu¨rzburg, 1998.
(3) (a) Fries, G.; Wolf, J .; Pfeiffer, M.; Stalke, D.; Werner, H. Angew.
Chem. 2000, 112, 575-578; Angew. Chem., Int. Ed. 2000, 39, 564-
566. (b) Fries, G. Dissertation, Universita¨t Wu¨rzburg, 2000.
(4) Werner, H.; Schneider, M. E.; Bosch, M.; Wolf, J .; Teuben, J .
H.; Meetsma, A.; Troyanov, S. I. Chem. Eur. J . 2000, 6, 3052-3059.
Resu lts a n d Discu ssion
1. Ar en er h odiu m (I) Com pou n ds with [Rh (olefin )-
(P iP r 3)]+ a s a Molecu la r Un it. Following our studies
on the coordination properties of unsymmetrical chelat-
10.1021/om0004646 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 10/12/2000

Half-Sandwich Type Rhodium(I) Complexes
Organometallics, Vol. 19, No. 23, 2000 4757
Sch em e 1
occurs, for PhC≡CPh and MeC≡CSiMe3 as well as for
HC≡CPh and HC≡CCO2Me as substrates mixtures of
products were formed, the NMR spectra of which
indicated that presumably a cleavage of both the Rh-
C8H14 and the Rh-arene bonds had taken place.
2. P r ep a r a tion of Ch ela tin g P h osp h in es iP r 2P -
(CH2)n C6H5. An obvious possibility to prevent a com-
plete elimination of the arene unit in the cationic
compounds [(η6-arene)Rh(L)(PiPr3)]+ is to link the six-
membered ring via a (CH2)n chain with the phosphorus
atom, thus generating a chelate system. Recently,
Mirkin et al. reported that upon treatment of [RhCl-
(C8H14)2]2 with AgBF4 in THF and subsequent reaction
of the intermediate with Ph2P(CH2)2XC6H4R (X ) CH2,
O), mononuclear rhodium(I) complexes are formed in
which the substituted diphenylphosphines can behave
as monodentate (P-bonded) or chelating ligands.5 More-
over, Noels and co-workers found that monomeric ru-
thenium(II) compounds of the general composition [{η6-
3.5-C6H3R2(CH2)3PCy2-κ-P}RuCl2] (R ) H, CH3) are
accessible, though catalytically less efficient in the
ATRP (atom transfer radical polymerization) reaction
than the nonchelate counterparts [(η6-arene)RuCl2-
(PCy3)].6
A well-known procedure for the preparation of alkyl-
diphenylphosphines Ph2P(CH2)nC6H5 (n ) 2, 3) consists
of the reaction of LiPPh2 or KPPh2 with the respective
benzene derivative C6H5(CH2)nX (X ) Cl, Br), but this
method could not be applied for the diisopropylphos-
phine analogues iPr2P(CH2)nC6H5. The reason is that,
in agreement with earlier work by Issleib and Mu¨ller,
dialkylphosphides MPR2 (R ) alkyl) upon treatment
with alkylhalides R′X undergo a halide-metal exchange
which yields via reaction of MPR2 with the intermedi-
arily formed R2PX the corresponding diphosphines
P2R4.7
Sch em e 2
excess benzene in CH2Cl2 as solvent affords the cationic
rhodium(I) compound 2 in excellent yield. The analogous
complexes 3-6 (Scheme 1) were prepared through a
similar route. While for the synthesis of 3, 4, and 5 the
substitution reaction of 1 was carried out in pure C6H5-
CF3, 1,3,5-C6H3Me3, or C6H5OMe as solvent, the related
complex 6 was obtained upon treatment of a suspension
of 1 in ether with 1,3,5-trismethoxybenzene. The yield
of 3, 5, and 6 was 93-98%. The mesitylene derivative
4 could not be isolated analytically pure, as it contained
even after repeated recrystallization an impurity, which
1
owing to the H NMR spectrum also has one arene and
one phosphine ligand coordinated to rhodium.
The half-sandwich type compounds 2, 3, 5, and 6 are
yellow, only moderately air-sensitive solids which are
readily soluble in polar organic solvents such as CH2-
Cl2 or THF. In nitromethane they exhibit the conductiv-
ity of 1:1 electrolytes. While the 1H and 13C NMR spectra
of 2-6 display the typical signals for the arene, phos-
phine, and cyclooctene protons and carbon nuclei, the
31P NMR spectra show, apart from the signal for the
However, we found that a convenient route to prepare
the wanted alkyldiisopropylphosphines iPr2P(CH2)nC6H5
(8, n ) 2; 9, n ) 3) proceeds via the trialkylphosphonium
bromides [iPr2PH(CH2)nC6H5]Br. These intermediates
are obtained by heating a mixture of HPiPr2 and
2-phenylethyl- or 3-phenylpropylbromide for 24 h at 90
°C in the absence of solvent. After cooling, the purified
phosphonium bromide was treated with a concentrated
aqueous solution of ammonia to give both 8 and 9 as
colorless viscous liquids in 89% (8) and 78% (9) yield
(Scheme 3). The new phosphines, which like PiPr3 are
-
PF6 anion, one resonance which due to phosphorus-
rhodium coupling is split into a doublet. In all cases,
the coupling constant 2J (31P103Rh) is 181-183 Hz. In
the 19F NMR spectrum of 3, the signal for the fluorine
atoms of the CF3 group appears as a singlet at δ -60.2.
It should be mentioned that although compound 3 can
be stored under argon at -60 °C for days, in acetone
solution in the absence of C6H5CF3 the staring material
1 is regenerated.
1
quite air-sensitive, were characterized by H, 13C, and
31P NMR spectroscopy and by mass spectra. Since 8 and
9 could not be correctly analyzed, these neutral com-
pounds were converted with CH3I to the corresponding
methylphosphonium salts 8a and 9a , which are stable
solids and gave correct elemental analyses. Typical
To find out whether the cyclooctene ligand in 2 can
be displaced by another olefin, a degassed solution of 2
in CH2Cl2 was brought under an ethene atmosphere.
Without cleaving the Rh-C6H6 bond, a smooth ligand
exchange of C8H14 for C2H4 takes place to give the
cationic ethenerhodium(I) compound 7 in 89% yield
(Scheme 2). The 1H NMR spectrum of 7 exhibits two
resonances at δ 3.33 and 2.27 for the “outer” and the
“inner” protons of the C2H4 unit, indicating that the
rotation of the ethene ligand around the Rh-C2H4 axis
is considerably hindered. Attempts to substitute the
cyclooctene moiety in 2 by either an internal or a
terminal alkyne failed. Although in each case a reaction
(5) (a) Singewald, E. T.; Mirkin, C. A.; Levy, A. D.; Stern, C. L.
Angew. Chem. 1994, 106, 2524-2526; Angew. Chem., Int. Ed. Engl.
1994, 33, 2473-2475. (b) Singewald, E. T.; Shi, X.; Mirkin, C. A.;
Schofer, S. J .; Stern, C. L. Organometallics 1996, 15, 3062-3069. (c)
Singewald, E. T.; Slone, C. S.; Stern, C. L.; Mirkin, C. A.; Yap, G. P.
A.; Liable-Sands, L. M.; Rheingold, A. L. J . Am. Chem. Soc. 1997, 119,
3048-3056. (d) Slone, C. S.; Mirkin, C. A.; Yap, G. P. A.; Guzei, I. A.;
Rheingold, A. L. J . Am. Chem. Soc. 1997, 119, 10743-10753. (e)
Allgeier, A. M.; Mirkin, C. A. Angew. Chem. 1998, 110, 936-952;
Angew. Chem., Int. Ed. 1998, 37, 894-908.
(6) Delaude, L.; Simal, F.; Demonceau, A.; Noels, A. F. International
Symposium on Organometallics and Catalysis; Rennes 1999, Abstr. p
1.
(7) Issleib, K.; Mu¨ller, D.-W. Chem. Ber. 1959, 92, 3175-3182.

4758 Organometallics, Vol. 19, No. 23, 2000
Werner et al.
F igu r e 1. ORTEP drawing of 11.
F igu r e 2. ORTEP drawing of 12.
Sch em e 3
Ta ble 1. Selected Bon d Dista n ces a n d An gles w ith
Esd ’s for Com p ou n d 11
Bond Distances (Å)
Rh-P1
Rh-C1
Rh-C2
Rh-C3
Rh-C4
2.236(1)
2.215(3)
2.308(3)
2.364(3)
2.364(4)
Rh-C5
2.377(4)
2.304(3)
2.158(3)
2.138(3)
1.403(5)
Rh-C6
Rh-C20
Rh-C21
C20-C21
Bond Angles (deg)
P1-Rh-C20
P1-Rh-C21
Rh-C20-C21
Rh-C21-C20
C20-C21-C22
C21-C20-C27
92.3(1)
95.9(1)
70.2(2)
71.7(2)
122.7(4)
124.3(3)
Rh-P1-C8
P1-C8-C7
C8-C7-C1
C7-C1-C2
C7-C1-C6
104.0(1)
112.7(3)
111.3(3)
120.7(4)
120.3(3)
NMR spectroscopic features of 8 and 9 are the two
doublets of doublets for the protons of the pairwise
anisochronous methyl groups of the isopropyl units and
the two or three resonances for the carbon atoms of the
bridging CH2 moieties. All of these 13C NMR resonances
are split into doublets, the value of the 13C-31P coupling
constant being almost the same for the PCH2 and the
PCH2CH2 carbon nuclei.
Ta ble 2. Selected Bon d Dista n ces a n d An gles w ith
Esd ’s for Com p ou n d 12
Bond Distances (Å)
Rh-P1
Rh-C1
Rh-C2
Rh-C3
Rh-C4
2.265(1)
2.295(4)
2.330(4)
2.330(4)
2.327(4)
Rh-C5
Rh-C6
Rh-C20
Rh-C21
C20-C21
2.355(4)
2.334(4)
2.151(4)
2.127(4)
1.403(6)
3. Ha lf-Sa n d w ich Typ e Rh od iu m (I) Com p lexes
w ith On e or Tw o iP r 2P (CH2)n C6H5 Liga n d s. The
highly reactive bis(acetone)rhodium(I) derivative 108 is
an appropriate starting material not only for the
synthesis of the above-mentioned compounds [(η6-arene)-
Rh(κ2-iPr2PCH2PCy2)]PF6 but also for that of the new
half-sandwich type complexes 11 and 12 (see Scheme
3). However, the success of the preparation of 11 and
12, in which one alkyldiisopropylphosphine iPr2P-
(CH2)nC6H5 (n ) 2 or 3) is coordinated in a chelating
fashion to rhodium, strictly depends on the reaction
conditions. After several unsuccessful attempts we
found that addition of a diluted solution of 8 in acetone
to a highly concentrated solution of 10 in the same
solvent at -20 °C affords, after warming to room
temperature, the wanted products in nearly quantita-
tive yields. Both 11 and 12 are yellow air-stable solids
that are significantly more stable in the crystalline state
and in solution than the nonchelate counterparts 2-6.
Bond Angles (deg)
86.8(1)
94.3(1)
69.9(2)
71.8(2)
P1-Rh-C20
P1-Rh-C21
Rh-C20-C21
Rh-C21-C20
C20-C21-C22
C21-C20-C27
Rh-P1-C9
P1-C9-C8
C9-C8-C7
C8-C7-C1
C7-C1-C2
C7-C1-C6
111.3(1)
117.2(3)
113.6(4)
113.9(4)
119.5(4)
121.0(4)
122.6(4)
124.6(4)
possesses a slightly inverse boat conformation, the
characteristic feature being that the ipso-carbon atom
C1 and, to a smaller extent, the carbon atom C4 in para
position are bent toward the metal center. The conse-
quence is that the distance Rh-C1 is ca. 0.1 Å shorter
than the distances Rh-C2 and Rh-C6 (Table 1). The
bond lengths Rh-C20 and Rh-C21 as well as the bond
angles P1-Rh-C20 and P1-Rh-C21 are nearly identi-
cal to those in the nonchelate complex [(η6-C6H6)Rh-
(C8H14)(PiPr3)]CF3SO3.2a
The molecular structure of 12 is shown in Figure 2.
Due to the reduced strain in the cyclic Rh-P1-C9-C8-
C7-C1 moiety, the arene ring is nearly planar and sym-
metrically coordinated to the metal center. As a conse-
quence of the steric release, the bond angle Rh-P1-
C9 (Table 2) is enlarged by approximately 7° compared
with the angle Rh-P1-C8 in compound 11. The piano
stool configuration of the P1,Rh,C20,C21 unit in 12 is
slightly distorted, as indicated by the difference between
the angles P1-Rh-C20 and P1-Rh-C21 of ca. 8°.
1
The H and 13C NMR data of 11 and 12 are noteworthy
insofar as the signals for the proton and the carbon
nuclei of the CH unit trans to the ipso-C atom of the
ring appear at much higher chemical shifts than in the
related compounds 3 and 5.
To compare the stereochemistry of 11 and 12, the
molecular structure of both complexes has been deter-
mined by X-ray crystallography. In compound 11 (Fig-
ure 1), in which the bridge between the arene and the
PiPr2 unit is shorter than in 12, the six-membered ring

Half-Sandwich Type Rhodium(I) Complexes
Organometallics, Vol. 19, No. 23, 2000 4759
Sch em e 4
exchange of the phenyl groups of the two phosphines
in the temperature range between 295 and 363 K does
not occur. It should be mentioned that 13 and 14 can
equally be obtained by treatment of the bis(acetone)-
rhodium(I) species 10 with 2 equiv of the phosphine.
The cyclooctene ligand in the chelate complex 11 is
displaced not only by the alkyldiisopropylphosphine 8
but also by ethene, maleicacid anhydride (MAA), ethyl
propiolate, and triisopropylstibine (see Scheme 5). These
reactions are rather slow, probably due to the fact that
the metal center in the 18-electron starting material is
significantly shielded. In contrast with the related
ethene derivative 7, the 1H NMR spectrum of 15
displays at room temperature only one signal (broad-
ened singlet) for the C2H4 protons at δ 2.94, which
indicates that under these conditions the rotation of the
olefin around the Rh-C2H4 axis is quite fast. The
rotation becomes slower by decreasing the temperature,
and it is frozen at 230 K. Coalescence is observed at ca.
270 K. We assume that the origin of the low-energy
barrier for the rotation of the ethene ligand in 15
compared to 7 lies in steric effects. The relatively short
C2-bridge between the PiPr2 unit and the arene could
lead either to a tilting of the Rh-C6H5X axis or to a
slippage of the six-membered ring to a more unsym-
metrical position, and both of these possibilities would
reduce the steric hindrance between the arene and the
olefin.
The MAA complex 16 is thermally considerably more
stable than the ethene compound 15, which is probably
due to an increase in back-bonding from Rh to MAA
compared with C2H4. The electron-withdrawing char-
acter of the maleic acid anhydride ligand might also be
responsible for the difference in the chemical shift of
the phosphorus resonance which appears in the 31P
NMR spectrum of 15 at δ 93.7 and in that of 16 at δ
102.5.
In contrast with phenylacetylene, which reacts with
11 to give a mixture of products, the reaction of 11 with
ethyl propiolate leads to the formation of compound 17
in 83% yield. To the best of our knowledge, 17 is the
Treatment of 11 and 12 with 1 equiv of the alkyldi-
isopropylphosphine 8 or 9 leads to a displacement of the
cyclooctene and the formation of the substitution prod-
ucts 13 and 14, respectively (Scheme 4). Both are orange
air-sensitive solids which have been characterized by
elemental analyses, conductivity measurements, and
spectroscopic techniques. The unequal coordination of
the two phosphine ligands is best illustrated by the 31P
NMR spectra in which two resonances at δ 83.6 and 48.7
(for 13) and at δ 51.6 and 46.6 (for 14) appear. In all
cases a doublet-of-doublet splitting is observed due to
31P-31P and 31P-103Rh couplings. On the basis of
selectively 31P-decoupled 13C NMR spectra, for both
compounds the signal at low field could be assigned to
the phosphorus atom of the chelating ligand and the
other to the phosphorus atom of the monodentate
phosphine. In contrast to the related Ph2P-containing
complex [(η6-p-FC6H4CH2CH2CH2PPh2-κ-P)(p-FC6H4-
CH2CH2CH2PPh2-κ-P)Rh]BF4 reported by Mirkin,5b the
1H and 31P NMR spectra of 13 are not temperature-
dependent, and thus a fluxional behavior in solution can
be excluded. Also for compound 14, an intramolecular
Sch em e 5

4760 Organometallics, Vol. 19, No. 23, 2000
Werner et al.
Sch em e 6
first arenerhodium(I) half-sandwich type complex con-
taining an alkyne ligand. Typical spectroscopic features
of 17 are the ν(C≡C) stretch at 1811 cm-1 in the IR
spectrum, the signal of the ≡CH proton at δ 5.97
(doublet due to 1H-103Rh coupling) in the 1H NMR, and
the two resonances for the alkyne carbon atoms at δ
82.0 and 73.5 (both doublets of doublets) in the 13C NMR
spectrum. Moreover, the appearance of two signals for
the PCH and four signals for the PCHCH3 carbon nuclei
indicate a C1 symmetry of the respective cation and thus
the presence of a chiral center at rhodium. The conclu-
sion is that the rotation of the alkyne around the Rh-
alkyne bond is severely hindered, as was also found in
some cyclopentadienyl and square-planar alkynerho-
dium compounds.9 We note that all attempts to rear-
range 17 to the corresponding vinylidenerhodium iso-
mer failed.
F igu r e 3. ORTEP drawing of 19.
Ta ble 3. Selected Bon d Dista n ces a n d An gles w ith
Esd ’s for Com p ou n d 19
Bond Distances (Å)
Rh-P1
Rh-C1
Rh-C2
Rh-C3
2.251(2)
2.266(6)
2.304(7)
2.296(7)
Rh-C4
Rh-C5
Rh-C6
2.268(6)
2.304(6)
2.311(6)
The preparation of the ethene complex 19 is outlined
in Scheme 6. Analogously as for 2 and 11 as starting
materials, the reaction of 12 with C2H4 is rather slow
and in order to obtain a good yield has to be performed
Bond Angles (deg)
Rh-P1-C9
P1-C9-C8
C9-C8-C7
111.5(2)
118.0(4)
114.1(6)
C8-C7-C1
C7-C1-C2
C7-C1-C6
115.1(5)
120.2(7)
120.2(6)
1
in a closed tube at 85 °C in dichloromethane. The H
Sch em e 7
NMR spectrum of 19 displays at room temperature two
rather broad resonances at δ 3.28 and 2.45 for the
ethene protons, indicating that the rotation around the
Rh-C2H4 axis is somewhat more hindered than in the
C2-bridged counterpart 15. At 233 K, the two signals
are very sharp, as was found for 15 at 220 K. Under
the conditions, where 11 reacts with ethyl propiolate
to give 17, compound 12 is completely inert toward this
terminal alkyne.
The molecular structure of 19 is shown in Figure 3.
Although the metal-carbon distances Rh-C1 to Rh-
C6 differ in the maximum only by 0.045 Å (see Table
3), the arene ring possesses a slightly inverse boat
conformation, which, however, is less pronounced than
in 11. The Rh-P bond lengths in 19 [2.251(2) Å] and
12 [2.265(1) Å] are almost identical, and also the bond
angles of the Rh,P1,C9,C8,C7 unit in both C3-bridged
compounds are nearly the same. The C2H4 ligand in 19
is disordered, and therefore no exact distances between
the metal and the ethene carbon atoms could be
determined.
Th e Mor e Bu lk y P h osp h in es tBu 2P (CH2)n XC6H5
a n d Th eir Rh od iu m (I) Com p lexes. The methodology
for the preparation of the di-tert-butylphosphine deriva-
tives 20, 21 and the corresponding methylphosphonium
salts 20a , 21a (Scheme 7) followed the routes already
developed for the iPr2P counterparts 8, 9 and 8a , 9a ,
respectively. We note that the temperature for the
reaction of HPtBu2 with PhOCH2CH2Br should not
exceed 80 °C since otherwise partial decomposition of
the functionalized phenyl ether occurs. Similarly to 8
and 9, also the sterically more demanding phosphines
20 and 21 are colorless oily liquids, which were char-
acterized by mass spectra and common spectroscopic
techniques. For the phosphonium salts 20a and 21a
correct elemental analyses were obtained.
The reactions of 10 with either phosphine 20 or 21 in
acetone led to the half-sandwich type complexes 22a and
23 in 93% and 90% isolated yield (Scheme 8). Both
compounds are yellow, slightly air-sensitive solids which
in nitromethane reveal the conductivity of 1:1 electro-
lytes. The anticipated lability of the rhodium-olefin
bond in 22a is illustrated by the substitution reaction
with ethyl propiolate, which gives almost quantitatively
the alkyne complex 24. While most of the relevant
spectroscopic data of 24 are quite similar to those of 17,
the stability of the tBu2P-containing species in solution
and in the solid state is enhanced compared with the
iPr2P analogue, probably due to a better shielding of
the metal center in 24 by the more bulky tert-butyl
groups. Attempts to rearrange the alkyne compound 24
(8) Windmu¨ller, B.; Wolf, J .; Werner, H. J . Organomet. Chem. 1995,
502, 147-161.
(9) (a) Werner, H.; Wolf, J .; Schubert, U.; Ackermann, K. J .
Organomet. Chem. 1986, 317, 327-356. (b) Werner, H.; Brekau, U. Z.
Naturforsch. Teil B 1989, 44, 1438-1446.

Half-Sandwich Type Rhodium(I) Complexes
Organometallics, Vol. 19, No. 23, 2000 4761
prepared as described in the literature. C6H5(CH2)nBr (n ) 2,
3) and C6H5O(CH2)2Br were commercial products from Aldrich.
IR spectra were recorded on a Bruker IFS 25 FT and NMR
spectra (at room temperature or at the temperature mentioned
in the appropriate procedure) on Bruker AC 200 and Bruker
AMX 400 instruments. Abbreviations used: s, singlet; d,
doublet; t, triplet; q, quartet; sept, septet; m, multiplet; br,
broadened signal. The conductivity Λ was measured in ni-
tromethane with a Schott Konduktometer CG 851, and melting
and decomposition points were determined by DTA. Mass
spectra were recorded on a Finnigan 90 MAT instrument.
Sch em e 8
P r ep a r a tion of [(η6-C6H6)Rh (C8H14)(P iP r 3)]P F 6 (2). A
solution of 1 (651 mg, 1.03 mmol) in 3 mL of CH2Cl2 was
treated with 3 mL of benzene and stirred for 5 min at room
temperature. After the solvent was evaporated in vacuo, the
residue was dissolved in 1 mL of CH2Cl2 and 7 mL of ether
was added to the solution. A yellow solid precipitated, which
was separated from the mother liquor, washed with 10 mL of
ether, and dried. The solid was recrystallized twice from CH2-
Cl2/ether (1:7), then washed with 7 mL of ether and 7 mL of
pentane, and dried: yield 546 mg (89%); mp 89 °C dec. Λ )
Sch em e 9
1
73 cm2 Ω-1 mol-1. H NMR (400 MHz, CD2Cl2): δ 6.67 (s, 6H,
C6H6), 3.05 (m, 2H, dCH of C8H14), 2.38 (m, 2H, CH2 of C8H14),
1.88 (m, 3H, PCHCH3), 1.70, 1.45 (both m, 10H, CH2 of C8H14),
1.26 [dd, J (PH) ) 14.1 Hz, J (HH) ) 7.3 Hz, 18H, PCHCH3].
13C NMR (100.6 MHz, CD2Cl2): δ 105.1 (s, C6H6), 68.0 [d,
J (RhC) ) 13.4 Hz, dCH of C8H14], 34.1, 32.3, 26.3 (all s, CH2
of C8H14), 25.5 [d, J (PC) ) 23.8 Hz, PCHCH3], 19.8 (s,
PCHCH3). 31P NMR (162.0 MHz, CD2Cl2): δ 63.4 [d, J (RhP)
) 183.1 Hz, PiPr3], -144.3 [sept, J (FP) ) 710.6 Hz, PF6-].
Anal. Calcd for C23H41F6P2Rh (596.4): C, 46.32; H, 6.93.
Found: C, 45.95; H, 6.70.
either thermally or photochemically to the vinylidene
isomer failed. The reaction of 23 with ethyl propiolate
proceeds much faster than that of 22a with the same
substrate but yields even at low temperature a mixture
of unidentified products.
The synthesis of the cationic chelate complex 22b with
triflate as the counterion, shown in Scheme 9, was an
unexpected result. Since we knew that the dimer 2510
reacts with 2 equiv of triisopropylphosphine to give the
mononuclear species [Rh{κ2-O2S(O)CF3}(C8H14)(PiPr3)],
we anticipated that a related compound would be
formed upon treatment of 25 with the alkyldi-tert-
butylphosphine 20. Instead the ionic product 22b was
isolated in 94% yield. While 22b is thermally somewhat
less stable than the PF6 salt 22a , the spectroscopic data
as well as the chemical properties of both compounds
are quite similar.
Current work in our laboratory is particullarly aimed
to explore the potential of the chelating rhodium(I)
complexes [{η6-RC6H4X(CH2)nPR′2-κ-P}Rh(L)]+ for cata-
lytic studies. Introducing electron-withdrawing sub-
stituents R at the ring should weaken the arene-
rhodium bond and thus open the possibility for the
coordination and subsequent coupling of reactive sub-
strates. Finally it should be mentioned that all attempts
to displace the olefin ligand in 11, 12, 15, or 19 by a
carbene C(R)Ph (R ) H, Ph) using Ph(R)CN2 as carbene
source failed.
P r ep a r a tion of [(η6-C6H5CF 3)Rh (C8H14)(P iP r 3)]P F 6 (3).
A sample of 1 (103 mg, 0.16 mmol) was treated at room
temperature with 2 mL of C6H5CF3. This led to the formation
of an orange solution, from which after a few seconds a yellow
solid precipitated. The precipitation was completed by addition
of 4 mL of pentane. The mother liquor was decanted, and the
yellow solid was washed three times with 5 mL of pentane
1
and dried: yield 106 mg (98%); mp 60 °C dec. H NMR (400
MHz, CD2Cl2): δ 7.77 (m, 1H, para-H of C6H5CF3), 6.60 (m,
2H, ortho-H of C6H5CF3), 6.50 (m, 2H, meta-H of C6H5CF3),
3.26 (m, 2H, dCH of C8H14), 2.40 (m, 2H, CH2 of C8H14), 1.92
(m, 3H, PCHCH3), 1.68, 1.43 (both m, 10H, CH2 of C8H14), 1.27
[dd, J (PH) ) 14.1 Hz, J (HH) ) 7.3 Hz, 18H, PCHCH3]. 13C
NMR (100.6 MHz, CD2Cl2): δ 122.8 [q, J (FC) ) 271.8 Hz, CF3],
115.1 [q, J (FC) ) 38.2 Hz, CCF3], 107.4, 103.9, 100.9 (all s,
C6H5), 71.2 [d, J (RhC) ) 14.3 Hz, dCH of C8H14], 33.9, 32.2,
26.2 (all s, CH2 of C8H14), 25.9 [d, J (PC) ) 24.8 Hz, PCHCH3],
19.7 (s, PCHCH3). 19F NMR (376.6 MHz, CD2Cl2): δ -60.2 (s,
CF3), -73.1 [d, J (PF) ) 710.6 Hz, PF6-]. 31P NMR (162.0 MHz,
CD2Cl2): δ 63.8 [d, J (RhP) ) 180.9 Hz, PiPr3], -144.3 [sept,
J (FP) ) 710.6 Hz, PF6-]. Anal. Calcd for C24H40F9P2Rh
(664.4): C, 43.39; H, 6.07. Found: C, 42.40; H, 6.03.
P r ep a r a tion of [{η6-1.3.5-C6H3(CH3)3}Rh (C8H14)(P iP r 3)]-
P F 6 (4). A suspension of 1 (135 mg, 0.21 mmol) in 5 mL of
mesitylene was stirred for 1 h at room temperature. After
addition of 5 mL of pentane, a yellow solid precipitated. The
mother liquor was decanted, and the remaining solid was
washed three times with 7 mL of pentane and dried. Owing
to the NMR spectra, the solid contained ca. 10% of a PiPr3-
containing impurity, which could not be removed by fractional
crystallization. NMR data for 4: 1H NMR (400 MHz, CD2Cl2):
δ 6.16 (s, 3H, C6H3), 2.79 (m, 2H, dCH of C8H14), 2.34 (s, 9H,
CH3 of mesitylene), 2.17 (m, 2H, CH2 of C8H14), 1.82 (m, 3H,
PCHCH3), 1.82, 1.43 (both m, 10H, CH2 of C8H14), 1.24 [dd,
J (PH) ) 13.8 Hz, J (HH) ) 7.0 Hz, 18H, PCHCH3]. 13C NMR
Exp er im en ta l Section
All experiments were carried out under an atmosphere of
argon by Schlenk techniques. Solvents were dried by known
procedures and distilled before used. The starting materials
12
1,4 10,8 25,10 HPR2 (R ) iPr, tBu),11 and SbiPr3
were
(10) Werner, H.; Bosch, M.; Schneider, M. E.; Hahn, C.; Kukla, F.;
Manger, M.; Windmu¨ller, B.; Weberndo¨rfer, B.; Laubender, M. J .
Chem. Soc., Dalton Trans. 1998, 3549-3558.
(11) Timmer, K.; Thewissen, D. H. M. W.; Marsman, J . W. Recl.
Trav. Chim. Pays-Bas 1988, 107, 249-255.
(12) SbiPr3 was prepared analogously as described for the n-propyl
derivative: Samaan, S. Methoden der Organischen Chemie (Houben-
Weyl) 4th ed.; 1978; Vol. XIII/8, pp 445-446.

4762 Organometallics, Vol. 19, No. 23, 2000
Werner et al.
(100.6 MHz, CD2Cl2): δ 124.2 (s, CCH3 of mesitylene), 104.4
(s, CH of mesitylene), 60.3 [d, J (RhC) ) 15.3 Hz, dCH of
C8H14], 31.8, 31.2, 26.3 (all s, CH2 of C8H14), 23.7 [d, J (PC) )
22.9 Hz, PCHCH3], 20.8 (s, CH3 of mesitylene), 19.9 (s,
PCHCH3). 31P NMR (162.0 MHz, CD2Cl2): δ 59.0 [d, J (RhP)
) 180.9 Hz, PiPr3], -144.4 [sept, J (FP) ) 710.6 Hz, PF6-].
P r ep a r a t ion of [(η6-C6H 5OCH 3)R h (C8H 14)(P iP r 3)]P F 6
(5). This compound was prepared as described for 3, using 1
(111 mg, 0.17 mmol) and 3 mL of C6H5OCH3 as starting
materials: yellow solid; yield 103 mg (97%); mp 97 °C dec. Λ
times with 60 mL of ether, dried, and dissolved in 25 mL of
degassed water. The aqueous solution was layered with 75 mL
of ether and then treated, under stirring, dropwise with
ammonia (concentrated in water) until the aqueous phase
became basic (pH ∼9). After the ethereal phase was separated,
it was washed twice with 25 mL of water, then dried with Na2-
SO4, and finally evaporated to dryness in vacuo. The oily
residue was distilled in vacuo to give a colorless viscous
1
liquid: yield 17.3 g (89%); bp 68-72 °C (0.05 mbar). H NMR
(400 MHz, C6D6): δ 7.12 (m, 5H, C6H5), 2.76 (m, 2H, PhCH2),
1.61-1.50 (m, 4H, PCH2 and PCHCH3), 1.02 [dd, J (PH) ) 13.5
Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3], 0.97 [dd, J (PH) ) 10.9
Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3]. 13C NMR (100.6 MHz,
C6D6): δ 143.8 [d, J (PC) ) 12.4 Hz, ipso-C of C6H5], 128.7,
128.5, 126.1 (all s, C6H5), 35.2 [d, J (PC) ) 21.9 Hz, PhCH2],
24.8 [d, J (PC) ) 21.0 Hz, PCH2], 23.7 [d, J (PC) ) 14.3 Hz,
PCHCH3], 20.3 [d, J (PC) ) 16.2 Hz, PCHCH3], 19.0 [d, J (PC)
) 9.5 Hz, PCHCH3]. 31P NMR (162.0 MHz, C6D6): δ 3.8 (s).
MS (70 eV) m/z 222 [34.6, M+], 221 [100, M+ - H], 131 [32.9,
CH2PiPr2+], 118 [32.5, HPiPr2+], 105 [55.6, C6H5CH2CH2+].
P r ep a r a tion of [C6H5CH2CH2P iP r 2Me]I (8a ). A solution
of 8 (1.33 g, 5.98 mmol) in 25 mL of hexane was treated with
CH3I (377 µL, 6.00 mmol) and stirred for 3 h at room
temperature. A colorless solid precipitated, which was sepa-
rated from the mother liquor, washed three times with 10 mL
of ether and twice with 10 mL of pentane, and dried in vacuo:
1
) 79 cm2 Ω-1 mol-1. H NMR (400 MHz, CD2Cl2): δ 6.65 (m,
1H, para-H of C6H5OCH3), 6.48 (m, 2H, meta-H of C6H5OCH3),
6.16 (m, 2H, ortho-H of C6H5OCH3), 3.97 (s, 3H, OCH3), 3.03
(m, 2H, dCH of C8H14), 2.18 (m, 2H, CH2 of C8H14), 1.91 (m,
3H, PCHCH3), 1.57 (m, 10H, CH2 of C8H14), 1.26 [dd, J (PH) )
14.1 Hz, J (HH) ) 7.0 Hz, 18H, PCHCH3]. 13C NMR (100.6
MHz, CD2Cl2): δ 150.6 (s, ipso-C of C6H5OCH3), 104.4 [d,
J (RhC) ) 2.9 Hz, C6H5], 98.4 [d, J (RhC) ) 1.9 Hz, C6H5], 90.0
(m, C6H5), 66.1 [d, J (RhC) ) 14.3 Hz, dCH of C8H14], 56.9 (s,
OCH3), 32.1, 32.0, 26.3 (all s, CH2 of C8H14), 25.3 [d, J (PC) )
23.8 Hz, PCHCH3], 19.8 (s, PCHCH3). 31P NMR (162.0 MHz,
CD2Cl2): δ 63.0 [d, J (RhP) ) 183.1 Hz, PiPr3], -144.4 [sept,
J (FP) ) 710.6 Hz, PF6-]. Anal. Calcd for C24H43F6OP2Rh
(626.4): C, 46.02; H, 6.92. Found: C, 45.76; H, 6.80.
P r epar ation of [{η6-1.3.5-C6H3(OCH3)3}Rh (C8H14)(P iP r 3)]-
P F 6 (6). A suspension of 1 (119 mg, 0.19 mmol) in 5 mL of
ether was treated with 1.3.5-C6H3(OCH3)3 (96 mg, 0.57 mmol)
and stirred for 30 min at room temperature. After addition of
5 mL of ether, a yellow solid precipitated, which was separated
from the mother liquor, washed twice with 5 mL of ether and
5 mL of pentane, and dried: yield 122 mg (93%); mp 72 °C
1
yield 1.97 g (90%); mp 154 °C. H NMR (400 MHz, CD3NO2):
δ 7.30 (m, 5H, C6H5), 3.03 (m, 2H, PhCH2), 2.76 (m, 2H,
PCHCH3), 2.58 (m, 2H, PCH2), 1.87 [d, J (PH) ) 12.6 Hz, 3H,
PCH3], 1.41 [dd, J (PH) ) 17.0 Hz, J (HH) ) 7.3 Hz, 6H,
PCHCH3], 1.40 [dd, J (PH) ) 17.0 Hz, J (HH) ) 7.0 Hz, 6H,
PCHCH3]. 13C NMR (100.6 MHz, CD3NO2): δ 140.9 [d, J (PC)
) 14.2 Hz, ipso-C of C6H5], 130.2, 129.5, 128.4 (all s, C6H5),
28.8 [d, J (PC) ) 4.1 Hz, PhCH2], 22.5 [d, J (PC) ) 46.8 Hz,
PCHCH3], 19.9 [d, J (PC) ) 43.8 Hz, PCH2], 16.3, 16.2 [both d,
J (PC) ) 3.1 Hz, PCHCH3], 0.8 [d, J (PC) ) 50.9 Hz, PCH3].
31P NMR (162.0 MHz, CD3NO2): δ 42.0 (s). Anal. Calcd for
dec. Λ ) 79 cm2 Ω-1 mol-1 1H NMR (400 MHz, CD2Cl2): δ
.
5.76 (s, 3H, C6H3), 3.95 (s, 9H, OCH3), 2.87 (m, 2H, dCH of
C8H14), 1.95 (m, 2H, CH2 of C8H14), 1.88 (m, 3H, PCHCH3),
1.72 (m, 2H, CH2 of C8H14), 1.43 (m, 8H, CH2 of C8H14), 1.27
[dd, J (PH) ) 13.5 Hz, J (HH) ) 7.0 Hz, 18H, PCHCH3]. 13C
NMR (100.6 MHz, CD2Cl2): δ 149.1 [d, J (RhC) ) 1.9 Hz,
COCH3 of C6H3(OCH3)3], 75.4 [s, CH of C6H3(OCH3)3], 60.9 [d,
J (RhC) ) 17.2 Hz, dCH of C8H14], 57.5 (s, OCH3), 31.5, 29.7,
26.4 (all s, CH2 of C8H14), 22.8 [d, J (PC) ) 22.9 Hz, PCHCH3],
19.9 (s, PCHCH3). 31P NMR (162.0 MHz, CD2Cl2): δ 56.6 [d,
J (RhP) ) 180.9 Hz, PiPr3], -144.4 [sept, J (FP) ) 710.6 Hz,
PF6-]. Anal. Calcd for C26H47F6O3P2Rh (686.5): C, 45.49; H,
6.90. Found: C, 45.44; H, 6.63.
P r ep a r a tion of [(η6-C6H6)Rh (C2H4)(P iP r 3)]P F 6 (7). A
solution of 2 (103 mg, 0.17 mmol) in 2 mL of CH2Cl2 was
degassed in vacuo, cooled to -20 °C, and then brought under
an atmosphere of ethene. After warming to room temperature,
the solution was layered with 8 mL of ether, which led to the
precipitation of a yellow solid. The mother liquor was sepa-
rated, and the residue was washed with 5 mL of ether and
dried. This procedure (dissolvation in CH2Cl2, treatment with
ethene, precipitation with ether) was repeated three times. The
finally obtained yellow solid was washed twice with 5 mL of
ether and twice with 5 mL of pentane and then dried in
vacuo: yield 79 mg (89%); mp 112 °C dec. Λ ) 73 cm2 Ω-1
mol-1. 1H NMR (400 MHz, CD2Cl2): δ 6.73 (s, 6H, C6H6), 3.33,
2.27 (both m, 2H each, C2H4), 1.83 (m, 3H, PCHCH3), 1.22 [dd,
J (PH) ) 14.1 Hz, J (HH) ) 7.0 Hz, 18H, PCHCH3]. 13C NMR
(100.6 MHz, CD2Cl2): δ 104.4 (s, C6H6), 40.8 [d, J (RhC) ) 14.3
Hz, C2H4], 25.3 [d, J (PC) ) 23.8 Hz, PCHCH3], 19.6 (s,
PCHCH3). 31P NMR (162.0 MHz, CD2Cl2): δ 65.9 [d, J (RhP)
) 176.6 Hz, PiPr3], -144.3 [sept, J (FP) ) 710.6 Hz, PF6-].
Anal. Calcd for C17H31F6P2Rh (514.3): C, 39.70; H, 6.08.
Found: C, 39.71; H, 6.11.
C
15H26IP (364.3): C, 49.46; H, 7.19. Found: C, 49.26; H, 6.79.
P r ep a r a tion of C6H5CH2CH2CH2P iP r 2 (9). The prepara-
tion was analogous with that described for 8, from HPiPr2 (5.82
g, 49.3 mmol) and 3-phenylpropylbromide (6.74 mL, 44.4
1
mmol). Colorless oil: yield 8.20 g (78%). H NMR (400 MHz,
C6D6): δ 7.22 (m, 5H, C6H5), 2.71 (m, 2H, PhCH2), 1.90 (m,
2H, PCH2CH2), 1.64 (m, 2H, PCHCH3), 1.37 (m, 2H, PCH2),
1.11 [dd, J (PH) ) 13.5 Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3],
1.06 [dd, J (PH) ) 10.9 Hz, J (HH) ) 6.9 Hz, 6H, PCHCH3].
13C NMR (100.6 MHz, C6D6): δ 142.4 (s, ipso-C of C6H5), 128.8,
128.6, 126.1 (all s, C6H5), 37.8 [d, J (PC) ) 11.5 Hz, PhCH2],
30.4 [d, J (PC) ) 20.0 Hz, PCH2 or PCH2CH2], 23.7 [d, J (PC)
) 14.3 Hz, PCHCH3], 21.7 [d, J (PC) ) 19.1 Hz, PCH2 or
PCH2CH2], 20.3 [d, J (PC) ) 16.2 Hz, PCHCH3], 19.0 [d, J (PC)
) 10.5 Hz, PCHCH3]. 31P NMR (162.0 MHz, C6D6): δ 2.1 (s).
MS (70 eV) m/z 236 (M+).
P r ep a r a tion of [C6H5CH2CH2CH2P iP r 2Me]I (9a ). The
preparation was analogous with that described for 8a , from 9
(1.35 g, 5.72 mmol) and CH3I (365 µL, 5.80 mmol). Colorless
solid: yield 2.01 g (93%); mp 109 °C. 1H NMR (400 MHz, CD3-
NO2): δ 7.25 (m, 5H, C6H5), 2.79 (m, 2H, PhCH2), 2.65 (m,
2H, PCHCH3), 2.27 (m, 2H, PCH2), 1.97 (m, 2H, PCH2CH2),
1.77 [d, J (PH) ) 12.6 Hz, 3H, PCH3], 1.32 [dd, J (PH) ) 17.0
Hz, J (HH) ) 7.3 Hz, 6H, PCHCH3], 1.31 [dd, J (PH) ) 17.0
Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3]. 13C NMR (100.6 MHz, CD3-
NO2): δ 142.0 (s, ipso-C of C6H5), 129.9, 129.8, 127.7 (all s,
C6H5), 37.4 [d, J (PC) ) 15.3 Hz, PhCH2], 25.0 [d, J (PC) ) 5.0
Hz, PCH2CH2], 22.3 [d, J (PC) ) 46.8 Hz, PCHCH3], 17.6 [d,
J (PC) ) 46.8 Hz, PCH2], 16.2, 16.1 [both d, J (PC) ) 3.0 Hz,
PCHCH3], 0.5 [d, J (PC) ) 50.9 Hz, PCH3]. 31P NMR (162.0
MHz, CD3NO2): δ 42.3 (s). Anal. Calcd for C16H28IP (378.3):
C, 50.80; H, 7.46. Found: C, 50.51; H, 7.20.
P r ep a r a tion of C6H5CH2CH2P iP r 2 (8). A mixture of
HPiPr2 (12.3 g, 0.10 mol) and 2-phenylethylbromide (12.0 mL,
0.09 mol) was heated under stirring for 24 h at 90 °C. After it
was cooled to room temperature, a colorless solid was obtained.
This solid was recrystallized from refluxing acetone. The
purified intermediate [iPr2PHCH2CH2Ph]Br was washed three
P r ep a r a tion of [(η6-C6H5CH2CH2P iP r 2-K-P )Rh (C8H14)]-
P F 6 (11). A solution of 10 (194 mg, 0.33 mmol) in 3 mL of

Half-Sandwich Type Rhodium(I) Complexes
Organometallics, Vol. 19, No. 23, 2000 4763
acetone, which was cooled to -20 °C, was treated dropwise
over a period of 15 min with an ice-cooled solution of 8 (74
mg, 0.33 mmol) in 20 mL of acetone. After the reaction mixture
was warmed to room temperature, the solvent was removed
in vacuo. The residue was dissolved in 1 mL of CH2Cl2, and
after the solution was layered with 7 mL of ether, a yellow
solid precipitated. The mother liquor was decanted, the solid
was washed three times with 6 mL of ether and twice with 6
mL of pentane, and dried in vacuo: yield 180 mg (94%); mp
7.29 (m, 2H, C6H5), 7.20 (m, 3H, C6H5), 7.02 (m, 4H, C6H5),
5.87 (m, 1H, para-H of η6-C6H5), 2.88 (m, 2H, PhCH2), 2.64
(m, 2H, PCH2), 2.40 (m, 2H, PhCH2), 2.17-1.95 (m, 6H,
PCHCH3 and PCH2), 1.31 [dd, J (PH) ) 15.8 Hz, J (HH) ) 7.0
Hz, 6H, PCHCH3], 1.28 [dd, J (PH) ) 14.1 Hz, J (HH) ) 6.9
Hz, 6H, PCHCH3], 1.25 [dd, J (PH) ) 15.9 Hz, J (HH) ) 6.9
Hz, 6H, PCHCH3], 1.21 [dd, J (PH) ) 14.7 Hz, J (HH) ) 6.8
Hz, 6H, PCHCH3]. 13C NMR (100.6 MHz, CD2Cl2): δ 141.5 [d,
J (PBC) ) 9.5 Hz, ipso-C of C6H5], 129.1, 127.7, 126.8 (all s,
C6H5), 113.2 [m; d in 13C{31P}, J (RhC) ) 3.8 Hz; dd in 13C-
{31PA}, J (PBC) ) 7.6 Hz, J (RhC) ) 3.8 Hz, ipso-C of η6-C6H5],
103.4, 103.2 [both br s; both d in 13C{31P}, J (RhC) ) 1.9 Hz,
ortho/meta-C of η6-C6H5], 91.1 [d, J (PAC) ) 8.6 Hz, para-C of
η6-C6H5], 40.8 [dd, J (PAC) ) 27.7 Hz, J (PBC) ) 2.9 Hz, PA-
CH2], 31.3 [d, J (PBC) ) 6.7 Hz, PhCH2], 30.6 (br s, η6-
C6H5CH2), 30.0 [m; d in 13C{31P}, J (RhC) ) 2.9 Hz, PBCH2],
28.1 [d, J (PBC) ) 24.8 Hz, PBCHCH3], 26.5 [dd, J (PAC) ) 22.9
Hz, J (RhC) ) 2.9 Hz, PACHCH3], 20.1 [d, J (PAC) ) 3.8 Hz,
PACHCH3], 19.8, 18.2 (both s, PCHCH3), 19.2 [d, J (PBC) ) 2.9
Hz, PBCHCH3]. 31P NMR (162.0 MHz, CD2Cl2, 295 K): δ 83.6
[dd, J (RhPA) ) 202.7 Hz, J (PBPA) ) 30.5 Hz, iPr2PA], 48.7 [dd,
J (RhPB) ) 202.7 Hz, J (PAPB) ) 30.5 Hz, iPr2PB], -144.4 [sept,
J (FP) ) 710.6 Hz, PF6-]. 31P NMR (162.0 MHz, CD3NO2, 368
K): δ 84.4 [dd, J (RhPA) ) 204.9 Hz, J (PBPA) ) 30.5 Hz, iPr2PA],
49.6 [dd, J (RhPB) ) 204.9 Hz, J (PAPB) ) 30.5 Hz, iPr2PB],
1
182 °C dec. Λ ) 75 cm2 Ω-1 mol-1. H NMR (400 MHz, CD2-
Cl2): δ 6.98, 6.89 (both m, 2H each, C6H5), 5.87 (m, 1H, C6H5),
3.43 (m, 2H, dCH of C8H14), 2.62-2.49 (br m, 4H, PhCH2 and
PCH2), 2.32 (m, 2H, CH2 of C8H14), 2.00 (m, 2H, PCHCH3),
1.85-1.29 (m, 10H, CH2 of C8H14), 1.23 [dd, J (PH) ) 15.6 Hz,
J (HH) ) 7.0 Hz, 6H, PCHCH3], 1.20 [dd, J (PH) ) 16.4 Hz,
J (HH) ) 7.0 Hz, 6H, PCHCH3]. 13C NMR (100.6 MHz, CD2-
Cl2): δ 119.3 [dd, J (PC) ) 5.4 Hz, J (RhC) ) 3.8 Hz; d in 13C-
{31P}, J (RhC) ) 3.8 Hz, ipso-C of C6H5], 112.0, 102.0 (both s,
C6H5), 97.7 [d, J (PC) ) 9.2 Hz, para-C of C6H5], 68.0 [d, J (RhC)
) 13.3 Hz, dCH of C8H14], 38.6 [d, J (PC) ) 28.5 Hz, PCH2],
34.3, 32.3, 31.0, 26.3 (all s, CH2 of C8H14 and PhCH2], 25.2
[dd, J (PC) ) 25.4 Hz, J (RhC) ) 2.0 Hz, PCHCH3], 18.9, 17.8
(both s, PCHCH3). 31P NMR (162.0 MHz, CD2Cl2): δ 92.4 [d,
J (RhP) ) 185.3 Hz, iPr2P], -144.3 [sept, J (FP) ) 710.6 Hz,
PF6-]. MS (FAB, 2-nitrophenyloctyl ether): m/z 435 (M+). Anal.
Calcd for C22H37F6P2Rh (580.4): C, 45.53; H, 6.43; Rh, 17.73.
Found: C, 45.18; H, 6.25; Rh, 17.54.
-144.3 [sept, J (FP) ) 706.3 Hz, PF6-]. For assignment: PA
)
31P nuclei of η6-C6H5CH2CH2PiPr2; PB 31P nuclei of C6H5-
)
P r ep a r a tion of [(η6-C6H5CH2CH2CH2P iP r 2-K-P )Rh (C8-
14)]P F 6 (12). The preparation was analogous with that
CH2CH2PiPr2-κ-P. MS (FAB, 2-nitrophenyloctyl ether): m/z
547 (M+). Anal. Calcd for C28H46F6P3Rh (692.5): C, 48.57; H,
6.70. Found: C, 48.60; H, 6.55.
H
described for 11, from 10 (340 mg, 0.59 mmol) and 9 (138 mg,
P r ep a r a tion of [(η6-C6H5CH2CH2CH2P iP r 2-K-P )(C6H5-
CH2CH2CH2P iP r 2-K-P )Rh ]P F 6 (14). The preparation was
analogous with that described for 13, from 12 (111 mg, 0.19
mmol) and 9 (47 mg, 0.20 mmol) in 2 mL of CH2Cl2. Orange
solid: yield 126 mg (92%). Alternatively, compound 14 was
also prepared from 10 (103 mg, 0.18 mmol) and 9 (90 mg, 0.38
mmol) in 2 mL of CH2Cl2: yield 115 mg (89%); mp 134 °C dec.
0.59 mmol). Yellow solid: yield 307 mg (88%); mp 187 °C dec.
1
Λ ) 80 cm2 Ω-1 mol-1. H NMR (400 MHz, CD2Cl2): δ 6.85,
6.77 (both m, 2H each, C6H5), 5.84 (m, 1H, C6H5), 3.18 (m, 2H,
dCH of C8H14), 2.45 (m, 2H, PhCH2), 2.33 (m, 2H, CH2 of
C8H14), 1.96-1.83 (br m, 4H, PCH2 and PCHCH3), 1.72-1.61
(m, 4H, CH2 of C8H14), 1.49 (m, 2H, CH2 of C8H14), 1.42-1.30
(m, 6H, CH2 of C8H14 and PCH2CH2), 1.20 [dd, J (PH) ) 15.8
Hz, J (HH) ) 7.2 Hz, 6H, PCHCH3], 1.18 [dd, J (PH) ) 14.4
Hz, J (HH) ) 6.8 Hz, 6H, PCHCH3]. 13C NMR (100.6 MHz, CD2-
Cl2): δ 111.6 [br s; d in 13C{31P}, J (RhC) ) 1.9 Hz, C6H5], 110.5
[d, J (RhC) ) 2.9 Hz, ipso-C of C6H5), 103.4 [d, J (RhC) ) 1.9
Hz, C6H5], 98.7 [dd, J (PC) ) 8.6 Hz, J (RhC) ) 1.9 Hz, para-C
of C6H5], 67.1 [d, J (RhC) ) 13.4 Hz, dCH of C8H14], 34.1, 32.3,
26.2 (all s, CH2 of C8H14), 32.1, 25.6 (both s, PhCH2 and
PCH2CH2), 25.1 [d, J (PC) ) 27.7 Hz, PCHCH3], 20.2 (s,
PCHCH3), 17.8 [d, J (PC) ) 1.9 Hz, PCHCH3], 15.8 [d, J (PC)
) 27.7 Hz, PCH2]. 31P NMR (162.0 MHz, CD2Cl2): δ 54.8 [d,
J (RhP) ) 178.7 Hz, iPr2P], -144.3 [sept, J (FP) ) 710.6 Hz,
PF6-]. Anal. Calcd for C23H39F6P2Rh (594.4): C, 46.48; H, 6.61;
Rh, 17.31. Found: C, 46.22; H, 6.67; Rh, 17.06.
1
Λ ) 76 cm2 Ω-1 mol-1. H NMR (400 MHz, CD2Cl2, 295 K): δ
7.29 (m, 2H, C6H5), 7.22 (m, 1H, C6H5), 7.12, 6.80, 6.71 (all m,
2H each, C6H5), 5.58 (m, 1H, para-H of η6-C6H5), 2.65, 2.31
(both m, 2H each, PhCH2), 2.10-1.83 (m, 4H, PCHCH3 and
PCH2), 1.72 (m, 2H, PCH2CH2), 1.54-1.38 (m, 4H, PCHCH3
and PCH2), 1.25 (m, 2H, PCH2CH2), 1.17 [dd, J (PH) ) 16.3
Hz, J (HH) ) 7.2 Hz, 6H, PCHCH3], 1.13 [dd, J (PH) ) 17.3
Hz, J (HH) ) 7.2 Hz, 6H, PCHCH3], 1.05 [dd, J (PH) ) 13.0
Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3], 1.04 [dd, J (PH) ) 14.1
1
Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3]. H NMR (400 MHz, CD3-
NO2, 363 K): δ 7.31 (m, 2H, C6H5), 7.22 (m, 3H, C6H5), 6.92,
6.85 (both m, 2H each, C6H5), 5.78 (m, 1H, para-H of η6-C6H5),
2.71, 2.37 (both m, 2H each, PhCH2), 2.10 (m, 2H, PACHCH3),
1.97 (m, 2H, PACH2), 1.87-1.69 (m, 4H, PBCH2CH2 and
PBCHCH3), 1.62 (m, 2H, PBCH2), 1.37 (m, 2H, PACH2CH2), 1.25
[dd, J (PH) ) 15.9 Hz, J (HH) ) 7.2 Hz, 6H, PCHCH3], 1.23
[dd, J (PH) ) 17.0 Hz, J (HH) ) 7.2 Hz, 6H, PCHCH3], 1.16
[dd, J (PH) ) 12.8 Hz, J (HH) ) 6.9 Hz, 6H, PCHCH3], 1.15
[dd, J (PH) ) 13.8 Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3]. 13C NMR
(100.6 MHz, CD2Cl2): δ 140.6 (s, ipso-C of C6H5), 129.0, 128.7,
126.8 (all s, C6H5), 104.7 [br s; d in 13C{31P}, J (RhC) ) 1.9 Hz,
ortho/meta-C of η6-C6H5], 104.6 (m, ipso-C of η6-C6H5), 103.3
[br s; d in 13C{31P}, J (RhC) ) 1.9 Hz, ortho/meta-C of η6-C6H5],
90.5 [d, J (PAC) ) 12.6 Hz, para-C of η6-C6H5], 37.1 [d, J (PBC)
) 9.5 Hz, PhCH2], 33.1 (s, PhCH2), 28.8 [d, J (PBC) ) 25.8 Hz,
PBCHCH3], 27.9 [d, J (PAC) ) 24.8 Hz, PACHCH3], 26.2 [m; d
in 13C{31P}, J (RhC) ) 1.9 Hz, PBCH2CH2], 24.8 [m; d in 13C-
{31P}, J (RhC) ) 2.9 Hz, PBCH2], 24.3 (s, PACH2CH2), 23.0 [d,
J (PAC) ) 4.8 Hz, PACHCH3], 19.1, 19.0 (both s, PBCHCH3),
18.2 [d, J (PAC) ) 5.7 Hz, PACHCH3], 14.0 [d, J (PAC) ) 24.8
Hz, PACH2]. 31P NMR (162.0 MHz, CD2Cl2, 295 K): δ 51.6 [dd,
J (RhPA) ) 200.5 Hz, J (PBPA) ) 32.7 Hz, iPr2PA], 46.6 [dd,
J (RhPB) ) 207.1 Hz, J (PAPB) ) 32.7 Hz, iPr2PB], -144.4 [sept,
J (FP) ) 710.6 Hz, PF6-]. 31P NMR (162.0 MHz, CD3NO2, 363
P r epar ation of [(η6-C6H5CH2CH2P iP r 2-K-P )(C6H5CH2CH2-
P iP r 2-K-P )Rh ]P F 6 (13). A solution of 11 (172 mg, 0.30 mmol)
in 2 mL of CH2Cl2 was treated with 8 (77.8 mg, 0.35 mmol)
and stirred for 6 h at room temperature. A change of color
from yellow to orange-red occurred. After removal of the
solvent in vacuo, the residue was dissolved in 2 mL of acetone,
and the solution was treated under stirring with 8 mL of ether.
An orange solid precipitated and was washed twice with 5 mL
of ether and twice with 5 mL of pentane and dried: yield 189
mg (91%). Alternatively, compound 13 was prepared from 10
(85 mg, 0.15 mmol) and 8 (88.9 mg, 0.40 mmol) in 2 mL of
CH2Cl2: yield 94 mg (90%); mp 146 °C dec. Λ ) 73 cm2 Ω-1
mol-1 1H NMR (400 MHz, CD2Cl2, 295 K): δ 7.30 (m, 2H,
.
C6H5), 7.21 (m, 1H, C6H5), 7.09 (m, 2H, C6H5), 6.91 (m, 4H,
C6H5), 5.69 (m, 1H, para-H of η6-C6H5), 2.75 (m, 2H, PhCH2),
2.52 (m, 2H, PCH2), 2.33 (m, 2H, PhCH2), 2.04-1.78 (m, 6H,
PCHCH3 and PCH2), 1.24 [dd, J (PH) ) 16.1 Hz, J (HH) ) 7.0
Hz, 6H, PCHCH3], 1.21 [dd, J (PH) ) 14.4 Hz, J (HH) ) 7.0
Hz, 6H, PCHCH3], 1.14 [dd, J (PH) ) 16.3 Hz, J (HH) ) 7.0
Hz, 6H, PCHCH3], 1.13 [dd, J (PH) ) 15.1 Hz, J (HH) ) 6.8
Hz, 6H, PCHCH3]. 1H NMR (400 MHz, CD3NO2, 368 K): δ

4764 Organometallics, Vol. 19, No. 23, 2000
Werner et al.
K): δ 51.6 [dd, J (RhPA) ) 200.5 Hz, J (PBPA) ) 32.7 Hz, iPr2PA],
47.3 [dd, J (RhPB) ) 207.1 Hz, J (PAPB) ) 32.7 Hz, iPr2PB],
5 mL of pentane and dried in vacuo: yield 102 mg (83%); mp
125 °C dec. Λ ) 63 cm2 Ω-1 mol-1. IR (CD2Cl2): ν(≡CH) 3079,
1
-144.3 [sept, J (FP) ) 706.3 Hz, PF6-]. For assignment: PA
)
(C≡C) 1808, (CdO) 1700 cm-1. H NMR (400 MHz, CD2Cl2):
31P nuclei of η6-C6H5CH2CH2CH2PiPr2; PB
)
31P nuclei of C6H5-
δ 7.37 (m, 2H, C6H5), 7.13, 7.03 (both m, 1H each, C6H5), 5.97
[d, J (RhH) ) 3.5 Hz, 1H, ≡CH], 5.86 (m, 1H, C6H5), 4.30 [dq,
J (HH) ) 7.0 Hz, J (PH) ) 2.6 Hz, 2H, OCH2CH3], 2.83-2.71
(m, 4H, PCH2 and PhCH2), 1.92 (m, 2H, PCHCH3), 1.36 [t,
J (HH) ) 7.0 Hz, 3H, OCH2CH3], 1.22 (m, 6H, PCHCH3), 1.13
[dd, J (PH) ) 17.0 Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3]. 13C NMR
(100.6 MHz, CD2Cl2, 233 K): δ 158.6 [d, J (RhC) ) 1.9 Hz, Cd
O], 125.4 [dd, J (PC) ) 5.7 Hz, J (RhC) ) 3.8 Hz; d in 13C{31P},
J (RhC) ) 3.8 Hz, ipso-C of C6H5], 113.2, 112.3 (both s, C6H5),
101.8 [d, J (PC) ) 11.5 Hz, para-C of C6H5], 100.8, 99.7 [both
d, J (RhC) ) 2.9 Hz, C6H5], 82.0 [dd, J (RhC) ) 15.3 Hz, J (PC)
) 3.8 Hz; d in 13C{31P}, J (RhC) ) 15.3 Hz, C≡CH], 73.5 [dd,
J (RhC) ) 17.2 Hz, J (PC) ) 4.8 Hz; d in 13C{31P}, J (RhC) )
17.2 Hz, C≡CH], 62.4 (s, OCH2CH3), 37.6 [d, J (PC) ) 28.6 Hz,
PCH2], 31.3 (s, PhCH2), 24.8 [d, J (PC) ) 26.7 Hz, PCHCH3],
24.7 [d, J (PC) ) 27.7 Hz, PCHCH3], 17.5, 17.3, 17.1, 17.0 (all
s, PCHCH3), 13.8 (s, OCH2CH3). 31P NMR (162.0 MHz, CD2-
Cl2): δ 95.9 [d, J (RhP) ) 170.0 Hz, iPr2P], -144.4 [sept, J (FP)
) 710.6 Hz, PF6-]. Anal. Calcd for C19H29F6O2P2Rh (568.3):
C, 40.16; H, 5.14. Found: C, 39.85; H, 4.88.
CH2CH2CH2PiPr2. Anal. Calcd for C30H50F6P3Rh (720.5): C,
50.01; H, 6.99. Found: C, 49.56; H, 6.86.
P r ep a r a tion of [(η6-C6H5CH2CH2P iP r 2-K-P )Rh (C2H4)]-
P F 6 (15). A solution of 11 (197 mg, 0.34 mmol) in 2 mL of
CH2Cl2 was heated under an ethene atmosphere for 1 h at 75
°C. After the solution was cooled to room temperature, 8 mL
of ether was added, which led to the precipitation of a yellow
solid. The mother liquor was decanted, and the solid was
washed with 5 mL of ether and dried. This procedure was
repeated twice. Finally, a yellow solid was obtained, which was
washed twice with 5 mL of ether and twice with 5 mL of
pentane and dried: yield 156 mg (92%); mp 104 °C dec. Λ )
81 cm2 Ω-1 mol-1. 1H NMR (400 MHz, CD2Cl2, 295 K): δ 7.12,
7.02 (both m, 2H each, C6H5), 5.58 (m, 1H, C6H5), 2.94 (br s,
4H, C2H4), 2.68-2.56 (m, 4H, PCH2 and PhCH2), 1.96 (m, 2H,
PCHCH3), 1.21 [dd, J (PH) ) 15.8 Hz, J (HH) ) 7.0 Hz, 6H,
PCHCH3], 1.15 [dd, J (PH) ) 17.0 Hz, J (HH) ) 7.2 Hz, 6H,
PCHCH3]. 1H NMR (200 MHz, CD2Cl2, 220 K): δ 7.07, 6.93
(both m, 2H each, C6H5), 5.52 (m, 1H, C6H5), 3.16 (m, 2H,
outer-H of C2H4), 2.64-2.39 (br m, 6H, PCH2, PhCH2 and
inner-H of C2H4), 1.89 (m, 2H, PCHCH3), 1.10 [dd, J (PH) )
15.7 Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3], 1.04 [dd, J (PH) )
16.9 Hz, J (HH) ) 7.3 Hz, 6H, PCHCH3]. 13C NMR (100.6 MHz,
CD2Cl2): δ 122.0 [dd, J (RhC) ) 4.8 Hz, J (PC) ) 4.7 Hz; d in
13C{31P}, J (RhC) ) 4.8 Hz, ipso-C of C6H5], 108.9 (s, C6H5),
102.8 [d, J (RhC) ) 2.9 Hz, C6H5], 95.4 [dd, J (PC) ) 10.5 Hz,
J (RhC) ) 2.0 Hz; d in 13C{31P}, J (RhC) ) 2.0 Hz, para-C of
C6H5], 41.8 [dd, J (RhC) ) 13.4 Hz, J (PC) ) 1.9 Hz; d in 13C-
{31P}, J (RhC) ) 13.4 Hz, C2H4], 40.1 [d, J (PC) ) 27.7 Hz,
PCH2], 31.3 (s, PhCH2), 24.9 [dd, J (PC) ) 25.7 Hz, J (RhC) )
1.9 Hz; d in 13C{31P}, J (RhC) ) 1.9 Hz, PCHCH3], 18.7, 17.6
(both s, PCHCH3). 31P NMR (162.0 MHz, CD2Cl2): δ 93.7 [d,
J (RhP) ) 178.7 Hz, iPr2P], -144.3 [sept, J (FP) ) 710.6 Hz,
PF6-]. Anal. Calcd for C16H27F6P2Rh (498.2): C, 38.57; H, 5.46.
Found: C, 38.22; H, 4.97.
P r ep a r a tion of [(η6-C6H5CH2CH2P iP r 2-K-P )Rh (SbiP r 3)]-
P F 6 (18). A solution of 11 (150 mg, 0.26 mmol) in 3 mL of
CH2Cl2 was treated with SbiPr3 (107 µL, 0.52 mmol) and
stirred for 8 h at room temperature. A change of color from
yellow to red occurred. The solution was evaporated to dryness
in vacuo, and the oily residue was washed twice with 5 mL of
pentane and then dissolved in 3 mL of acetone. After the
solution was layered with 7 mL of ether, a light red solid
precipitated. The mother liquor was decanted, and the solid
was washed with 5 mL of ether and twice with 5 mL of pentane
and dried: yield 152 mg (81%); mp 114 °C dec. Λ ) 71 cm2
1
Ω-1 mol-1. H NMR (400 MHz, CD2Cl2): δ 6.88, 6.81 (both m,
2H each, C6H5), 5.74 (m, 1H, C6H5), 2.58 [ddd, J (PH) ) 8.8
Hz, J (HH) ) 7.6 Hz, J (HH) ) 7.3 Hz, 2H, PCH2], 2.39 [ddd,
J (PH) ) 19.4 Hz, J (HH) ) 7.6 Hz, J (HH) ) 7.3 Hz, 2H,
PhCH2], 2.15 [sept, J (HH) ) 7.3 Hz, 3H, SbCHCH3], 1.81 (m,
2H, PCHCH3), 1.30 [d, J (HH) ) 7.3 Hz, 18H, SbCHCH3], 1.16
[dd, J (PH) ) 15.0 Hz, J (HH) ) 6.9 Hz, 6H, PCHCH3], 1.14
[dd, J (PH) ) 17.3 Hz, J (HH) ) 7.3 Hz, 6H, PCHCH3]. 13C NMR
(100.6 MHz, CD2Cl2): δ 110.8 [dd, J (PC) ) 5.4 Hz, J (RhC) )
4.8 Hz; d in 13C{31P}, J (RhC) ) 4.8 Hz, ipso-C of C6H5], 101.6
(s, C6H5), 100.5 [d, J (RhC) ) 3.1 Hz, C6H5], 88.4 [dd, J (PC) )
9.2 Hz, J (RhC) ) 2.0 Hz; d in 13C{31P}, J (RhC) ) 2.0 Hz,
para-C of C6H5], 39.9 [d, J (PC) ) 26.5 Hz, PCH2], 31.0 (s,
PhCH2), 27.2 [dd, J (PC) ) 26.4 Hz, J (RhC) ) 2.0 Hz; d in 13C-
{31P}, J (RhC) ) 2.0 Hz, PCHCH3], 21.6 (s, SbCHCH3), 21.0
[d, J (RhC) ) 3.0 Hz, PCHCH3], 20.3 [d, J (PC) ) 4.1 Hz,
PCHCH3], 18.2 (s, SbCHCH3). 31P NMR (162.0 MHz, CD2Cl2):
δ 99.8 [d, J (RhP) ) 180.9 Hz, iPr2P], -144.4 [sept, J (FP) )
710.6 Hz, PF6-]. Anal. Calcd for C23H44F6P2RhSb (721.2): C,
38.31; H, 6.15. Found: C, 38.19; H, 6.39.
P r ep a r a tion of [(η6-C6H5CH2CH2P iP r 2-K-P )Rh (C4H2O3)]-
P F 6 (16). The preparation was analogous with that described
for 15, from 11 (103 mg, 0.18 mmol) and maleic acid anhydride
(33.2 mg, 0.36 mmol) in 3 mL of CH2Cl2. Yellow solid: yield
1
85 mg (83%); mp 186 °C dec. Λ ) 74 cm2 Ω-1 mol-1. H NMR
(400 MHz, acetone-d6): δ 7.64, 7.36 (both m, 2H each, C6H5),
5.80 (m, 1H, C6H5), 4.24 [dd, J (PH) ) 4.1 Hz, J (RhH) ) 2.6
Hz, 2H, dCH of C4H2O3], 3.19 [ddd, J (PH) ) 9.7 Hz, J (HH) )
7.6 Hz, J (HH) ) 7.3 Hz, 2H, PCH2], 2.98 [ddd, J (PH) ) 22.6
Hz, J (HH) ) 7.6 Hz, J (HH) ) 7.3 Hz, 2H, PhCH2], 2.44 (m,
2H, PCHCH3), 1.36 [dd, J (PH) ) 16.4 Hz, J (HH) ) 6.8 Hz,
6H, PCHCH3], 1.32 [dd, J (PH) ) 17.2 Hz, J (HH) ) 7.2 Hz,
6H, PCHCH3]. 13C NMR (100.6 MHz, d6-acetone): δ 172.2 (s,
CdO of C4H2O3), 130.6 [dd, J (PC) ) 5.7 Hz, J (RhC) ) 4.8 Hz;
d in 13C{31P}, J (RhC) ) 4.8 Hz, ipso-C of C6H5], 115.3 (s, C6H5),
106.9 [d, J (PC) ) 8.6 Hz, para-C of C6H5], 102.8 [d, J (RhC) )
2.9 Hz, C6H5], 46.2 [dd, J (RhC) ) 15.3 Hz, J (PC) ) 2.9 Hz; d
in 13C{31P}, J (RhC) ) 15.3 Hz, dCH of C4H2O3], 39.9 [d, J (PC)
) 29.6 Hz, PCH2], 31.7 (s, PhCH2), 26.1 [d, J (PC) ) 25.8 Hz,
PCHCH3], 19.0 (s, PCHCH3), 17.7 [d, J (PC) ) 1.9 Hz, PCHCH3].
31P NMR (162.0 MHz, acetone-d6): δ 102.5 [d, J (RhP) ) 150.4
Hz, iPr2P], -144.2 [sept, J (FP) ) 708.4 Hz, PF6-]. Anal. Calcd
for C18H25F6O3P2Rh (568.2): C, 38.05; H, 4.43. Found: C,
37.91; H, 4.63.
P r ep a r a tion of [(η6-C6H5CH2CH2P iP r 2-K-P )Rh (HC≡C-
CO2Et)]P F 6 (17). A solution of 11 (126 mg, 0.22 mmol) in 3
mL of CH2Cl2 was treated at -20 °C with ethyl propiolate (111
µL, 110 mmol). After warming to room temperature, the
reaction mixture was stirred for 12 h, which led to a change
of color from yellow to red. Upon addition of 7 mL of ether, a
yellow solid precipitated. The mother liquor was decanted, and
the solid was washed twice with 5 mL of ether and twice with
P r epar ation of [(η6-C6H5CH2CH2CH2P iP r 2-K-P )Rh (C2H4)]-
P F 6 (19). The preparation was analogous with that described
for 15, from 12 (143 mg, 0.24 mmol). Reaction conditions: 1.5
h at 85 °C, repeating the procedure four times. Yellow solid:
1
yield 97 mg (79%); mp 180 °C dec. Λ ) 73 cm2 Ω-1 mol-1. H
NMR (400 MHz, CD2Cl2): δ 7.05, 6.90 (both m, 2H each, C6H5),
5.45 (m, 1H, C6H5), 3.28 (br s, 2H, exo-H of C2H4), 2.52 (m,
2H, PhCH2), 2.45 (br s, 2H, endo-H of C2H4), 2.01-1.76 (m,
4H, PCH2 and PCHCH3), 1.32 (m, 2H, PCH2CH2), 1.15 [dd,
J (PH) ) 14.6 Hz, J (HH) ) 6.8 Hz, 6H, PCHCH3], 1.13 [dd,
J (PH) ) 16.2 Hz, J (HH) ) 7.0 Hz, 6H, PCHCH3]. 1H NMR
(400 MHz, CD2Cl2, 233 K): δ 7.01, 6.84 (both m, 2H each,
C6H5), 5.44 (m, 1H, C6H5), 3.21 (m, 2H, exo-H of C2H4), 2.46
(m, 2H, PhCH2), 2.33 (m, 2H, endo-H of C2H4), 1.94-1.68 (m,
4H, PCH2 and PCHCH3), 1.25 (m, 2H, PCH2CH2), 1.08 [dd,
J (PH) ) 14.9 Hz, J (HH) ) 6.9 Hz, 6H, PCHCH3], 1.06 [dd,
J (PH) ) 16.4 Hz, J (HH) ) 7.1 Hz, 6H, PCHCH3]. 13C NMR

Half-Sandwich Type Rhodium(I) Complexes
Organometallics, Vol. 19, No. 23, 2000 4765
(100.6 MHz, CD2Cl2): δ 112.3 [d, J (RhC) ) 2.9 Hz, ipso-C of
C6H5], 108.7 [d, J (RhC) ) 1.9 Hz, C6H5], 104.3 [d, J (RhC) )
2.9 Hz, C6H5], 96.3 [dd, J (PC) ) 10.5 Hz, J (RhC) ) 1.9 Hz; d
in 13C{31P}, J (RhC) ) 1.9 Hz, para-C of C6H5], 39.9 [dd, J (RhC)
) 13.3 Hz, J (PC) ) 1.9 Hz; d in 13C{31P}, J (RhC) ) 13.3 Hz,
C2H4], 31.9, 26.2 (both s, PCH2CH2 and PhCH2), 25.0 [d, J (PC)
) 27.7 Hz, PCHCH3], 19.7, 17.6 (both s, PCHCH3), 15.4 [d,
J (PC) ) 27.6 Hz, PCH2]. 31P NMR (162.0 MHz, CD2Cl2): δ
56.0 [d, J (RhP) ) 172.2 Hz, iPr2P], -144.3 [sept, J (FP) ) 710.6
Hz, PF6-]. Anal. Calcd for C17H29F6P2Rh (512.3): C, 39.86; H,
5.71. Found: C, 39.58; H, 5.43.
P r ep a r a tion of [(η6-C6H5CH2CH2P tBu 2-K-P )Rh (C8H14)]-
P F 6 (22a ). A solution of 10 (1.00 g, 1.73 mmol) in 3 mL of
acetone was treated at -20 °C dropwise over a period of 25
min with an ice-cooled solution of 20 (474 mg, 1.73 mmol) in
10 mL of acetone. After the reaction mixture was warmed to
room temperature, the solution was concentrated to ca. 3 mL
in vacuo and then treated with 12 mL of ether. A yellow solid
precipitated, which was separated from the mother liquor,
washed three times with 7 mL of ether and twice with 7 mL
of pentane, and dried: yield 983 mg (93%); mp 144 °C dec. Λ
) 93 cm2 Ω-1 mol-1. 1H NMR (400 MHz, CD2Cl2): δ 7.01, 6.86
(both m, 2H each, C6H5), 5.69 (m, 1H, C6H5) 3.91 (m, 2H, dCH
of C8H14), 2.66, 2.55 (both m, 2H each, PhCH2 and PCH2), 2.33
(m, 2H, CH2 of C8H14), 1.71-1.33 (m, 10H, CH2 of C8H14), 1.31
[d, J (PH) ) 13.8 Hz, 18H, PCCH3]. 13C NMR (100.6 MHz, CD2-
Cl2): δ 118.4 [dd, J (PC) ) 4.8 Hz, J (RhC) ) 3.8 Hz; d in 13C-
{31P}, J (RhC) ) 3.8 Hz, ipso-C of C6H5], 111.6 (s, C6H5), 103.6
[d, J (RhC) ) 1.9 Hz, C6H5], 95.0 [dd, J (PC) ) 9.5 Hz, J (RhC)
) 1.9 Hz; d in 13C{31P}, J (RhC) ) 1.9 Hz, para-C of C6H5],
69.2 [d, J (RhC) ) 13.4 Hz, dCH of C8H14], 40.1 [d, J (PC) )
24.8 Hz, PCH2], 37.2 [dd, J (PC) ) 15.3 Hz, J (RhC) ) 1.9 Hz;
d in 13C{31P}, J (RhC) ) 1.9 Hz, PCCH3], 34.0, 32.3, 31.2 and
26.3 (all s, CH2 of C8H14 and PhCH2), 30.4 [d, J (PC) ) 2.9 Hz,
PCCH3]. 31P NMR (162.0 MHz, CD2Cl2): δ 96.0 [d, J (RhP) )
189.6 Hz, tBu2P], -144.3 [sept, J (FP) ) 710.6 Hz, PF6-]. Anal.
Calcd for C24H41F6P2Rh (608.4): C, 47.38; H, 6.79; Rh, 16.91.
Found: C, 47.44; H, 6.54; Rh, 16.86.
P r ep a r a tion of C6H5CH2CH2P tBu 2 (20). A mixture of
HPtBu2 (7.4 g, 50.7 mmol) and 2-phenylethylbromide (6.2 mL,
45.7 mmol) was heated under stirring for 4 days at 90 °C. After
the reaction mixture was cooled to room temperature, a
colorless oily liquid was obtained. The liquid was dissolved in
30 mL of degassed water, and the solution was washed five
times with 20 mL of ether. The aqueous solution was layered
with 80 mL of ether and then treated under stirring with KOH
until the aqueous phase became basic (pH ∼9). The ethereal
phase was separated, washed three times with 20 mL of water,
and then dried with Na2SO4. The solvent was removed in
vacuo, and the residue was distilled to give a colorless oily
1
liquid: yield 9.7 g (85%); bp 77-78 °C (0.04 mbar). H NMR
(200 MHz, CDCl3): δ 7.24 (m, 5H, C6H5), 2.82 (m, 2H, PhCH2),
1.67 (m, 2H, PCH2), 1.15 [d, J (PH) ) 10.6 Hz, 18H, PCCH3].
13C NMR (50.3 MHz, CDCl3): δ 143.7 [d, J (PC) ) 14.8 Hz,
ipso-C of C6H5], 128.4, 128.1, 125.9 (all s, C6H5), 36.7 [d, J (PC)
) 24.0 Hz, PhCH2], 31.4 [d, J (PC) ) 20.3 Hz, PCCH3], 29.7
[d, J (PC) ) 13.9 Hz, PCCH3], 23.8 [d, J (PC) ) 21.3 Hz, PCH2].
31P NMR (81.0 MHz, CDCl3): δ 30.4 (s). MS (70 eV) m/z 251
(M+ + H).
P r ep a r a tion of [(η6-C6H5CH2CH2P tBu 2-K-P )Rh (C8H14)]-
CF 3SO3 (22b). A solution of 25 (230 mg, 0.24 mmol) in 10 mL
of ether was treated at -70 °C dropwise with a cooled (-20
°C) solution of 20 (134 mg, 0.54 mmol) in 3 mL of ether. Almost
instantaneously, a yellow solid precipitated, which was sepa-
rated from the mother liquor, washed three times with 5 mL
of ether and three times with 5 mL of pentane, and dried: yield
280 mg (94%); mp 117 °C dec. Λ ) 73 cm2 Ω-1 mol-1. IR (CH2-
P r epar ation of [C6H5CH2CH2P tBu 2Me]I (20a). The prepa-
ration was analogous with that described for 8a , from 20 (1.38
g, 5.52 mmol) and CH3I (350 µL, 5.60 mmol). Colorless solid:
1
Cl2): ν(O3S) 1242 and 1031, ν(CF3) 1158 cm-1. H NMR (400
1
yield 1.99 g (92%); mp 174 °C. H NMR (200 MHz, CDCl3): δ
MHz, CD2Cl2): δ 7.08, 6.87 (both m, 2H each, C6H5), 5.70 (m,
1H, C6H5), 3.90 (m, 2H, dCH of C8H14), 2.69 [ddd, J (PH) )
7.35 (m, 5H, C6H5), 3.19 (m, 2H, PhCH2), 2.52 (m, 2H, PCH2),
2.20 [d, J (PH) ) 11.7 Hz, 3H, PCH3], 1.53 [d, J (PH) ) 15.0
Hz, 18H, PCCH3]. 13C NMR (50.3 MHz, CDCl3): δ 138.9 [d,
J (PC) ) 12.0 Hz, ipso-C of C6H5], 129.0, 128.5, 127.2 (all s,
C6H5), 33.9 [d, J (PC) ) 38.8 Hz, PCCH3], 29.6 [d, J (PC) ) 4.6
Hz, PhCH2], 27.2 (s, PCCH3), 18.9 [d, J (PC) ) 39.8 Hz, PCH2],
1.8 [d, J (PC) ) 45.3 Hz, PCH3]. 31P NMR (81.0 MHz, CDCl3):
δ 47.8 (s). Anal. Calcd for C17H30IP (392.3): C, 52.05; H, 7.71.
Found: C, 51.83; H, 7.56.
1
9.3 Hz, J (HH) ) 7.2 Hz, J (HH) ) 6.8 Hz; dd in H{31P}, J (HH)
) 7.2 Hz, J (HH) ) 6.8 Hz, 2H, PCH2], 2.57 [ddd, J (PH) ) 19.4
Hz, J (HH) ) 7.2 Hz, J (HH) ) 6.8 Hz; dd in 1H{31P}, J (HH) )
7.2 Hz, J (HH) ) 6.8 Hz, 2H, PhCH2], 2.33 (m, 2H, CH2 of
C8H14), 1.70-1.30 (m, 10H, CH2 of C8H14), 1.32 [d, J (PH) )
13.8 Hz, 18H, PCCH3]. 13C NMR (100.6 MHz, CD2Cl2): δ 121.3
[q, J (FC) ) 321.4 Hz, CF3], 118.7 [dd, J (PC) ) 4.8 Hz, J (RhC)
) 3.8 Hz; d in 13C{31P}, J (RhC) ) 3.8 Hz, ipso-C of C6H5], 111.6,
103.6 (both s, C6H5), 95.0 [dd, J (PC) ) 9.5 Hz, J (RhC) ) 1.9
Hz; d in 13C{31P}, J (RhC) ) 1.9 Hz, para-C of C6H5], 69.0 [d,
J (RhC) ) 12.4 Hz, dCH of C8H14], 40.1 [d, J (PC) ) 24.8 Hz,
PCH2], 37.2 [d, J (PC) ) 16.2 Hz, PCCH3], 34.0, 32.3, 31.2, 26.2
(all s, CH2 of C8H14 and PhCH2), 30.4 [d, J (PC) ) 3.8 Hz,
PCCH3]. 19F NMR (188.3 MHz, CD2Cl2): δ -78.7 (s). 31P NMR
(162.0 MHz, CD2Cl2): δ 96.0 [d, J (RhP) ) 189.9 Hz]. Anal.
Calcd for C25H41F3O3PSRh (612.5): C, 49.02; H, 6.75; S, 5.23.
Found: C, 48.81; H, 6.46; S, 5.29.
P r epar ation of [(η6-C6H5OCH2CH2P tBu 2-K-P )Rh (C8H14)]-
P F 6 (23). The preparation was analogous with that described
for 11, from 10 (197 mg, 0.34 mmol) and 21 (91 mg, 0.34 mmol).
Yellow solid: yield 192 mg (90%); mp 122 °C dec. Λ ) 102
cm2 Ω-1 mol-1. 1H NMR (400 MHz, CD2Cl2): δ 6.90, 6.79 (both
m, 2H each, C6H5), 5.51 (m, 1H, C6H5), 4.43 (m, 2H, PCH2CH2),
4.01 (m, 2H, dCH of C8H14), 2.34 (m, 2H, CH2 of C8H14), 1.76-
1.36 (m, 12H, CH2 of C8H14 and PCH2), 1.32 [d, J (PH) ) 13.8
Hz, 18H, PCCH3]. 13C NMR (100.6 MHz, CD2Cl2): δ 129.2 [d,
J (RhC) ) 2.9 Hz, ipso-C of C6H5], 112.2, 97.6 (both s, C6H5),
91.9 [dd, J (PC) ) 8.6 Hz, J (RhC) ) 3.8 Hz; d in 13C{31P},
J (RhC) ) 3.8 Hz, para-C of C6H5], 69.4 (s, PCH2CH2), 66.4 [d,
J (RhC) ) 14.3 Hz, dCH of C8H14], 37.8 [dd, J (PC) ) 16.2 Hz,
J (RhC) ) 1.9 Hz; d in 13C{31P}, J (RhC) ) 1.9 Hz, PCCH3],
33.6, 32.3, 26.3 (all s, CH2 of C8H14), 31.1 [d, J (PC) ) 2.9 Hz,
PCCH3], 15.2 [d, J (PC) ) 21.9 Hz, PCH2]. 31P NMR (162.0
P r ep a r a tion of C6H5OCH2CH2P tBu 2 (21). The prepara-
tion was analogous with that described for 20, from HPtBu2
(4.49 g, 30.7 mmol) and PhOCH2CH2Br (5.56 g, 27.6 mmol).
Reaction conditions: 3 days at 80 °C. Colorless oily liquid:
yield 8.20 g (81%). 1H NMR (400 MHz, C6D6): δ 7.13, 6.91 (both
m, 2H each, C6H5), 6.84 (m, 1H, C6H5), 4.07 (m, 2H, PCH2CH2),
1.85 (m, 2H, PCH2), 1.01 [d, J (PH) ) 11.2 Hz, 18H, PCCH3].
13C NMR (100.6 MHz, C6D6): δ 159.4 (s, ipso-C of C6H5), 129.8,
120.8, 114.9 (all s, C6H5), 69.0 [d, J (PC) ) 5.8 Hz, PCH2CH2],
31.1 [d, J (PC) ) 21.0 Hz, PCCH3], 29.6 [d, J (PC) ) 14.3 Hz,
PCCH3], 22.2 [d, J (PC) ) 21.9 Hz, PCH2]. 31P NMR (162.0
MHz, C6D6): δ 19.4 (s). MS (70 eV) m/z 267 (M+ + H).
P r ep a r a tion of [C6H5OCH2CH2P tBu 2Me]I (21a ). The
preparation was analogous with that described for 8a , from
21 (400 mg, 1.50 mmol) and CH3I (95 µL, 1.52 mmol). Colorless
solid: yield 541 mg (88%); mp 138 °C. 1H NMR (200 MHz,
CD3NO2): δ 7.32 (m, 2H, C6H5), 7.00 (m, 3H, C6H5), 4.45 (m,
2H, PCH2CH2), 2.82 (m, 2H, PCH2), 1.96 [d, J (PH) ) 12.1 Hz,
3H, PCH3], 1.51 [d, J (PH) ) 15.7 Hz, 18H, PCCH3]. 13C NMR
(50.3 MHz, CD3NO2): δ 158.8 (s, ipso-C of C6H5), 131.0, 123.1,
115.7 (all s, C6H5), 63.3 [d, J (PC) ) 5.9 Hz, PCH2CH2], 34.8
[d, J (PC) ) 38.3 Hz, PCCH3], 26.8 (s, PCCH3), 18.5 [d, J (PC)
) 44.8 Hz, PCH2], 0.3 [d, J (PC) ) 47.4 Hz, PCH3]. 31P NMR
(81.0 MHz, CD3NO2): δ 49.3 (s). Anal. Calcd for C17H30OIP
(408.3): C, 50.01; H, 7.41. Found: C, 49.67; H, 7.28.

4766 Organometallics, Vol. 19, No. 23, 2000
Ta ble 4. Cr ysta llogr a p h ic Da ta for 11, 12, a n d 19
Werner et al.
formula
fw
C22H37F6P2Rh (11)
580.37
C23H39F6P2Rh (12)
594.39
C17H29F6P2Rh (19)
512.25
cryst size, mm3
cryst syst
space group
cell dimens
determn
a, Å
0.22 × 0.18 × 0.17
monoclinic
P21/c (No. 14)
5000 reflns,
2° < θ < 25°
13.403(1)
9.945(1)
18.974(2)
99.89(1)
2491.5(5)
4
1.547
173(2)
0.866
Φ
50
25 465
4290
0.19 × 0.15 × 0.14
monoclinic
P21/c (No. 14)
5000 reflns,
2° < θ < 25°
13.436(2)
9.7565(8)
20.086(2)
104.02(1)
2554.7(5)
4
1.530
173(2)
0.847
Φ
50
21 382
4506
0.18 × 0.16 × 0.15
monoclinic
P21/n (No. 14)
25 reflns,
10° < θ < 15°
8.749(2)
17.578(4)
13.270(3)
92.91(3)
2038.1(7)
4
1.669
193(2)
1.047
Ω/φ
50
4505
3584
b, Å
c, Å
â, deg
V, Å3
Z
d
calc, g‚cm-3
temp, K
µ, mm-1
scan method
2θ(max), deg
total no. of reflns
no. of unique reflns
[R(int) ) 0.0719]
[R(int) ) 0.0562]
[R(int) ) 0.0275]
no. of obsd reflns
[I > 2σ(I)]
no. of reflns used for refinement
no. of params refined
final R indices
3463
3539
2620
4290
285
4506
331
3584
276
R1 ) 0.0484
wR2 ) 0.1027a
R1 ) 0.0761,
wR2 ) 0.1207a
R1 ) 0.0386,
wR2 ) 0.1010a
R1 ) 0.0465,
wR2 ) 0.1052a
0.0053(7)
R1 ) 0.0413,
wR2 ) 0.1046a
R1 ) 0.0535,
wR2 ) 0.1105a
0.0031(5)
[I > 2σ(I)]
R indices (all data)
extinction coeff
resid electron density, e Å-3
0.784/-0.647
0.683/-1.409
0.615/-0.668
a
2
2
2
w-1 ) [σ2Fo + (0.0764P)2 + 0.0000P] (11), w-1 ) [σ2Fo + (0.0773P)2 + 0.0000P] (12), w-1 ) [σ2Fo + (0.0452P)2 + 6.7551P] (19),
where P ) (Fo + 2Fc2)/3.
2
MHz, CD2Cl2): δ 47.1 [d, J (RhP) ) 185.3 Hz, tBu2P], -144.3
[sept, J (FP) ) 710.6 Hz, PF6-]. Anal. Calcd for C24H41F6OP2-
Rh (624.4): C, 46.16; H, 6.62. Found: C, 46.07; H, 6.38.
P r ep a r a tion of [(η6-C6H5CH2CH2P tBu 2-K-P )Rh (HC≡C-
CO2Et)]P F 6 (24). The preparation was analogous with that
described for 17, from 22a (110 mg, 0.18 mmol) and ethyl
propiolate (92 µL, 0.90 mmol). Yellow solid: yield 98 mg (91%);
mp 136 °C dec. Λ ) 81 cm2 Ω-1 mol-1. IR (CH2Cl2): ν(≡CH)
(11, 12) and an Enraf-Nonius CAD4 diffractometer (19) using
monochromated Mo KR radiation (λ ) 0.71073 Å). Crystal data
collection parameters are summarized in Table 4. Intensity
data were corrected by Lorentz and polarization effects, and
for 19 an empirical absorption correction was applied (Ψ-scan
method, minimum transmission 80%). The structures were
solved by direct methods (SHELXS-97).14 Atomic coordinates
and anisotropic thermal parameters of non-hydrogen atoms
were refined by full-matrix least squares on F2 (SHELXL-97).15
The ethene ligand in 19 was found layer disordered. Two
geometrically independent positions were found and refined
anisotropically with restraints (SIMU, DELU) and the oc-
cupancy factors 0.50:0.50. In 12 and 19 also the PF6- ion was
found disordered (occupation factors 0.82:0.12 (12) and 0.83:
0.17 (19)). The positions of all hydrogen atoms were calculated
according to ideal geometry and refined by using the riding
method.
3042, ν(C≡C) 1811, ν(CdO) 1700 cm-1
.
1H NMR (400 MHz,
CD2Cl2): δ 7.41, 7.30, 7.13, 7.03 (all m, 1H each, C6H5), 6.07
[d, J (RhH) ) 3.5 Hz, 1H, ≡CH], 5.61 (m, 1H, C6H5), 4.30 [dq,
J (HH) ) 7.0 Hz, J (PH) ) 1.6 Hz, 2H, OCH2CH3], 2.88-2.70
(m, 4H, PCH2 and PCH2CH2), 1.35 [t, J (HH) ) 7.0 Hz, 3H,
OCH2CH3], 1.26 [d, J (PH) ) 14.6 Hz, 9H, PCCH3], 1.23 [d,
J (PH) ) 14.6 Hz, 9H, PCCH3]. 13C NMR (100.6 MHz, CD2Cl2,
233 K): δ 158.8 [d, J (RhC) ) 1.9 Hz, CdO], 125.9 [dd, J (PC)
) 5.7 Hz, J (RhC) ) 3.8 Hz; d in 13C{31P}, J (RhC) ) 3.8 Hz,
ipso-C of C6H5], 113.5 [d, J (RhC) ) 1.9 Hz, C6H5], 112.7 (s,
C6H5), 103.2, 102.1 [both d, J (RhC) ) 2.9 Hz, C6H5], 100.7 [d,
J (PC) ) 11.4 Hz, para-C of C6H5], 81.1 [dd, J (RhC) ) 15.3
Hz, J (PC) ) 3.8 Hz; d in 13C{31P}, J (RhC) ) 15.3 Hz, C≡CH],
72.5 [dd, J (RhC) ) 17.2 Hz, J (PC) ) 3.8 Hz; d in 13C{31P},
J (RhC) ) 17.2 Hz, C≡CH], 62.9 (s, OCH2CH3), 39.9 [d, J (PC)
) 25.8 Hz, PCH2], 37.2 [d, J (PC) ) 17.2 Hz, PCCH3], 37.1 [d,
J (PC) ) 16.2 Hz, PCCH3], 32.2 (s, PCH2CH2), 29.5 [d, J (PC)
) 1.9 Hz, PCCH3], 29.3 [d, J (PC) ) 2.9 Hz, PCCH3], 14.3 (s,
OCH2CH3). 31P NMR (162.0 MHz, CD2Cl2): δ 109.5 [d, J (RhP)
) 176.6 Hz, tBu2P], -144.3 [sept, J (FP) ) 710.6 Hz, PF6-].
Anal. Calcd for C21H33F6O2P2Rh (596.3): C, 42.30; H, 5.58.
Found: C, 42.48; H, 5.26.
Ack n ow led gm en t. We thank the Deutsche For-
schungsgemeinschaft (Grant No. SFB 347) and the
Fonds der Chemischen Industrie for financial support,
the latter in particular for two Ph. D. scholarships (for
G.C. and K.I.). Moreover, we gratefully acknowledge
support by R. Schedl and C. P. Kneis (DTA and
elemental analysis), F. Dadrich and Dr. G. Lange (mass
spectra), M.-L. Scha¨fer and Dr. W. Buchner (NMR
spectra), B. Weberndo¨rfer (X-ray structure analysis),
and BASF AG (gifts of chemicals).
Su p p or tin g In for m a tion Ava ila ble: Tables of data col-
lection parameters, bond lengths and angles, positional and
thermal parameters, and least-squares planes for 11, 12, and
19. This material is available free of charge via the Internet
at http://pubs.acs.org.
X-r a y Str u ctu r a l Deter m in a tion of Com p ou n d s 11, 12,
a n d 19. Single crystals were grown by diffusion of ether into
a concentrated solution of 11, 12, and 19 in acetone at room
temperature. The data were collected from a shock-cooled
crystal protected by an oil drop13 on a Stoe IPDS diffractometer
OM0004646
(13) (a) Kottke, T.; Stalke, D. J . Appl. Crystallogr. 1993, 26, 615-
619. (b) Kottke, T.; Lagow, R. J .; Stalke, D. J . Appl. Crystallogr. 1996,
29, 465-468. (c) Stalke, D. Chem. Soc. Rev. 1998, 27, 171-178.
(14) Sheldrick, G. M. Acta Crystallogr. Sect. A 1990, 46, 467-473.
(15) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; Universita¨t Go¨ttingen, 1997.