Syntheses, molecular structures, and reactivities of (π-allyl)rhodium(I) complexes containing bulky bis(phosphino)methanes R′2PCH2PiPr2 as ligands

Article abstract of DOI:10.1021/om980062m

The π-allyl complexes [Rh(η³-2-RC₃H₄)(κ ²-R′₂PCH₂PiPr₂)] (R = H, Me; R′ = iPr, Cy, Ph) (2-7) were prepared from [RhCl(η⁴-C₈H₁₂)]₂, 2-RC₃H₄MgX, and R′₂PCH₂PiPr₂ via [Rh(η³-2-RC₃H₄)(η⁴-C ₈H₁₂)] as the intermediate. Reaction of 2-4 (R = H) with Broensted acids HX (X = Cl, CF₃CO₂, CF₃SO₃) led to cleavage of the allyl-metal bond and to the formation of the monohydridorhodium(III) compounds [RhHX₂(κ²-R′₂PCH ₂PiPr₂)] (8-12). Variable-temperature NMR measurements of 8-12 confirm that these compounds are fluctional in solution. The reaction of 2-4 with CO gave in the initial step the 1:1 adducts [Rh(η³-C₃H₅)(CO)(κ ²-R′₂PCH₂PiPr₂)] (16-18), of which that with R′ = iPr was characterized by X-ray structure analysis. Compounds 16 (R′ = iPr) and 18 (R′ = Ph) reacted with excess carbon monoxide via migratory insertion of CO into the allyl-metal bond to yield the five-coordinate acylrhodium(I) complexes [Rh{C(O)CH₂CH=CH₂}(CO)₂(κ ²-R′₂PCH₂PiPr₂)] (19, 20). This insertion reaction is reversible. The analogous acyl compound [Rh{C(O)CH₂Ph}(CO)₂(κ²-iPr ₂PCH₂PiPr₂)] (22) was obtained from [Rh(η³-CH₂Ph)(κ²-iPr ₂PCH₂PiPr₂)] and CO. Acid cleavage of the acyl-metal bond of 19 (R′ = iPr) afforded the aldehyde CH₂=CHCH₂CHO (26) and a mixture of 8 and [RhHCl₂(CO)(κ₂-iPr₂PCH ₂PiPr₂)] (25).

Full text of DOI:10.1021/om980062m

3210
Organometallics 1998, 17, 3210-3221
Syn th eses, Molecu la r Str u ctu r es, a n d Rea ctivities of
(π-Allyl)r h od iu m (I) Com p lexes Con ta in in g Bu lk y
Bis(p h osp h in o)m eth a n es R′2P CH2P iP r 2 a s Liga n d s
Matthias Manger, J ustin Wolf, Markus Teichert, Dietmar Stalke, and
Helmut Werner*
Institut fu¨r Anorganische Chemie, Universita¨t Wu¨rzburg, Am Hubland,
D-97074 Wu¨rzburg, Germany
Received J anuary 30, 1998
The π-allyl complexes [Rh(η3-2-RC3H4)(κ2-R′2PCH2PiPr2)] (R ) H, Me; R′ ) iPr, Cy, Ph)
(2-7) were prepared from [RhCl(η4-C8H12)]2, 2-RC3H4MgX, and R′2PCH2PiPr2 via [Rh(η3-2-
RC3H4)(η4-C8H12)] as the intermediate. Reaction of 2-4 (R ) H) with Broensted acids HX
(X ) Cl, CF3CO2, CF3SO3) led to cleavage of the allyl-metal bond and to the formation of
the monohydridorhodium(III) compounds [RhHX2(κ2-R′2PCH2PiPr2)] (8-12). Variable-
temperature NMR measurements of 8-12 confirm that these compounds are fluctional in
solution. The reaction of 2-4 with CO gave in the initial step the 1:1 adducts [Rh(η3-
C3H5)(CO)(κ2-R′2PCH2PiPr2)] (16-18), of which that with R′ ) iPr was characterized by X-ray
structure analysis. Compounds 16 (R′ ) iPr) and 18 (R′ ) Ph) reacted with excess carbon
monoxide via migratory insertion of CO into the allyl-metal bond to yield the five-coordinate
acylrhodium(I) complexes [Rh{C(O)CH2CHdCH2}(CO)2(κ2-R′2PCH2PiPr2)] (19, 20). This
insertion reaction is reversible. The analogous acyl compound [Rh{C(O)CH2Ph}(CO)2(κ2-
iPr2PCH2PiPr2)] (22) was obtained from [Rh(η3-CH2Ph)(κ2-iPr2PCH2PiPr2)] and CO. Acid
cleavage of the acyl-metal bond of 19 (R′ ) iPr) afforded the aldehyde CH2dCHCH2CHO
(26) and a mixture of 8 and [RhHCl2(CO)(κ2-iPr2PCH2PiPr2)] (25).
In tr od u ction
as the precursor.5 With this methodology, also phos-
phino(stibino)methanes and arsino(phosphino)methanes
have been obtained.6 Some preliminary results regard-
ing the synthesis of the unsymmetrical bis(phosphino)-
methanes R′2PCH2PiPr2 and their rhodium complexes
were already communicated.7
In the context of our investigations on low-valent
rhodium complexes containing Rh(PiPr3)2 as a molec-
ular unit, we recently reported a high-yield synthesis
of the π-allyl compounds [Rh(η3-2-RC3H4)(PiPr3)2] (R )
H, Me, Ph) using [RhCl(PiPr3)2]2 as the starting mate-
rial.1 This preparative route is somewhat different from
that developed by Sivak and Muetterties,2 who gener-
ated from [RhCl(η4-C8H12)]2 (1) and C3H5MgBr the
cyclooctadiene derivative [Rh(η3-C3H5)(η4-C8H12)] as an
intermediate which on treatment with tertiary phos-
phines PR3 gave [Rh(η3-C3H5)(PR3)2].2,3 Similarly, the
Resu lts a n d Discu ssion
P r ep a r a tion s of th e π-Allyl Com p lexes. The
method first reported by Sivak and Muetterties could
be successfully applied for the preparation of compounds
2-7 with R′2PCH2PiPr2 (R′ ) iPr, Cy, Ph) as chelating
ligands (Scheme 1). Treatment of a suspension of 1 in
ether with an equimolar amount of C3H5MgBr in ether
or 2-MeC3H4MgCl in THF at -20 °C results in the
formation of a yellow solution which contains the
cyclooctadiene derivative [Rh(η3-2-RC3H4)(η4-C8H12)] (R
) H, Me) as the main component. The addition of 2
equiv of the bis(phosphino)methane R′2PCH2PiPr2 in
hexane to the reaction mixture generates a deep yellow
solution from which the chelate complexes 2-7 are
corresponding chelate
complexes
[Rh(η3-C3H5)-
{R′2P(CH2)nPR′2}] (n ) 2, 3) have been obtained.4
This paper describes the syntheses of the π-allyl
compounds [Rh(η3-2-RC3H4)(κ2-R′2PCH2PiPr2)] and in
particular their reactivities toward CO and Broensted
acids. As chelating bis(phosphino)methanes, those with
R′ ) iPr, C6H11 (Cy), and Ph have been used, which were
prepared by a new synthetic route from Ph3SnCH2PiPr2
(1) (a) Scha¨fer, M.; Wolf, J .; Werner, H. J . Chem. Soc., Chem.
Commun. 1991, 1341-1343. (b) Werner, H.; Scha¨fer, M.; Nu¨rnberg,
O.; Wolf, J . Chem. Ber. 1994, 127, 27-38.
(5) (a) Manger, M. Dissertation, Universita¨t Wu¨rzburg, 1997. (b)
Wolf, J .; Manger, M.; Barth, D.; Werner, H. To be submitted for
publication.
(6) (a) Manger, M.; Wolf, J .; Laubender, M.; Teichert, M.; Stalke,
D.; Werner, H. Chem.sEur. J . 1997, 3, 1442-1450. (b) Werner, H.;
Manger, M.; Schmidt, U.; Weberndo¨rfer, B. Organometallics 1998, 17,
2617-2627.
(7) Werner, H.; Stalke, D.; Wolf, J .; Manger, M.; Schmidt, U.; Gevert,
O.; Laubender, M.; Teichert, M. In Selective Reactions of Metal-
Activated-Molecules, Vol. 3; Werner, H.; Schreier, P., Eds.; Vieweg
Verlag: Braunschweig, Germany, 1998.
(2) Sivak, A. J .; Muetterties, E. L. J . Am. Chem. Soc. 1979, 101,
4878-4887.
(3) (a) Thorn, D. L.; Ibers, J . A. Adv. Chem. Ser. 1982, 196, 117-
131. (b) Murray, B. D.; Power, P. P. Organometallics 1984, 3, 1199-
1204.
(4) (a) Fryzuk, M. D. Inorg. Chem. 1982, 21, 2134-2139. (b) Fryzuk,
M. D. Can. J . Chem. 1983, 61, 1347-1351. (c) Fryzuk, M. D.; J ones,
T.; Einstein, F. W. B. Organometallics 1984, 3, 185-191. (d) Fryzuk,
M. D.; Piers, W. E. Organomet. Synth. 1986, 3, 128-135. (e) Fryzuk,
M. D.; Piers, W. E. Can. J . Chem. 1989, 67, 883-896.
S0276-7333(98)00062-4 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 06/26/1998

(π-Allyl)rhodium(I) Complexes
Sch em e 1
Organometallics, Vol. 17, No. 15, 1998 3211
Sch em e 2
isolated in 60-80% yield. The yellow to orange-yellow
solids are quite air-sensitive, are thermally only mod-
erately stable, but can be stored at -20 °C for days. In
chlorinated solvents, they slowly decompose. With
regard to the mechanism of formation of 2-7 from the
intermediate [Rh(η3-C3H5)(η4-C8H12)], we assume that
in the initial step a nucleophilic attack of the phosphine
on the metal occurs which is followed by the displace-
ment of the diolefin. This mechanistic scheme is sup-
ported by recent investigations of Power et al., who
isolated the 18-electron compounds [M(η3-2-MeC3H4)-
(η4-C8H12)(PHtBu2)] (M ) Rh, Ir) upon treatment of the
(π-allyl)rhodium and -iridium precursors with PHtBu2.3b
The 1H, 13C, and 31P NMR data of the new bis-
(phosphino)methane rhodium complexes support the
structural proposal shown in Scheme 1. Besides the
expected sets of signals for the C3H5 and 2-CH3C3H4
ligands,1-3,8 the 1H NMR spectra of 2-7 display four
resonances for the protons of the diastereotopic methyl
groups of the PiPr2 unit(s), which due to 31P,1H and
1H,1H coupling are split into doublets of doublets. The
most characteristic feature of the 1H NMR spectra,
however, is that the signal for the methylene protons
of the PCH2P′ fragment appears as a multiplet which
after 31P decoupling gives the line shape of an AB
system. The geminal coupling between the CH2 protons
is ca. 15 Hz. The fact that only one of the signals for
the methylene protons shows an 103Rh,1H coupling could
be explained by the difference in the torsional angles
at the PCH2P′ unit of the (unsymmetrical) four-
membered chelate ring, similar to the situation of the
Karplus type.9
largest in the Rh(iPr2PCH2CH2PiPr2) and smallest in
the Rh(R′2PCH2PiPr2) derivatives. With this stereo-
chemical argument, the size of the 103Rh,31P coupling
constant can also be rationalized, which for the bis-
(phosphino)methane complexes 2-7 is smaller by about
20-25 Hz compared with those of [Rh(η3-1-MeC3H4)(κ2-
iPr2PCH2CH2PiPr2)] and [Rh(η3-2-MeC3H4)(PMe3)-
(PiPr3)].
Rea ction s of th e π-Allyl Com p lexes w ith Br oen -
sted Acid s. Following recent work from our labora-
tory,1,10 which showed that, in rhodium(I) complexes of
the general composition [Rh(η3-2-RC3H4)(L)2], the allyl-
metal bond can be easily cleaved by protic reagents, the
reactivity of 2-4 toward Broensted acids HX was
investigated. If a solution of 2, 3, or 4 in ether is stirred
under an atmosphere of HCl at -30 °C, a rapid change
of color from orange-yellow to almost colorless occurs.
After a short period of time, an off-white or pale yellow
solid precipitates, the elemental analysis of which
corresponds to [RhHCl2(κ2-R′2PCH2PiPr2)] (8-10). To
explain the formation of these compounds, we assume
(see Scheme 2) that, in agreement with recent results,1b
in the initial step of the reaction an oxidative addition
of HCl to the metal center takes place, followed by
elimination of propene to afford the short-lived inter-
mediate [RhCl(κ2-R′2PCH2PiPr2)]. This 14-electron spe-
cies then reacts with a second molecule of the acid to
give the final product.
The 31P NMR data of 2-7 deserve one more comment.
While the spectra of 2 and 5 with iPr2PCH2PiPr2 as
ligand display a sharp doublet, the spectra of 3, 4 and
6, 7 show two doublet of doublets due to the inequiva-
lence of the two 31P nuclei. The values for the coupling
constants 1J (103Rh,31P) are in the range 168-177 Hz,
and in the case of 3, 4, 6, and 7, those of 2J (31P,31P) are
between 66 and 73 Hz. In particular, the size of the
phosphorus-phosphorus coupling is considerably dif-
ferent from that of the nonchelate compound [Rh(η3-2-
MeC3H4)(PMe3)(PiPr3)] (25.5 Hz)1 and of the unsym-
metrical chelate complex [Rh(η3-1-MeC3H4)(κ2-iPr2-
PCH2CH2PiPr2)] (17.1 Hz).4c A reasonable explanation
for this result is that in the (π-allyl)rhodium compounds
the P-Rh-P bond angles differ significantly, being
1
The H NMR spectra of the hydrido complexes 8-10,
which are formed from 2-4 in virtually quantitative
yield, display a resonance in the high-field region at δ
-15 to -16. At room temperature, this signal is
somewhat broadened, but in the case of 8, it sharpens
upon warming to 318 K to give a doublet of triplets. For
9 and 10, both at 295 and 325 K, a multiplet for the
hydride ligand is observed.
The conclusion, which can be drawn from the vari-
able-temperature 1H NMR spectra, that the five-
coordinate compounds 8-10 possess a fluctional struc-
(8) (a) Clerici, M. G.; Di Gioacchino, S.; Maspero, F.; Perotti, E.;
Zanobi, A. J . Organomet. Chem. 1977, 84, 379-388. (b) Stu¨hler, H.-
O.; Mu¨ller, J . Chem. Ber. 1979, 112, 1359-1364. (c) Stu¨hler, H.-O. Z.
Naturforsch., B: Anorg. Chem., Org. Chem. 1980, 35, 340-342.
(9) (a) Karplus, M. J . Chem. Phys. 1959, 30, 11-15. (b) Bothner-
By, A. A.; Cox, R. H. J . Phys. Chem. 1969, 73, 1830-1834.
(10) Kukla, F. Dissertation, Universita¨t Wu¨rzburg, 1997.

3212 Organometallics, Vol. 17, No. 15, 1998
Manger et al.
K a further splitting of the resonance appearing at
higher field is observed. At 263 K, the pattern of this
signal is consistent with the AB part of an ABX
spectrum and confirms the stereochemical inequivalence
of the two PiPr2 units. Continuous cooling of the
solution of 8 in CDCl3 to 248 K leads only to a slight
high-field shift of the ABX-type resonance while the
position of the doublet signal remains unchanged.
To rationalize the temperature dependence of the 31
P
NMR spectrum of 8, we assume that at low-temperature
two diastereomers 8′ and 8′′ exist in solution which both
have a square-pyramidal configuration. At higher tem-
perature, these isomers interconvert into each other.
The argument that five-coordinate rhodium(III) com-
plexes of the general type [RhXY2(L)2] prefer instead of
a trigonal-bipyramidal a square-pyramidal geometry is
supported by the X-ray crystal structure analysis of [Rh-
(COMe)I2(κ2-Ph2PCH2PPh2)]11e as well as by the struc-
tural and spectroscopic data of related compounds with
two monodentate phosphine ligands in cis disposi-
tion.11,12
By use of an updated program for NMR spectral
analysis,13 the values of the chemical shifts and coupling
constants of the AB part of the ABX spectrum of isomer
8′′ have been calculated. The calculation provides two
sets of data of which one [δ(PA) 16.0, δ(PB) 15.3; 2J (PAPB)
) 68.2, 1J (RhPA) ) 112.9, 1J (RhPB) ) 113.8 Hz] fits
quite well with the experiment.14 Isomer 8′′, which has
a rigid structure below 263 K on the NMR time scale,
rearranges at higher temperature reversibly to 8′,
possibly by a variation of the Berry mechanism.15 We
assume that a similar intramolecular fluctuation also
occurs for compounds 9 and 10, although an exact
analysis of the 31P NMR spectra is not possible in these
cases.
The reactions of 2 and 3 with trifluoracetic acid and
trifluoromethanesulfonic acid also lead to the formation
of rhodium(III) complexes of the general composition
[RhHX2(κ2-R′2PCH2PiPr2)] (Scheme 3). By analogy to
the behavior of [Rh(η3-C3H5)(PiPr3)2] toward CF3CO2H1
and CF3SO3H,16 we anticipated that the starting ma-
terials 2 and 3 would react with 1 equiv of these acids
to afford four-coordinate rhodium(I) compounds [Rh(η2-
X)(κ2-R′2PCH2PiPr2)] (X ) O2CCF3, O3SCF3). Indeed,
these species could be formed as intermediates, but in
the presence of HX, they are probably very labile and
rapidly react with HX to give the isolated products 11
and 12. Even if a solution of 2 in ether/pentane is
treated at -78 °C with an equimolar amount of CF3-
SO3H (or a solution of 3 is treated with an equimolar
amount of CF3CO2H), compounds 11 and 12 are exclu-
sively formed with a yield of 50%. For the preparation
of pure samples of 11 and 12, however, it is important
F igu r e 1. Variable-temperature 31P NMR spectra of
compound 8 (in CDCl3).
ture in solution, is substantiated by the VT 31P NMR
data. For 8 as the most symmetrical molecule, the
temperature dependence of the 31P NMR spectra is
shown in Figure 1. At 295 K, two broadened doublets
appear at δ 16.5 and 15.7, revealing a 103Rh,31P coupling
of ca. 113 Hz that is typical for rhodium(III) complexes
with two cis-disposed phosphine ligands.11 Upon an
increase in temperature, the two signals coalesce and,
at 318 K, finally give one relatively sharp doublet with
1J (RhP) ) 114.1 Hz. Under these conditions, the two
31P nuclei are chemically equivalent on the NMR time
scale. When the temperature is lowered, already at 288
(12) Harlow, R. L.; Thorn, D. L.; Baker, R. T.; J ones, N. L. Inorg.
Chem. 1992, 31, 993-997.
(13) Fuhler, R.; Lenzen, Th.; Ha¨gele, G. SpinA-AT Spin-Analyse
Programm V 1.00. Universita¨t Du¨sseldorf, 1993.
(14) For details of the simulation of the spectra, see ref 5a.
(15) (a) Ugi, I.; Marquarding, D.; Klusacek, H.; Gockel, G.; Gillespie,
P. Angew. Chem. 1970, 82, 741-771; Angew. Chem., Int. Ed. Engl.
1970, 9, 703-730. (b) Gillespie, P.; Hoffmann, P.; Klusacek, H.;
Marquarding, D.; Pfohl, S.; Ramirez, F.; Tsolis, E. A.; Ugi, I. Angew.
Chem. 1971, 83, 691-721; Angew. Chem., Int. Ed. Engl. 1971, 10, 687-
715. (c) Ugi, I.; Marquarding, D.; Klusacek, H.; Gillespie, P.; Ramirez,
F. Acc. Chem. Res. 1971, 4, 288-296. (d) Kutzelnigg, W.; Wasilewski,
J . J . Am. Chem. Soc. 1982, 104, 953-960.
(11) (a) Cheng, C.; Spivack, B. D.; Eisenberg, R. J . Am. Chem. Soc.
1977, 99, 3003-3011. (b) Cheng, C.; Eisenberg, R. Inorg. Chem. 1979,
18, 1418-1424. (c) McGuiggan, M. F.; Doughty, D. H.; Pignolet, L. H.
J . Organomet. Chem. 1980, 185, 241-249. (d) Shie, J .-Y.; Lin, Y.-C.;
Wang, Y. J . Organomet. Chem. 1989, 371, 383-392. (e) Adams, H.;
Bailey, N. A.; Mann, B. E.; Manuel, C. P. Inorg. Chim. Acta 1992, 198-
200, 111-118.
(16) Schneider, M. E. Dissertation, Universita¨t Wu¨rzburg, 1997.

(π-Allyl)rhodium(I) Complexes
Organometallics, Vol. 17, No. 15, 1998 3213
Sch em e 3
to use not more than 2 equiv of the corresponding acid
because an excess of acid is difficult to remove.
Like the chloro derivatives 8 and 9, the hydridobis-
(trifluoracetato)- and hydridobis(triflato)rhodium(III)
complexes 11 and 12 are air-stable solids which are
readily soluble in polar organic solvents. In solution
(even in CHCl3), both 11 and 12 slowly decompose. In
contrast to the IR spectrum of 11, which indicates that
one monodentate and one bidentate carboxylato ligand
is coordinated,17,18 the IR spectrum of 12 at room
temperature provides no evidence for a chelating bond-
ing mode of the O3SCF3 units.19
F igu r e 2. 31P NMR spectrum of compound 12 (in CD2Cl2)
at 243 K. The asterisks represent the isomer with chemi-
cally equivalent 31P nuclei.
The NMR spectra of 11 and 12 indicate that both
complexes are fluctional in solution. The 31P NMR
spectrum of 11 displays (in CD2Cl2) at room tempera-
ture two very broad signals for the PiPr2 and PCy2
phosphorus nuclei at δ ca. 17.5 and 7.7. At 313 K, the
AB pattern of the PAPBRh ABX spin system is observed
which represents the high-temperature limiting spec-
trum of the fluctional process. Upon a decrease in
temperature below 295 K, further broadening of the
phosphorus resonances occurs and a complicated signal
pattern at 193 K points to a transitional dynamic
regime. It proved impossible to obtain the low-temper-
ature limiting spectrum. That the high-temperature
dynamics observed in the 31P NMR spectra indeed
reflect a ligand-scrambling process is supported by the
appearance of two broad hydride resonances at δ -17.60
Sch em e 4
gous to the dichloro derivatives 8′ and 8′′ (see Scheme
2), respectively. Further cooling of the solution of 12
in CD2Cl2 leads to an additional splitting of the signals
which due to its complexity cannot be exactly analyzed.
We suppose that, under these conditions, the molecule
possesses a rigid configuration with one monodentate
and one bidentate O3SCF3 unit.
1
and -17.85 in the H NMR spectrum at 295 K which
To test whether the dynamic behavior observed for 8
and 12 also exists for related species not underlying the
ring strain of the Rh(κ2-R′2PCH2PiPr2) system, the
π-allyl complex 13 was treated with excess HCl as well
as with 2 equiv of CF3SO3H. In both cases, elimination
of propene occurred and the corresponding hydrido-
rhodium(III) compounds 14 and 15 (Scheme 4) were
formed in nearly quantitative yield. The pale yellow
solids are air-stable and can be stored at room temper-
ature for weeks. In contrast to the chloro derivative 14,
which according to the spectroscopic data has a rigid
structure at room temperature, the triflato complex 15
coalesce upon raising the temperature. In the case of
the bis(triflato) compound 12, a single doublet resonance
is observed in the 31P NMR spectrum (in CD2Cl2) at 313
K, which indicates a rapid scrambling of the hydrido
and triflato ligand positions. Upon cooling, at 243 K
two 31P resonance patterns are observed representing
an AA′X and an ABX spin system which appear super-
imposed in Figure 2. We assign these resonances to the
two possible configurational isomers 12′ and 12′′ analo-
(17) For IR data of (carboxylato)metal complexes, see: (a) Robinson,
S. D.; Uttley, M. F. J . Chem. Soc., Dalton Trans. 1973, 1912-1920.
(b) Deacon, G. B.; Phillips, R. J . Coord. Chem. Rev. 1980, 33, 227-
250. (c) Tocher, D. A.; Gould, R. O.; Stephenson, T. A.; Bennett, M. A.;
Ennett, J . P.; Matheson, T. E.; Sawyer, L.; Shah, V. K. J . Chem. Soc.,
Dalton Trans. 1983, 1571-1581. (d) Oldham, C. In Comprehensive
Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J .
A., Eds.; Pergamon: Oxford, U.K., 1987; Vol. 2, pp 435-439.
(18) Scha¨fer, M.; Wolf, J .; Werner, H. J . Organomet. Chem. 1994,
476, 85-91.
under these conditions is fluctional in solution. The 31
P
NMR spectrum of 15 displays at 295 K a broad multiplet
which upon an increase in temperature sharpens and
at 308 K becomes a doublet with a 103Rh,31P coupling
of 141 Hz. A similar observation has been made for the
hydride resonance in the 1H NMR spectrum of 15. Due
to the number and splitting of the signals for the CH3
(19) (a) Lawrance, G. A. Chem. Rev. 1986, 86, 17-33. (b) Harding,
P. A.; Robinson, S. D. J . Chem. Soc., Dalton Trans. 1987, 947-952.

3214 Organometallics, Vol. 17, No. 15, 1998
Manger et al.
Sch em e 5
F igu r e 3. Molecular structure (ORTEP plot) of compound
16.
The 31P NMR spectrum of 16 shows at 295 K one
broadened doublet which sharpens upon lowering the
temperature. Compared to that of the precursor com-
plex 2, the 103Rh,31P coupling constant decreases from
169 to 129 Hz. The assumption that 16 (as well as 17
and 18) possesses a nonrigid structure in solution is
confirmed by VT 1H NMR measurements. While at 295
1
K the H NMR spectrum of 16 displays one unresolved
broad signal at δ 2.56 (with the relative intensity of 4H)
for the CH2 protons of the allyl ligand, at 233 K two
resonances at δ 2.90 and 2.09 appear, the latter over-
lapping with the signal of the PCH2P protons. In
agreement with previous studies,2-4,22 the signal at
lower field (δ 2.90) is assigned to the syn and that at
higher field (δ 2.09) to the anti protons of the CH2
groups. The nonrigidity of 16 (and also of 17 and 18),
which is likewise indicated by the line shape of the
resonances in the 13C NMR spectra, is probably due to
a π-σ-π rearrangement of the C3H5 unit as is known
for other compounds of the general type [M(η3-RC3H4)-
(L)(L′)2].23
protons of the isopropyl groups, we assume that the
average structure of 15 is a square pyramid of symmetry
CS with η1-bonded triflato ligands. Therefore, the
fluctionality of the molecule probably consists of a
concerted change of hapticity between η1 and η2 but not
in a Berry-type rearrangement as discussed for com-
pound 8.
The structural proposal for 16, as shown in Scheme
5, has been substantiated by an X-ray crystal structure
analysis. The ORTEP drawing (Figure 3) reveals that,
provided that the C3H5 moiety is taken as a bidentate
ligand, the rhodium is coordinated in a distorted square-
pyramidal fashion. Thereby, the basal plane of the
pyramid is occupied by the phosphorus atoms and the
allylic CH2 carbon atoms, in close analogy to the
situation found for the related cationic complex [Ir(η3-
C3H5)(NO)(PPh3)2]+.24 The configuration of the C3H5
unit of 16 is such that the anti protons of the allyl
moiety point into the direction of the apical CO group.
Since the angle between the planes [C(1),C(2),C(3)] and
[P(1),Rh,P(2)] is 64.3°, the distance Rh-C(2) is shorter
than the corresponding distances Rh-C(1) and Rh-C(3)
Rea ction s of th e π-Allyl Com p lexes w ith CO.
Like the bis(triisopropylphosphine) compound [Rh(η3-
C3H5)(PiPr3)2],1,20 the bis(phosphino)methane deriva-
tives 2-4 also react quite rapidly with CO, in pentane
even at -40 °C (Scheme 5). During the reaction, a
characteristic change of color from orange-yellow to
orange-red and finally to pale yellow is observed. In
the case of 2 and 3 as the starting materials, after
removal of the solvent, deep yellow or orange-yellow
solids are isolated, the elemental analyses of which
correspond to [Rh(C3H5)(CO)(R′2PCH2PiPr2)] (16, 17).
The product 18 obtained from 4 and CO is an oily
substance which could only be characterized by spec-
troscopic techniques. Compounds 16 and 17 are only
moderately air-sensitive but thermally rather unstable.
In solvents such as CHCl3, CH2Cl2, or CH3OH, they
slowly decompose. A typical feature of 16-18 is the
strong ν(CO) stretch at 1940-2000 cm-1 in the IR
spectra, which appears at positions similar to those of
(22) Reilly, C. A.; Thyret, H. J . Am. Chem. Soc. 1967, 89, 5144-
5149.
(23) (a) Vrieze, K.; Volger, H. C.; van Leeuwen, P. W. N. M. Inorg.
Chim. Acta Rev. 1969, 3, 109-128. (b) Vrieze, K.; van Leeuwen, P. W.
N. M. Prog. Inorg. Chem. 1971, 14, 1-63. (c) Muetterties, E. L.;
Hirsekorn, F. J . J . Am. Chem. Soc. 1974, 96, 7920-7926. (d) Faller, J .
W. Adv. Organomet. Chem. 1977, 16, 211-239. (e) Thompson, M. R.;
Day, V. W.; Tau, K. D.; Muetterties, E. L. Inorg. Chem. 1981, 20, 1237-
1241. (f) Calligaris, M.; Carturan, G.; Nardin, G.; Scrivanti, A.;
Wojcicki, A. Organometallics 1983, 2, 865-873.
[Rh(η3-C3H5)(CO)(PiPr3)2] (1960 cm-1 20
C3H5)(CO)(PPh3)2] (1955 cm-1).21
)
and [Rh(η3-
(20) Scha¨fer, M. Dissertation, Universita¨t Wu¨rzburg, 1994.
(21) Brown, C. K.; Mowat, W.; Yagupsky, G.; Wilkinson, G. J . Chem.
Soc. A 1971, 850-859.
(24) Schoonover, M. W.; Baker, E. C.; Eisenberg, R. J . Am. Chem.
Soc. 1979, 101, 1880-1882.

(π-Allyl)rhodium(I) Complexes
Organometallics, Vol. 17, No. 15, 1998 3215
Ta ble 1. Selected Bon d Dista n ces a n d An gles
w ith Esd ’s for Com p ou n d 16
the intensity ratio 1:1:1:2, the chemical shift and
coupling constants of which are similar to those of
related acylmetal compounds.27 The most typical reso-
nance is that of the single CHd proton, which, owing
to the different H,H couplings with the adjacent four
protons of the CH2CHdCH2 moiety, is split into a
doublet of doublets of triplets.
Bond Distances (Å)
Rh-C(1)
Rh-C(2)
Rh-C(3)
C(1)-C(2)
C(2)-C(3)
2.213(2)
2.125(2)
2.187(2)
1.404(3)
1.408(3)
Rh-P(1)
2.303(1)
2.286(1)
1.927(2)
1.140(2)
1.853(2)
1.846(2)
Rh-P(2)
Rh-C(4)
C(4)-O(1)
P(1)-C(10)
P(2)-C(10)
Reliable 13C NMR data of 19 providing valuable
information about the structure of this complex have
been obtained from the isotopomer 19a generated from
2 and 13CO. The 13C NMR spectrum (measured under
an atmosphere of 13CO) of this product in the region of
the CO nuclei is shown in Figure 4. For the carbon
atoms of the two carbonyl ligands, only one resonance
appears at δ 201.5, which confirms the equivalence of
these ligands. The resonance is split into a doublet of
doublets of doublets of doublets due to couplings with
the 103Rh, the two different 31P, and the acylic 13C(O)
nuclei. A similar splitting results for the signal of the
acyl carbon atom at δ 235.1, which is a doublet of
doublets of doublets of triplets. The small value of 2.4
Hz for the coupling constant 2J (13CE,13CAc) (for the
assignment of the hydrogen, carbon, and phosphorus
atoms of 19, 19a , and 20 see the Experimental Section)
indicates that the carbonyl and the acyl ligands are
probably orthogonal to each other.
The 31P NMR spectrum of the 13CO-labeled isoto-
pomer 19a is also in excellent agreement with the
proposed structure for the insertion product. Instead
of two doublets of doublets for the nonlabeled complex,
it displays two doublets of doublets of doublets of
triplets, the additional splitting being due to couplings
between 31P and the different 13CO nuclei. A charac-
teristic feature is the large coupling between the phos-
phorus in the apical position and the acyl carbon atom,
which confirms that these two nuclei are trans disposed.
By using 13CO and compound 16 as the starting
materials, we can obtain some information about the
course of the insertion process. The 13C NMR spectrum
of the product, which is formed upon passing a slow
stream of 13CO through a solution of 16 in toluene-d8
at 233 K, displays for the carbon atoms of the CO
ligands a doublet of doublets of doublets due to 103Rh,13C
and 31P,13C couplings. Since no coupling between CE
and CAc (see Experimental Section) can be observed, we
conclude that the π-allyl complex 16 is in equilibrium
with the σ-bonded isomer 23, which after attack of 13CO
affords the acylcarbonyl derivative 24 (Scheme 6). This
species obviously reacts faster with a second molecule
of 13CO than it rearranges to the isomeric 18-electron
compound [Rh(η1-C3H5)(CO)2(κ2-iPr2PCH2PiPr2)]. We
note that the formation of the acyliridium complex [Ir-
{C(O)C3H4R}(CO)2(PPh3)2] from [Ir(η3-RC3H4)(CO)2-
(PPh3)2] and carbon monoxide proceeds by a different
mechanism, the initial step being the substitution of one
phosphine ligand by CO.21
Bond Angles (deg)
P(1)-Rh-P(2)
P(1)-C(10)-P(2)
Rh-P(1)-C(10)
Rh-P(2)-C(10)
P(1)-Rh-C(4)
P(2)-Rh-C(4)
72.42(2)
Rh-C(4)-O(1)
C(1)-C(2)-C(3)
Rh-C(1)-C(2)
Rh-C(2)-C(1)
Rh-C(2)-C(3)
Rh-C(3)-C(2)
177.2(2)
116.8(2)
67.77(11)
74.53(11)
73.33(12)
68.59(11)
94.27(8)
96.05(6)
96.84(6)
108.16(6)
111.10(6)
(Table 1). The bond length between the metal and the
CO ligand is 1.927(2) Å and thus about 0.1 Å larger than
those in square-planar rhodium(I) compounds trans-
[Rh(R)(CO)(PiPr3)2].25
The (π-allyl)carbonylrhodium(I) complexes 16-18 are
not the only products obtained from the starting materi-
als and carbon monoxide. As mentioned above, from
2-4 and excess CO, a pale yellow solution is formed
from which, after removal of the solvent in vacuo, deep
yellow or orange-yellow compounds 16-18 are isolated.
However, if the pale yellow solution formed from 2 is
stored under a CO atmosphere at -78 °C, an almost
white solid precipitates. According to the IR and NMR
spectroscopic data, its composition corresponds to that
of the acyl complex [Rh{C(O)CH2CHdCH2}(CO)2(κ2-
iPr2PCH2PiPr2)] (19). From 4 and CO, as well as from
the π-benzyl derivative 21, first prepared by Fryzuk
et al.,26 and carbon monoxide related products,
[Rh{C(O)CH2CHdCH2}(CO)2(κ2-Ph2PCH2PiPr2)] (20) and
[Rh{C(O)CH2Ph}(CO)2(κ2-iPr2PCH2PiPr2)] (22) are ob-
tained. Compound 20 is extremely labile and loses CO
rapidly upon removing the CO atmosphere. The dicar-
bonyl complexes 19 and 20 can also be generated from
16 or 18 and carbon monoxide.
The structural proposals (based on the spectroscopic
data) for 19, 20, and 22 are shown in Scheme 5. The
IR spectrum of 19 confirms that, besides two metal-
bonded CO ligands (exemplified by ν(CO) bands at 1974
and 1940 cm-1), an acyl unit is present. The CdO
stretching frequency appears at 1699 cm-1, which is in
the same region as that for the corresponding iridium
complex [Ir{C(O)C3H5}(CO)2(PPh3)2].21 The 31P NMR
spectrum of 19 (which, like those of 20 and 22, has to
be measured at low temperature in the presence of CO)
displays in toluene-d8 two doublets of doublets at δ 10.3
and 3.2, which differ considerably in the sizes of the
103Rh,31P coupling constants. For 22, similar data have
been obtained. In contrast, the 31P NMR spectrum of
20 displays, due to the asymmetry of the bis(phosphino)-
methane ligand, two sets of signals, indicating that in
solution two isomers exist. We assume that both have
a trigonal-bipyramidal configuration, one with the PiPr2
and the other with the PPh2 unit in an apical position.
The carbon-metal bond of 19 is easily cleaved in the
presence of HCl. If a slow stream of HCl is passed
through a solution, which is generated from 2 and excess
CO in ether/hexane at -40 °C, a pale yellow solid
1
In the H NMR spectra of 19 and 20, four signals for
the protons of the C(O)CH2CHdCH2 ligand appear in
(25) (a) Wiedemann, R.; Steinert, P.; Scha¨fer, M.; Werner, H. J . Am.
Chem. Soc. 1993, 115, 9864-9865. (b) Werner, H.; Wiedemann, R.;
Mahr, N.; Steinert, P.; Wolf, J . Chem.sEur. J . 1997, 3, 127-137.
(26) Fryzuk, M. D.; McConville, D. H.; Rettig, S. J . J . Organomet.
Chem. 1993, 445, 245-256.
(27) (a) Volger, H. C.; Vrieze, K. J . Organomet. Chem. 1968, 13, 495-
503. (b) Ozawa, F.; Son, T.; Osakada, K.; Yamamoto, A. J . Chem. Soc.,
Chem. Commun. 1989, 1067-1068. (c) Dire`, S.; Campostrini, R.;
Carturan, G.; Calligaris, M.; Nardin, G. J . Organomet. Chem. 1990,
390, 267-274.

3216 Organometallics, Vol. 17, No. 15, 1998
Manger et al.
F igu r e 4. 13C NMR spectrum of compound 19a (in toluene-d8) at 233 K in the region of the signals of the Rh-CO and the
acyl CO carbon atoms.
(CO)2(κ2-R′2PCH2PiPr2)] as the final products. These
Sch em e 6
novel five-coordinate (albeit very labile) rhodium(I)
compounds are formed via the 1:1 adducts [Rh(η3-
C3H5)(CO)(κ2-R′2PCH2PiPr2)], of which one (with R′ )
iPr) has been characterized by X-ray crystal structure
analysis. At 233 K, the 18-electron acyl complexes are
relatively inert but, at room temperature, lose CO
reversibly to generate the monocarbonyl species. The
stepwise conversion, e.g. of 2 via 16 to 19 (Scheme 5),
is reminiscent of the mechanistic scheme proposed for
the hydroformylation reaction, where the insertion/
deinsertion of CO into an alkyl-metal bond plays a
dominant role.28,29
The π-allyl complexes [Rh(η3-C3H5)(κ2-R′2PCH2PiPr2)]
are highly reactive not only toward CO but also toward
Broensted acids HX. With the latter they react smoothly
by complete cleavage of the allyl-metal bond. Despite
several attempts, it has not been possible, however, to
prove that the attack of HX leads initially to the
formation of the expected (π-allyl)hydridorhodium(III)
precipitates, which, from the IR and NMR spectroscopic
species [RhH(η3-C3H5)X(κ2-R′2PCH2PiPr2)]. Since com-
data, is a mixture of 8 and 25 (see Scheme 7) in a ratio
of approximately 1:5. In the solution, the unsaturated
aldehyde CH2dCHCH2CHO (26) can be detected by
pounds of this type with Rh(PiPr3)2 instead of Rh(κ2-
R′2PCH2PiPr2) as the building block are known,1,20 we
assume that it is the ring strain of the chelate system
which determines the lability of the products formed by
oxidative addition of HX to the metal center.
1
both GC/MS and H NMR spectroscopy. The carbonyl
complex 25 is rather labile and in chloroform at room
temperature loses CO slowly to give 8. Under the same
conditions, in the presence of excess carbon monoxide,
the reverse reaction from 8 to 25 does not occur. Since
attempts to separate the two hydridorhodium(III) com-
pounds by fractional crystallization or column chroma-
tography failed, the carbonyl derivative was character-
ized by spectroscopic techniques. The 31P NMR spectrum
of 25 displays two doublets of doublets at δ 17.4 and
-12.2, both of which show a 103Rh,31P coupling of about
90 Hz. This is in agreement with the oxidation state
+III for rhodium. In the 13C NMR spectrum of 25, the
carbonyl resonance appears at δ 183.2 as a doublet of
doublets of doublets. The two phosphorus-carbon
coupling constants of this signal are extremely different
(144.1 and 4.4 Hz), indicating that one 31P nucleus is
trans and the other is cis disposed to the CO ligand.
Exp er im en ta l Section
All reactions were carried out under an atmosphere of argon
by Schlenk tube techniques. The starting materials [RhCl-
(η4-C8H12)]2 (1),30 [Rh(η3-CH2Ph)(κ2-iPr2PCH2PiPr2)] (21),26 and
R′2PCH2PiPr2 (R′ ) iPr, Cy, Ph)5 were prepared as described
in the literature. NMR spectra were recorded on Bruker AC
200 and AMX 400 instruments, and IR spectra, on a Perkin-
Elmer 1420 infrared spectrophotometer. Melting points were
measured by DTA. Assignment for protons of η3-allyl
ligands: HM ) proton at central carbon; HA and HA′ ) protons
of CH2 groups anti to HM; HS and HS′ ) protons of CH2 groups
3
5
4
syn to HM. N ) J (PH) + J (PH) or 2J (PC) + J (PC).
P r ep a r a tion of [Rh (η3-C3H5)(K2-iP r 2P CH2P iP r 2)] (2). A
suspension of 1 (237 mg, 0.49 mmol) in 10 mL of ether was
(28) (a) Collman, J . P.; Hegedus, L. S.; Norton, J . R.; Finke, R. G.
Principles and Application of Organotransition Metal Chemistry;
University Science Books: Mill Valley, CA, 1987. (b) Elschenbroich,
C.; Salzer, A. Organometallchemie, 3rd ed.; Teubner: Stuttgart,
Germany, 1990. (c) Yamamoto, A. Organotransition Metal Chemistry;
Wiley: New York, 1986.
Con clu sion s
The present work has shown that the (π-allyl)-
rhodium(I) complexes [Rh(η3-C3H5)(κ2-R′2PCH2PiPr2)],
which contain bulky symmetrical or unsymmetrical bis-
(phosphino)methanes as ligands, react with CO stepwise
to give the acyl derivatives [Rh{C(O)CH2CHdCH2}-
(29) For acylrhodium complexes, see: (a) Keim, W. J . Organomet.
Chem. 1969, 19, 161-168. (b) Yagupsky, G.; Brown, C. K.; Wilkinson,
G. J . Chem. Soc. A 1970, 1392-1401. (c) Casey, C. P.; Whiteker, G.
T.; Melville, M. G.; Petrovich, L. M.; Gavney, J . A., J r.; Powell, D. R.
J . Am. Chem. Soc. 1992, 114, 5535-5543.
(30) Crabtree, R. H.; Giordano, G. Inorg. Synth. 1990, 28, 88-90.

(π-Allyl)rhodium(I) Complexes
Organometallics, Vol. 17, No. 15, 1998 3217
Sch em e 7
1
treated under vigorous stirring at -20 °C with a 1.22 M
solution of C3H5MgBr (0.80 mL, 0.98 mmol) in ether. A change
of color from orange-yellow to yellow occurred, and a white
solid precipitated. The reaction mixture was stirred for 15
min, and then a solution of iPr2PCH2PiPr2 (241 mg, 0.98 mmol)
in 3 mL of hexane was added dropwise. After the solution
was slowly warmed to room temperature, the solvent was
removed in vacuo. The remaining residue was extracted three
times with 10-mL portions of pentane, the combined extracts
were filtered, and the filtrate was brought to dryness in vacuo.
The oily residue was dissolved in 3 mL of acetone, and after
the solution was stored for 18 h at -78 °C, orange-yellow
crystals were isolated: yield 310 mg (81%); mp 73 °C dec. Anal.
Calcd for C16H35P2Rh: C, 48.99; H, 8.99. Found: C, 48.68; H,
8.89. 1H NMR (C6D6, 400 MHz): δ 4.80 (dtt, J (RhHM) ) 1.6,
Hz, 1H, PCH2P), 2.21, 2.19 (both m, in H{31P} both d, J (HMH)
) 13.1 Hz, 2H, HA and HA′), 2.02-1.23 (br m, 24H, PCHCH3
and C6H11), 1.16 (dd, J (PH) ) 14.8, J (HH) ) 7.2 Hz, 6H,
PCHCH3), 1.09 (dd, J (PH) ) 14.8, J (HH) ) 7.2 Hz, 3H,
PCHCH3), 1.07 (dd, J (PH) ) 14.0, J (HH) ) 7.1 Hz, 3H,
PCHCH3). 13C NMR (C6D6, 100.6 MHz): δ 108.3 (br m, η3-
H2C-CH-CH2), 47.9 (dd, J (RhC) ) 6.3, J (PC) ) 27.4 Hz, η3-
H2C-CH-CH2], 47.5 (dd, J (RhC) ) 6.5, J (PC) ) 27.0 Hz, η3-
H2C-CH-CH2), 37.1 (ddd, J (RhC) ) 2.5, J (P1C) ) 10.9, J (P2C)
) 5.7 Hz, PCHCH2), 36.7 (dd, J (RhC) ) 2.9, J (PC) ) 9.1 Hz,
PCHCH2), 35.1 (dt, J (RhC) ) 1.9, J (P1C) ) J (P2C) ) 13.3 Hz,
P1CH2P2), 30.5 (d, J (PC) ) 3.3 Hz, CH2 of C6H11), 30.4 (d, J (PC)
) 5.5 Hz, CH2 of C6H11), 30.2 (d, J (PC) ) 3.0 Hz, CH2 of C6H11),
29.9 (d, J (PC) ) 4.5 Hz, CH2 of C6H11), 27.7, 27.6, 27.5, 27.4,
26.9, 26.6 (all s, CH2 of C6H11), 26.5 (m, PCHCH3), 26.3 (dd,
J (RhC) ) 4.2, J (PC) ) 9.1 Hz, PCHCH3), 20.1 (d, J (PC) ) 4.7
Hz, PCHCH3), 19.9 (br s, PCHCH3), 19.9 (d, J (PC) ) 2.2 Hz,
PCHCH3), 19.4 (d, J (PC) ) 6.0 Hz, PCHCH3). 31P NMR (C6D6,
162.0 MHz): δ 17.8 (dd, J (RhP2) ) 169.0, J (PP) ) 66.5 Hz,
iPr2P), 7.3 (dd, J (RhP1) ) 169.2, J (PP) ) 66.5 Hz, Cy2P).
P r ep a r a tion of [Rh (η3-C3H5)(K2-P h 2P CH2P iP r 2)] (4).
This compound was prepared as described for 2, using 1 (271
mg, 0.55 mmol), a 1.26 M solution of C3H5MgBr (0.88 mL, 1.11
mmol) in ether, and Ph2PCH2PiPr2 (351 mg, 1.11 mmol) as
starting materials. An orange-yellow microcrystalline solid
was obtained: yield 305 mg (60%); mp 78 °C dec. Anal. Calcd
for C22H31P2Rh: C, 57.40; H, 6.79. Found: C, 57.02; H, 7.28.
1H NMR (C6D6, 200 MHz): δ 7.84, 7.09 (both m, 10H, C6H5),
5.00 (br m, 1H, HM), 4.25 (br d, J (HMHS) ) 7.4 Hz, 1H, HS),
4.06 (br d, J (HMHS′) ) 7.2 Hz, 1H, HS′), 3.59 (m, 2H, PCH2P),
2.52 (br dd, J (P2HA) ) 6.4, J (HMHA) ) 13.4 Hz, 1H, HA), 2.31
(br dd, J (P1HA′) ) 7.2, J (HMHA′) ) 13.4 Hz, 1H, HA′), 1.72 (br
m, 2H, PCHCH3), 1.06 (dd, J (PH) ) 14.1, J (HH) ) 7.0 Hz,
3H, PCHCH3), 0.98 (dd, J (PH) ) 14.2, J (HH) ) 7.0 Hz, 3H,
PCHCH3), 0.91 (dd, J (PH) ) 14.2, J (HH) ) 7.0 Hz, 3H,
PCHCH3), 0.82 (dd, J (PH) ) 14.3, J (HH) ) 6.9 Hz, 3H,
PCHCH3). 13C NMR (C6D6, 100.6 MHz): δ 139.4 (d, J (PC) )
6.2 Hz, ipso-C of C6H5), 138.9 (d, J (PC) ) 5.6 Hz, ipso-C of
C6H5), 132.9 (d, J (PC) ) 15.5 Hz, ortho-C of C6H5), 132.6 (d,
J (PC) ) 16.0 Hz, ortho-C of C6H5), 129.2 (d, J (PC) ) 2.1 Hz,
para-C of C6H5), 129.0 (d, J (PC) ) 1.6 Hz, para-C of C6H5),
128.4 (d, J (PC) ) 9.3 Hz, meta-C of C6H5), 128.2 (d, J (PC) )
9.5 Hz, meta-C of C6H5), 109.7 (br m, η3-H2C-CH-C′H2), 50.9
(dd, J (RhC) ) 6.2, J (P2C) ) 26.1, η3-H2C-CH-C′H2), 48.0 (dd,
J (RhC) ) 6.6, J (P1C) ) 28.3, η3-H2C-CH-C′H2), 42.7 (ddd,
J (RhC) ) 2.3, J (P1C) ) 20.1, J (P2C) ) 12.5 Hz, P1CH2P2), 25.7
(m, PCHCH3), 19.7, 19.2 (both d, J (PC) ) 8.6 Hz, PCHCH3),
18.8 (br d, J (PC) ) 8.1 Hz, PCHCH3). 31P NMR (C6D6, 81.0
MHz): δ 19.0 (dd, J (RhP2) ) 169.1, J (PP) ) 72.5 Hz, iPr2P),
-8.4 (dd, J (RhP1) ) 176.8, J (PP) ) 72.5 Hz, Ph2P).
2
J (HAHM) ) J (HA′HM) ) 13.2, J (HSHM) ) J (HS′HM) ) 7.4 Hz,
1H, HM), 3.97 (d, J (HMHS) ) J (HMHS′) ) 7.4 Hz, 2H, HS and
HS′), 2.69 (m, in 1H{31P} dd, J (RhH) ) 1.2, J (HH) ) 15.6 Hz,
1H, PCH2P), 2.58 (m, in 1H{31P} d, J (HH) ) 15.6 Hz, 1H,
PCH2P), 2.20 (dvt, N ) 6.8, J (HMH) ) 13.5 Hz, 2H, HA and
1
HA′), 1.83, 1.72 (both m, in H{31P} both sept, J (HH) ) 7.2 Hz,
2H each, PCHCH3), 1.12 (dd, J (PH) ) 17.2, J (HH) ) 7.0 Hz,
6H, PCHCH3), 1.11 (dd, J (PH) ) 18.8, J (HH) ) 7.2 Hz, 6H,
PCHCH3), 1.04 (dd, J (PH) ) 14.4, J (HH) ) 7.0 Hz, 6H,
PCHCH3), 1.03 (dd, J (PH) ) 14.8, J (HH) ) 7.0 Hz, 6H,
PCHCH3). 13C NMR (C6D6, 50.3 MHz): δ 108.3 (dt, J (RhC) )
4.9, J (PC) ) 2.5 Hz, η3-CH2-CH-CH2), 47.7 (dvt, J (RhC) )
6.5, N ) 27.1 Hz, η3-CH2-CH-CH2), 35.7 (dt, J (RhC) ) 1.8,
J (PC) ) 13.2 Hz, PCH2P), 26.5 (dvt, J (RhC) ) 3.0, N ) 17.2
Hz, PCHCH3), 26.3 (dvt, J (RhC) ) 1.0, N ) 13.5 Hz, PCHCH3),
20.1, 19.9, 19.8, 19.4 (all br s, PCHCH3). 31P NMR (C6D6, 81.0
MHz): δ 17.7 (d, J (RhP) ) 168.6 Hz).
P r ep a r a tion of [Rh (η3-C3H5)(K2-Cy2P CH2P iP r 2)] (3).
This compound was prepared as described for 2, using 1 (477
mg, 0.97 mmol), a 1.10 M solution of C3H5MgBr (1.76 mL, 1.94
mmol) in ether, and Cy2PCH2PiPr2 (641 mg, 1.95 mmol) as
starting materials. Orange-yellow crystals were isolated: yield
700 mg (76%); mp 78 °C dec. Anal. Calcd for C22H43P2Rh: C,
55.93; H, 9.17. Found: C, 55.75; H, 9.56. 1H NMR (C6D6, 400
P r ep a r a tion of [Rh (η3-2-MeC3H4)(K2-iP r 2P CH2P iP r 2)]
(5). This compound was prepared as described for 2, using 1
(77 mg, 0.16 mmol), a 0.95 M solution of 2-MeC3H4MgCl (0.33
mL, 0.32 mmol) in THF, and iPr2PCH2PiPr2 (0.32 mmol) as
starting materials. An orange-yellow microcrystalline solid
was obtained: yield 98 mg (75%); mp 38 °C dec. Anal. Calcd
for C17H37P2Rh: C, 50.20; H, 8.68. Found: C, 49.72; H, 8.71.
1H NMR (C6D6, 400 MHz): δ 3.60 (br s, 2H, HS and HS′), 2.67
(m, in 1H{31P} dd, J (RhH) ) 1.6, J (HH) ) 15.4 Hz, 1H,
3
MHz): δ 4.80 (br tt, J (HAHM) ) J (HA′HM) ) 13.1, J (HSHM) )
J (HS′HM) ) 7.2, 1H, HM), 3.97, 3.95 (both d, J (HMH) ) 7.2 Hz,
2H, HS and HS′), 2.82 (m, in 1H{31P} dd, J (RhH) ) 1.4, J (HH)
) 15.4 Hz, 1H, PCH2P), 2.70 (m, in 1H{31P} d, J (HH) ) 15.4
1
PCH2P), 2.48 (m, in H{31P} d, J (HH) ) 15.4 Hz, 1H, PCH2P),
2.10 (vt, N ) 8.0 Hz, 2H, HA and HA′), 1.75 (br m, 4H,

3218 Organometallics, Vol. 17, No. 15, 1998
Manger et al.
PCHCH3), 1.72 (d, J (RhH) ) 2.1 Hz, 3H, η3-H2C-C(CH3)-
CH2), 1.14 (dd, J (PH) ) 14.4, J (HH) ) 7.0 Hz, 6H, PCHCH3),
1.13 (dd, J (PH) ) 14.4, J (HH) ) 7.1 Hz, 6H, PCHCH3), 1.06
(dd, J (PH) ) 15.5, J (HH) ) 7.0 Hz, 6H, PCHCH3), 1.01 (dd,
J (PH) ) 14.5, J (HH) ) 7.0 Hz, 6H, PCHCH3). 13C NMR (C6D6,
50.3 MHz): δ 119.4 (dt, J (RhC) ) 5.8, J (PC) ) 2.1 Hz, η3-
CH2-C(CH3)-CH2), 47.7 (dvt, J (RhC) ) 6.5, N ) 27.8 Hz, η3-
CH2-C(CH3)-CH2), 36.0 (dt, J (RhC) ) 1.9, J (PC) ) 13.0 Hz,
PCH2P), 27.7 (d, J (RhC) ) 1.4 Hz, η3-H2C-C(CH3)-CH2), 26.4
(dvt, J (RhC) ) 0.9, N ) 13.0 Hz, PCHCH3), 25.9 (dvt, J (RhC)
) 3.0, N ) 17.3 Hz, PCHCH3), 20.1-19.5 (br m, PCHCH3).
31P NMR (C6D6, 81.0 MHz): δ 19.6 (d, J (RhP) ) 167.9 Hz).
P r ep a r a tion of [Rh (η3-2-MeC3H4)(K2-Cy2P CH2P iP r 2)]
(6). This compound was prepared as described for 2, using 1
(125 mg, 0.25 mmol), a 0.90 M solution of 2-MeC3H4MgCl (0.58
mL, 0.51 mmol) in THF, and Cy2PCH2PiPr2 (0.51 mmol) as
starting materials. Yellow crystals: yield 166 mg (67%); mp
56 °C dec. Anal. Calcd for C23H45P2Rh: C, 56.79; H, 9.32.
Found: C, 57.00; H, 9.45. 1H NMR (C6D6, 200 MHz): δ 3.62
(m, 2H, HS and HS′), 2.72 (m, 2H, PCH2P), 2.14 (br m, 2H, HA
and HA′), 1.76 (d, J (RhH) ) 2.2 Hz, 3H, η3-H2C-C(CH3)-C′H2),
2.02-1.18 (br m, 24H, PCHCH3 and C6H11), 1.18 (dd, J (PH)
) 14.3, J (HH) ) 7.0 Hz, 3H, PCHCH3), 1.17 (dd, J (PH) ) 14.7,
J (HH) ) 7.1 Hz, 3H, PCHCH3), 1.08 (m, 6H, PCHCH3). 13C
NMR (C6D6, 50.3 MHz): δ 119.3 (br m, η3-H2C-C(CH3)-CH2),
47.9 (dd, J (RhC) ) 6.5, J (PC) ) 28.0, η3-H2C-C(CH3)-CH2),
47.4 (dd, J (RhC) ) 6.5, J (PC) ) 27.7 Hz, η3-H2C-C(CH3)-
CH2), 37.0 (br dd, J (P1C) ) 18.4, J (P2C) ) 3.6 Hz, PCHCH2),
36.3 (ddd, J (RhC) ) 2.8, J (P1C) ) 11.1, J (P2C) ) 6.2 Hz,
PCHCH2), 35.4 (dt, J (RhC) ) 2.0, J (P1C) ) J (P2C) ) 13.2 Hz,
PCH2P), 30.3 (br m, PCHCH2), 27.7 (br s, η3-H2C-C(CH3)-
CH2), 27.4 (m, CH2 of C6H11), 26.7 (s, CH2 of C6H11), 26.4 (br
dd, J (P2C) ) 8.0, J (P1C) ) 4.0 Hz, PCHCH3), 26.0 (ddd, J (RhC)
) 3.0, J (P2C) ) 10.9, J (P1C) ) 6.5 Hz, PCHCH3), 20.2-19.6
(br m, PCHCH3). 31P NMR (C6D6, 162.0 MHz): δ 20.1 (dd,
J (RhP2) ) 167.1, J (PP) ) 65.4 Hz, iPr2P), 10.0 (dd, J (RhP1) )
166.4, J (PP) ) 65.4 Hz, Cy2P).
(d, J (PC) ) 16.9 Hz, ortho-C of C6H5), 129.1 (d, J (PC) ) 1.6
Hz, para-C of C6H5), 129.0 (d, J (PC) ) 1.9 Hz, para-C of C6H5),
128.4 (d, J (PC) ) 9.5 Hz, meta-C of C6H5), 128.2 (d, J (PC) )
10.0 Hz, meta-C of C6H5), 121.2 (m, η3-H2C′-C(CH3)-CH2),
51.0 (dd, J (RhC) ) 6.3, J (P2C) ) 27.3, η3-H2C-C(CH3)-C′H2),
47.8 (dd, J (RhC) ) 6.5, J (P1C) ) 29.6, η3-H2C-C(CH3)-C′H2),
43.1 (ddd, J (RhC) ) 2.3, J (P1C) ) 20.0, J (P2C) ) 12.4 Hz,
PCH2P), 27.6 (d, J (RhC) ) 1.4 Hz, η3-H2C-C(CH3)-C′H2), 23.4
(m, PCHCH3), 19.8, 19.3 (both d, J (PC) ) 8.8 Hz, PCHCH3),
18.8 (br s, PCHCH3). 31P NMR (C6D6, 81.0 MHz): δ 20.8 (dd,
J (RhP2) ) 166.8, J (PP) ) 71.6 Hz, iPr2P), -6.7 (dd, J (RhP1)
) 174.8, J (PP) ) 71.6 Hz, Ph2P).
P r ep a r a tion of [Rh HCl2(K2-iP r 2P CH2P iP r 2)] (8). A de-
gassed solution of 2 (85 mg, 0.22 mmol) in 10 mL of ether was
saturated at -30 °C with HCl, and the mixture was stirred
for 5 min. A rapid change of color from orange-yellow to almost
colorless occurred, and an off-white solid precipitated. After
the mother liquor was removed, the remaining solid was
washed five times with 5-mL portions of ether and twice with
5-mL portions of pentane and dried. An off-white solid was
isolated: yield 90 mg (98%); mp 111 °C dec. Anal. Calcd for
C
13H31Cl2P2Rh: C, 36.90; H, 7.38. Found: C, 37.35; H, 6.97.
IR (CH2Cl2): ν(RhH) 2100 cm-1 1H NMR (CDCl3, 200 MHz,
.
295 K): δ 3.14 (br m, 2H, PCH2P), 2.55, 2.23 (both m, 2H each,
PCHCH3), 1.46 (br dvt, N ) 17.8, J (HH) ) 7.3 Hz, 6H,
PCHCH3), 1.27 (br m, 18H, PCHCH3), -15.80 (br dt, J (RhH)
) 20.0, J (PH) ) 20.2 Hz, 1H, RhH). 1H NMR (CDCl3, 200
MHz, 318 K): δ 3.29 (br m, 2H, PCH2P), 2.58, 2.24 (both m,
2H each, PCHCH3), 1.49 (dvt, N ) 18.2, J (HH) ) 7.3 Hz, 6H,
PCHCH3), 1.30 (br m, 18H, PCHCH3), -15.80 (dt, J (RhH) )
J (PH) ) 20.0 Hz, 1H, RhH). 13C NMR (CDCl3, 50.3 MHz, 295
K): δ 30.0 (m, PCH2P), 28.4 (vt, N ) 16.4 Hz, PCHCH3), 26.9
(vt, N ) 18.0 Hz, PCHCH3), 20.0, 19.2, 18.2, 17.5 (all s,
PCHCH3). 31P NMR (CDCl3, 81.0 MHz, 263 K): δ 16.8 (d,
J (RhP) ) 113.7 Hz), 16.0 (A-part of the ABX spin system,
J (RhPA) ) 112.9, J (PP) ) 68.2 Hz, PA), 15.3 (B-part of the ABX
spin system, J (RhPB) ) 113.8, J (PP) ) 68.2 Hz, PB). 31P NMR
(CDCl3, 81.0 MHz, 295 K): δ 16.5 (br d, J (RhP) ) 114.4 Hz),
15.7 (br d, J (RhP) ) 112.0 Hz). 31P NMR (CDCl3, 81.0 MHz,
318 K): δ 16.0 (d, J (RhP) ) 114.1 Hz).
P r ep a r a tion of [Rh (η3-2-MeC3H4)(K2-P h 2P CH2P iP r 2)]
(7). This compound was prepared as described for 2, using 1
(129 mg, 0.26 mmol), a 0.90 M solution of 2-MeC3H4MgCl (0.58
mL, 0.52 mmol) in THF, and Ph2PCH2PiPr2 (0.52 mmol) as
starting materials. A yellow microcrystalline solid was ob-
tained: yield 173 mg (70%); mp 51 °C dec. Anal. Calcd for
P r ep a r a tion of [Rh HCl2(K2-Cy2P CH2P iP r 2)] (9). This
compound was prepared as described for 8, using 3 (120 mg,
0.25 mmol) as starting material. A pale yellow solid was
obtained: yield 114 mg (91%); mp 89 °C dec. Anal. Calcd for
C
19H39Cl2P2Rh: C, 45.34; H, 7.81. Found: C, 45.74; H, 7.25.
IR (KBr): ν(RhH) 2110 cm-1 1H NMR (CDCl3, 200 MHz, 295
.
K): δ 3.12 (br m, 2H, PCH2P), 2.53 (br m, 1H, PCHCH3), 2.40-
1.19 (br m, 32H, PCHCH3 and C6H11), 1.46 (dd, J (PH) ) 18.2,
J (HH) ) 6.9 Hz, 3H, PCHCH3), -15.91 (br m, 1H, RhH). 13C
NMR (CDCl3, 50.3 MHz, 295 K): δ 36.9 (d, J (PC) ) 19.6 Hz,
PCHCH2), 34.6 (d, J (PC) ) 23.9 Hz, PCHCH2), 29.3 (m,
PCH2P), 27.5, 26.0, 25.6, 25.3, 25.2, 24.3, 24.0 (all s, CH2 of
C6H11), 26.9 (br m, PCHCH3), 18.7, 17.8, 16.8, 16.0 (all s,
PCHCH3). 31P NMR (CDCl3, 81.0 MHz, 295 K): δ 18.2-14.8
(br m, iPr2P), 8.9-5.4 (br m, Cy2P). 31P NMR (CDCl3, 81.0
MHz, 328 K): δ 16.3 (br dd, J (RhP2) ) 113.7 Hz, J (PP) ) 66.1
Hz, iPr2P), 7.0 (br dd, J (RhP1) ) 114.8, J (PP) ) 66.1 Hz, Cy2P),
6.8 (br dd, J (RhP1) ) 113.7, J (PP) ) 66.1 Hz, Cy2P).
7
1
C
23H33P2Rh: C, 58.24; H, 7.01. Found: C, 57.88; H, 6.59. H
NMR (C6D6, 400 MHz): δ 7.90, 7.06 (both m, 10H, C6H5), 3.94
(d, J (RhHS) ) 2.4 Hz, 1H, HS), 3.70 (d, J (RhHS′) ) 1.8 Hz, 1H,
HS′), 3.46 (m; in 1H{31P} dd, J (RhH) ) 1.4, J (HH) ) 15.1 Hz;
in H{31PiPr2} ddd, J (RhH) ) 1.4, J (P1H) ) 8.4, J (HH) ) 15.1
P r ep a r a tion of [Rh HCl2(K2-P h 2P CH2P iP r 2)] (10). This
compound was prepared as described for 8, using 4 (300 mg,
0.65 mmol) as starting material. A pale yellow solid was
obtained: yield 242 mg (88%); mp 56 °C dec. Anal. Calcd for
C19H27Cl2P2Rh: C, 46.46; H, 5.54. Found: C, 46.19; H, 5.27.
1
Hz; in 1H{31PPh2} ddd, J (RhH) ) 1.4, J (P2H) ) 7.2, J (HH) )
15.1 Hz, 1H, PCH2P), 3.29 (m; in H{31P} d, J (HH) ) 15.1 Hz;
1
in 1H{31PiPr2} dd, J (P1H) ) 8.5, J (HH) ) 15.1 Hz; in
1H{31PPh2} dd, J (P2H) ) 7.2, J (HH) ) 15.1 Hz, 1H, PCH2P),
2.44 (d, J (P2HA) ) 6.0, 1H, HA), 2.21 (d, J (P1HA′) ) 6.4, 1H,
HA′), 1.82 (d, J (RhH) ) 2.0 Hz, 3H, η3-H2C-C(CH3)-C′H2],
1.75, 1.62 (both m, 1H each, PCHCH3), 1.07 (dd, J (PH) ) 14.9,
J (HH) ) 7.3 Hz, 3H, PCHCH3), 1.00 (dd, J (PH) ) 14.9, J (HH)
) 7.0 Hz, 3H, PCHCH3), 0.99 (dd, J (PH) ) 15.6, J (HH) ) 7.2
Hz, 3H, PCHCH3), 0.92 (dd, J (PH) ) 12.5, J (HH) ) 6.9 Hz,
3H, PCHCH3). 13C NMR (C6D6, 50.3 MHz): δ 139.4 (m, ipso-C
of C6H5), 132.9 (d, J (PC) ) 16.2 Hz, ortho-C of C6H5), 132.7
IR (KBr): ν(RhH) 2110 cm-1 1H NMR (CDCl3, 200 MHz, 295
.
K): δ 7.87 (m, 4H, ortho-H of C6H5), 7.38 (m, 6H, meta-H and
para-H of C6H5), 4.29, 3.74 (both br m, 1H each, PCH2P), 2.54,
2.24 (both m, 1H each, PCHCH3), 1.11 (br m, 12H, PCHCH3),
-14.49 to -15.24 (m, 1H, RhH). 1H NMR (CDCl3, 200 MHz,
323 K): δ 7.89 (m, 4H, ortho-H of C6H5), 7.37 (m, 6H, meta-H
and para-H of C6H5), 4.29, 3.75 (both br m, 1H each, PCH2P),
2.58, 2.27 (both m, 1H each, PCHCH3), 1.32 (dd, J (PH) ) 17.8,

(π-Allyl)rhodium(I) Complexes
Organometallics, Vol. 17, No. 15, 1998 3219
J (HH) ) 6.9 Hz, 3H, PCHCH3), 1.23 (dd, J (PH) ) 19.3, J (HH)
) 6.9 Hz, 3H, PCHCH3), 1.20 (m, 3H, PCHCH3), 1.04 (dd,
J (PH) ) 18.5, J (HH) ) 7.0 Hz, 3H, PCHCH3), -14.90 (m, 1H,
RhH). 13C NMR (CDCl3, 50.3 MHz, 295 K): δ 134.7 (br m,
ipso-C of C6H5), 132.7 (br d, J (PC) ) 11.4 Hz, ortho-C of C6H5),
131.6 (d, J (PC) ) 13.5 Hz, ortho-C of C6H5), 128.8 (m, meta-C
and para-C of C6H5), 37.0 (dd, J (P1C) ) 29.2, J (P2C) ) 24.0
Hz, PCH2P), 28.5 (dd, J (P2C) ) 20.7, J (P1C) ) 4.3 Hz,
PCHCH3), 25.9 (d, J (PC) ) 22.5 Hz, PCHCH3), 19.5, 18.8, 18.2,
17.6 (all s, PCHCH3). 31P NMR (CDCl3, 81.0 MHz, 295 K): δ
20.2 (dd, J (RhP2) ) 111.9, J (PP) ) 77.0 Hz, iPr2P), 19.6-17.2
(m, iPr2P), -12.5 (dd, J (RhP1) ) 117.0, J (PP) ) 77.0 Hz, Ph2P),
-10.3 to -16.5 (m, Ph2P). 31P NMR (CDCl3, 81.0 MHz, 328
K): δ 21.0-18.8 (m, iPr2P), -11.2 to -14.7 (br m, Ph2P).
P r ep a r a tion of [Rh H(O2CCF 3)2(K2-Cy2P CH2P iP r 2)] (11).
A solution of 3 (118 mg, 0.25 mmol) in 4 mL of pentane/ether
(3:1) was treated at -78 °C with CF3CO2H (39 µL, 0.50 mmol).
Quite rapidly, an orange-yellow oily solid precipitated. After
the reaction mixture was stirred for 5 min, the solvent was
removed in vacuo. The residue was washed at -20 °C three
times with 4-mL portions of pentane/ether (3:1) and twice with
4-mL portions of pentane and dried. A pale yellow solid was
obtained: yield 140 mg (85%); mp 41 °C dec. Anal. Calcd for
1H, RhH). 13C NMR (CDCl3, 50.3 MHz): δ 27.8 (d, J (PC) )
25.0 Hz, PCHCH3), 26.0 (d, J (PC) ) 33.5 Hz, PCHCH3), 21.4,
20.7 (both br m, PCH2CH2P), 19.7, 17.9, 17.8 (all s, PCHCH3).
31P NMR (CDCl3, 81.0 MHz): δ 105.0 (d, J (RhP) ) 134.4 Hz).
P r ep a r a tion of [Rh H(O3SCF 3)2(K2-iP r 2P CH2CH2P iP r 2)]
(15). This compound was prepared as described for 12, using
13 (208 mg, 0.51 mmol) as starting material. A pale yellow
solid was obtained: yield 280 mg (82%); mp 80 °C dec. Anal.
Calcd for C16H33F6O6P2RhS2: C, 28.92; H, 5.00; S, 9.65.
Found: C, 28.85; H, 4.95; S, 9.27. IR (CH2Cl2): ν(OSOasym
1297, ν(OSOasym) and ν(CF) 1265-1228, ν(OSOsym) 1213, 1168,
ν(SdO) 1025 cm-1 1H NMR (CD2Cl2, 200 MHz, 295 K): δ 2.49
)
.
(br m, 4H, PCH2CH2P), 1.89 (m, 4H, PCHCH3), 1.27 (m, 24H,
PCHCH3), -21.02 (m, 1H, RhH). 1H NMR (CDCl3, 200 MHz,
308 K): δ 2.53 (br m, 4H, PCH2CH2P), 1.87 (br m, 4H,
PCHCH3), 1.38 (dd, J (PH) ) 16.7, J (HH) ) 6.9 Hz, 6H,
PCHCH3), 1.34 (dd, J (PH) ) 15.6, J (HH) ) 7.3 Hz, 6H,
PCHCH3), 1.31 (dd, J (PH) ) 13.8, J (HH) ) 6.9 Hz, 6 H,
PCHCH3), 1.23 (dd, J (PH) ) 15.3, J (HH) ) 6.9 Hz, 6H,
PCHCH3), -21.01 (br dt, J (RhH) ) 21.8, J (PH) ) 21.4 Hz,
1H, RhH). 13C NMR (CD2Cl2, 50.3 MHz, 308 K): δ 120.2 (q,
J (FC) ) 323.9 Hz, CF3), 27.3 (d, J (PC) ) 25.0 Hz, PCHCH3),
25.7 (d, J (PC) ) 31.7 Hz, PCHCH3), 21.5, 20.7 (both br m,
PCH2CH2P), 20.1, 18.0, 17.8, 17.4 (all s, PCHCH3). 19F NMR
(CDCl3, 188.3 MHz, 308 K): δ -78.6 (s). 31P NMR (CD2Cl2,
81.0 MHz, 295 K): δ 106.8 (br m). 31P NMR (CDCl3, 81.0 MHz,
308 K): δ 106.9 (d, J (RhP) ) 141.0 Hz).
C
23H39F6O4P2Rh: C, 41.96; H, 5.97. Found: C, 41.40; H, 5.19.
IR (CH2Cl2): ν(RhH) 2115, ν(OCOasym) 1715, 1668, ν(OCOsym
1455, 1443, ν(CF) 1195 cm-1 1H NMR (CD2Cl2, 400 MHz, 295
)
.
K): δ 3.03, 2.85 (both m, 1H each, PCH2P), 2.57 (br m, 1H,
PCHCH2), 2.28 (m, 2H, PCHCH3), 1.91 (br m, 9H, PCHCH2),
1.34 (br m, 24H, C6H11 and PCHCH3), -17.60 (br m, RhH),
-17.85 (br dt, J (RhH) ) J (PH) ) 21.0 Hz, RhH). 1H NMR
(CD2Cl2, 200 MHz, 313 K): δ 2.98 (br m, 2H, PCH2P), 2.70-
1.30 (br m, 36H, C6H11 and PCHCH3), -17.89 (br m, 1H, RhH).
13C NMR (CD2Cl2, 100.6 MHz, 308 K): δ 163.8 (br m, O2CCF3),
116.2 (q, J (FC) ) 287.3 Hz, O2CCF3), 36.9 (br d, J (PC) ) 19.9
Hz, PCHCH2), 36.0 (br d, J (PC) ) 25.3 Hz, PCHCH2), 29.3
(m, PCH2P), 30.6, 28.0 (both s, PCHCH2), 27.6-26.3 (m,
PCHCH3 and CH2 of C6H11), 26.1, 25.9 (both s, CH2 of C6H11),
19.8, 19.0, 17.8, 17.3 (all s, PCHCH3). 19F NMR (CD2Cl2, 376.6
Hz): δ -75.9 (s). 31P NMR (CD2Cl2, 162.0 MHz, 295 K): δ
17.5 (br m, iPr2P), 7.7 (br m, Cy2P). 31P NMR (CD2Cl2, 81.0
MHz, 318 K): δ 18.6 (br dd, J (RhP2) ) 117.5 Hz, J (PP) ) 71.0
Hz, iPr2P), 8.4 (br dd, J (RhP1) ) 113.4, J (PP) ) 71.0 Hz, Cy2P).
31P NMR (CD2Cl2, 81.0 MHz, 195 K): δ 19.2-16.0 (br m,
iPr2P), 9.9-7.2 (br m, Cy2P).
P r ep a r a t ion of [R h (η3-C3H5)(CO)(K2-iP r 2P CH2P iP r 2)]
(16). A degassed solution of 2 (111 mg, 0.28 mmol) in 15 mL
of pentane was treated at -40 °C with CO and then under
continuous stirring slowly (ca. 10 min) warmed to room
temperature. A rapid change of color from orange-yellow to
orange-red and finally to pale yellow occurred. After removal
of the solvent in vacuo, the remaining yellow solid was washed
at -40 °C twice with 2-mL portions of pentane and dried: yield
99 mg (83%); mp 32 °C dec. Anal. Calcd for C17H35OP2Rh:
C, 48.58; H, 8.39. Found: C, 48.77; H, 8.12. IR (C6H6): ν(Ct
O) 1980 cm-1 1H NMR (C6D6, 200 MHz, 295 K): δ 5.06 (m,
.
1H, HM), 2.56 (m, 4H, HA and HS), 2.16 (br m, 2H, PCH2P),
1.72 (m, 4H, PCHCH3), 1.02, 0.95 (both dd, J (PH) ) 14.6,
J (HH) ) 7.0 Hz, 12H each, PCHCH3). 1H NMR (C6D5CD3, 200
MHz, 233 K): δ 5.12 (br m, 1H, HM), 2.90 (br d, J (HMHS) )
5.6 Hz, 2H, HS), 2.09 (br m, 4H, PCH2P and HA), 1.59 (br m,
4H, PCHCH3), 0.98 (m, 24H, PCHCH3). 13C NMR (C6D5CD3,
50.3 MHz, 295 K): δ 201.4 (dt, J (RhC) ) 76.8, J (PC) ) 6.5
Hz, Rh-CO), 82.8 (br s, η3-H2C-CH-CH2), 47.8 (br d, J (RhC)
) 7.4 Hz, η3-H2C-CH-CH2), 29.5 (br m, PCH2P), 27.5 (br s,
PCHCH3), 19.1, 18.8 (both s, PCHCH3). 31P NMR (C6D6, 81.0
MHz, 295 K): δ 9.1 (br d, J (RhP) ) 122.8 Hz). 31P NMR (C6D5-
CD3, 81.0 MHz, 233 K): δ 9.5 (d, J (RhP) ) 129.0 Hz).
P r epar ation of [Rh H(O3SCF3)2(K2-iP r 2P CH2P iP r 2)] (12).
A solution of 2 (78 mg, 0.20 mmol) in 4 mL of pentane/ether
(3:1) was treated at -78 °C with a solution of CF3SO3H (36
µL, 0.40 mmol) in 3 mL of ether. A pale yellow solid
precipitated. After the reaction mixture was stirred for 5 min,
it was worked up as described for 11. An off-white solid was
obtained: yield 117 mg (90%); mp 50 °C dec. Anal. Calcd for
P r ep a r a tion of [Rh (η3-C3H5)(CO)(K2-Cy2P CH2P iP r 2)]
(17). This compound was prepared as described for 16, using
3 (156 mg, 0.33 mmol) as starting material. An orange-yellow
solid was obtained: yield 132 mg (80%); mp 41 °C dec. Anal.
Calcd for C23H43OP2Rh: C, 55.24; H, 8.66. Found: C, 55.73;
C
15H31F6O6P2RhS2: C, 27.70; H, 4.80; S, 9.86. Found: C,
27.32; H, 4.84; S, 9.48. IR (CH2Cl2): ν(OSOasym) 1300, ν(OSO-
sym) and ν(CF) 1225-1195, ν(SdO) 1025 cm-1 1H NMR (CD2-
.
Cl2, 200 MHz, 295 K): δ 3.20-2.79 (m, 2H, PCH2P), 2.38, 2.30
(both m, 2H each, PCHCH3), 1.37 (br m, 24H, PCHCH3),
-18.56 (m, 1H, RhH). 19F NMR (CDCl3, 188.3 Hz): δ -78.3
(s). 31P NMR (CD2Cl2, 81.0 MHz, 295 K): δ 15.7 (d, J (RhP) )
117.0 Hz). 31P NMR (CD2Cl2, 81.0 MHz, 243 K): δ 17.9 (d,
J (RhP) ) 115.2 Hz), 18.5 (A-part of the ABX spin system,
J (RhPA) ) 121.0, J (PP) ) 73.3 Hz, PA), 17.2 (B-part of the ABX
spin system, J (RhPB) ) 113.6, J (PP) ) 73.3 Hz, PB).
H, 8.10. IR (C6H6): ν(CtO) 1940 cm-1 1H NMR (C6D6, 400
.
MHz): δ 5.25 (m, 1H, HM), 2.79 (br m, 4H, HA and HS), 2.35
(t, J (P1H) ) J (P2H) ) 6.0 Hz, 2H, PCH2P), 1.73 (br m, 12H,
PCHCH3 and PCHCH2), 1.23 (br m, 12H, C6H11), 1.07 (dd,
J (PH) ) 14.4, J (HH) ) 7.2 Hz, 6H, PCHCH3), 1.00 (dd, J (PH)
) 14.4, J (HH) ) 7.0 Hz, 6H, PCHCH3). 13C NMR (C6D6, 100.6
MHz): δ 201.0 (br d, J (RhC) ) 78.5 Hz, Rh-CO), 87.4 (br s,
η3-H2C-CH-CH2), 40.4 (br s, η3-H2C-CH-CH2), 37.9 (br s,
PCHCH2), 29.6, 29.5, 29.4, 29.3 (all s, PCHCH2), 27.7, 27.6
(both s, CH2 of C6H11), 27.6 (m, PCHCH3), 27.5, 27.4 (both s,
CH2 of C6H11), 27.2 (br m, PCH2P), 26.7 (s, CH2 of C6H11), 19.2,
19.2, 19.0, 18.9 (all s, PCHCH3). 31P NMR (C6D6, 81.0 MHz):
δ 14.2 (dd, J (RhP2) ) 127.2, J (PP) ) 19.1 Hz, iPr2P), 2.0 (dd,
J (RhP1) ) 110.0, J (PP) ) 19.1 Hz, Cy2P).
P r ep a r a tion of [Rh HCl2(K2-iP r 2P CH2CH2P iP r 2)] (14).
This compound was prepared as described for 8, using [Rh-
(η3-C3H5)(κ2-iPr2PCH2CH2PiPr2)] (13) (230 mg, 0.57 mmol) as
starting material. A pale yellow solid was obtained: yield 235
mg (95%); mp 96 °C dec. Anal. Calcd for C14H33Cl2P2Rh: C,
38.46; H, 7.61. Found: C, 38.28; H, 7.07. IR (CH2Cl2): ν(RhH)
2140 cm-1
.
1H NMR (CDCl3, 200 MHz): δ 2.18 (m, 4H,
PCH2CH2P), 1.70 (m, 4H, PCHCH3), 1.27, 1.08 (both m, 24H,
PCHCH3), -18.40 (br dt, J (RhH) ) 18.9, J (PH) ) 19.3 Hz,
P r ep a r a tion of [Rh (η3-C3H5)(CO)(K2-P h 2P CH2P iP r 2)]
(18). This compound was prepared as described for 16, using

3220 Organometallics, Vol. 17, No. 15, 1998
Manger et al.
4 (85 mg, 0.18 mmol) as starting material. An orange-red oil
(ν(CdO) could not be exactly located); 1H NMR (C6D5CD3, 200
MHz, 233 K) 7.91 (m, ortho-H of C6H5), 7.01 (m, meta-H and
para-H of C6H5), 6.27 (m, HA), 4.95 (m, HC and HT), 3.95 (d,
J (HAHB) ) 7.0 Hz, 2H, HB), 2.66 (m, PCH2P), 1.88 (m,
PCHCH3), 0.70 (m, PCHCH3); 31P NMR (C6D5CD3, 81.0 MHz,
233 K) δ 8.0 (dd, J (RhP) ) 142.4, J (PP) ) 54.5 Hz, iPr2P),
-13.0 (dd, J (RhP) ) 64.7, J (PP) ) 54.5 Hz, Ph2P).
was obtained which according to the NMR spectra contained
some impurities. IR (C6H6): ν(CtO) 2005 cm-1
.
1H NMR
(C6D6, 200 MHz, 295 K): δ 7.54 (m, 4 H, ortho-H of C6H5),
7.03 (m, 6 H, meta-H and para-H of C6H5), 4.96 (br m, 1H,
HM), 2.77-2.40 (br m, 6H, PCH2P and HA and HS), 1.82 (m,
2H, PCHCH3), 0.92 (br dd, J (PH) ) 14.6, J (HH) ) 7.0 Hz, 12H,
PCHCH3). 31P NMR (C6D6, 81.0 MHz): δ 31.7 (br m, iPr2P),
-19.7 (br m, Ph2P).
P r ep a r a t ion of [R h {C(O)CH2P h }(CO)2(K2-iP r 2P CH2-
P iP r 2)] (22). This compound was prepared similarly to
method a for 19, using [Rh(η3-CH2Ph)(κ2-iPr2PCH2PiPr2)] (21)
(58 mg, 0.13 mmol) as starting material. A white solid was
obtained: yield 25 mg (37%). IR (pentane): ν(CtO) 1984,
P r ep a r a t ion of [R h {C(O)CH2CH dCH 2}(CO)2(K2-iP r 2-
P CH2P iP r 2)] (19). (a) A degassed solution of 2 (100 mg, 0.25
mmol) in 6 mL of pentane was treated at -40 °C with CO,
and the mixture was stirred for 10 min. A rapid change of
color from orange-yellow to orange-red and finally to pale
yellow occurred, and a white solid precipitated. While the CO
atmosphere was maintained, the reaction mixture was cooled
to -78 °C and the mother liquor was removed. The remaining
white solid was washed at -78 °C with 1 mL of pentane and
dried with a slow stream of CO: yield 46 mg (38%). (b) The
method as described for (a) was used, with 16 (100 mg, 0.24
mmol) as starting material: yield 40 mg (35%).
1940, ν(CdO) 1714 cm-1 1H NMR (C6D5CD3, 200 MHz, 233
.
K): δ 7.19 (m, 5H, C6H5), 4.40 (s, 2H, CH2Ph), 1.81 (br m, 4H,
PCH2P and PCHCH3), 1.57 (m, 2H, PCHCH3), 0.98 (m, 24H,
PCHCH3). 31P NMR (C6D5CD3, 81.0 MHz, 233 K): δ 10.2 (dd,
J (RhP) ) 63.5, J (PP) ) 55.1 Hz, PA), 3.0 (dd, J (RhP) ) 138.8,
J (PP) ) 55.1 Hz, PB).
P r ep a r a t ion of [R h {*C(O)CH 2CH dCH 2}(*CO)2(K2-
iP r 2P CH2P iP r 2)] (19a ). A degassed solution of 2 (54 mg, 0.14
mmol) in 1 mL of C6D5CD3 was treated at -40 °C with 13CO,
and the mixture was stirred for 1 min. The resulting solution
was studied by NMR spectroscopy. 1H NMR (C6D5CD3, 200
19a
19
MHz, 233 K): δ 6.34 (m, 1H, HA), 5.08 (m, 2H, HC and HT),
3.94 (m, 2H, HB), 1.84 (m, 4H, PCH2P and PCHCH3), 1.55 (m,
2H, PCHCH3), 1.15 (dd, J (PH) ) 17.2, J (HH) ) 7.0 Hz, 6H,
PCHCH3), 0.95 (dd, J (PH) ) 16.2, J (HH) ) 7.2 Hz, 6H,
PCHCH3), 0.88, 0.75 (both dd, J (PH) ) 14.3, J (HH) ) 6.9 Hz,
6H each, PCHCH3). 13C NMR (C6D5CD3, 50.3 MHz, 233 K):
δ 235.1 (br dddt, J (RhCAc) ) 21.4, J (PACAc) ) 87.6, J (PBCAc) )
3.0, J (CECAc) ) 2.4 Hz, CAC), 201.5 (dddd, J (RhCE) ) 75.7,
J (PBCE) ) 28.6, J (PACE) ) 13.8, J (CAcCE) ) 2.4 Hz, CE); under
the experimental conditions the signals of the other carbon
atoms were not exactly located. 31P NMR (C6D5CD3, 81.0 MHz,
233 K): δ 10.3 (dddt, J (RhP) ) 63.5, J (PP) ) 54.2, J (CAcPA) )
87.6, J (CEPA) ) 13.8 Hz, PA), 3.2 (dddt, J (RhP) ) 139.3, J (PP)
) 54.2, J (CEPB) ) 28.6, J (CAcPB) ) 3.0 Hz, PB).
IR (pentane): ν(CtO) 1974, 1940, ν(CdO) 1699 cm-1
.
1H
NMR (C6D5CD3, 200 MHz, 233 K): δ 6.38 (ddt, J (HTHA) ) 16.8,
J (HCHA) ) 10.5, J (HBHA) ) 7.2 Hz, 1H, HA), 5.09 (m, 2H, HC
and HT), 3.96 (d, J (HAHB) ) 7.2 Hz, 2H, HB), 1.82 (m, 4H,
PCH2P and PCHCH3), 1.55 (m, 2H, PCHCH3), 1.16 (dd, J (PH)
) 17.2, J (HH) ) 7.0 Hz, 6H, PCHCH3), 0.95 (dd, J (PH) ) 16.2,
J (HH) ) 7.2 Hz, 6H, PCHCH3), 0.87 (dd, J (PH) ) 15.4, J (HH)
) 7.0 Hz, 6H, PCHCH3), 0.74 (dd, J (PH) ) 14.2, J (HH) ) 7.0
Hz, 6H, PCHCH3). 31P NMR (C6D5CD3, 81.0 MHz, 233 K): δ
10.3 (dd, J (RhP) ) 63.5, J (PP) ) 54.2 Hz, PA), 3.2 (dd, J (RhP)
) 139.3, J (PP) ) 54.2 Hz, PB).
P r ep a r a t ion of [R h {C(O)CH2CH dCH 2}(CO)2(K2-P h 2-
P CH2P iP r 2)] (20). This compound was prepared similarly
to method a for 19, using 4 (95 mg, 0.21 mmol) as starting
material. A pale yellow solid was obtained: yield 50 mg (45%).
A mixture of two diastereoisomers in a 20A:20B ratio of 60:
40 was obtained. Isomer 20A: IR (pentane) ν(CtO) 1990,
P r ep a r a tion of [Rh {C(O)CH2CHdCH2}(*CO)2(K2-iP r 2-
P CH2P iP r 2)] (19b). A degassed solution of 16 (37 mg, 0.09
mmol) in 0.4 mL of C6D5CD3 was treated at -40 °C with 13CO,
and the mixture was stirred for 1 min. The resulting solution
was studied by NMR spectroscopy. 13C NMR (C6D5CD3, 50.3
MHz, 233 K): δ 201.6 (ddd, J (RhC) ) 75.1, J (PBC) ) 28.4,
J (PAC) ) 13.8 Hz, Rh-CO); under the experimental conditions
the signals of the other carbon atoms were not exactly located.
31P NMR (C6D5CD3, 81.0 MHz, 233 K): δ 10.0 (ddt, J (RhPA)
) 62.8, J (PP) ) 54.2, J (CEPA) ) 13.8 Hz, PA), 3.1 (ddt, J (RhPB)
) 138.8, J (PP) ) 54.2, J (CEPB) ) 28.6 Hz, PB).
20A
1945 (ν(CdO) could not be exactly located); 1H NMR (C6D5-
CD3, 200 MHz, 233 K) 7.79 (m, ortho-H of C6H5), 7.01 (m,
meta-H and para-H of C6H5), 6.27 (m, HA), 4.95 (m, HC and
HT), 3.87 (d, J (HAHB) ) 7.0 Hz, 2H, HB), 2.66 (m, PCH2P),
Rea ction of 19 w ith HCl. A degassed solution of 2 (132
mg, 0.34 mmol) in 10 mL of ether was treated at -40 °C with
CO, and the mixture was stirred for 10 min. As described
above, under these conditions the acyl complex 19 was formed.
While the CO atmosphere was maintained, a slow stream of
HCl was passed through the reaction mixture, which led to
the rapid formation of a pale yellow precipitate. After the
mother liquor was removed, the remaining solid was washed
at room temperature three times with 5-mL portions of ether
and twice with 5-mL portions of pentane and dried with a slow
stream of CO. A pale yellow solid was obtained, which
according to the spectroscopic data consisted of a mixture of 8
and 25 in the ratio of approximately 1:5. Data for 25 are as
follows. IR (CH2Cl2): ν(RhH) 2098, ν(CtO) 1958. 1H NMR
(CDCl3, 200 MHz): δ ) 3.32 (br m, 1H, PCH2P), 3.07-2.67
1.34-1.10 (m, PCHCH3 and PCHCH3), 0.70 (m, PCHCH3); 31
P
NMR (C6D5CD3, 81.0 MHz, 233 K) δ 15.5 (dd, J (RhP) ) 63.2,
J (PP) ) 50.9 Hz, iPr2P), -25.7 (dd, J (RhP) ) 143.1, J (PP) )
50.9 Hz, Ph2P). Isomer 20B: IR (pentane) ν(CtO) 2010, 1960
20B

(π-Allyl)rhodium(I) Complexes
Organometallics, Vol. 17, No. 15, 1998 3221
were refined with isotropic displacement parameters. C-H
distances were restrained to a fixed value; H-H 1,3-distances
were restrained to be equal. A semiempirical absorption
correction was applied. The structure was solved by Patterson
and Fourier methods with SHELXS-9733 and refined by full-
matrix least-squares procedures on F2 (SHELXL-97).34 Atomic
coordinates, bond lengths and angles, and thermal parameters
have been deposited at the Cambridge Crystallographic Data
Centre (CCDC).
25
(m, 2H, PCH2P and PCHCH3), 2.48, 2.34, 2.18 (all m, 1H each,
PCHCH3), 1.29 (m, 24H, PCHCH3), -13.27 (br dt, J (RhH) )
J (PAH) ) J (PBH) ) 16.0 Hz, RhH). 13C NMR (CDCl3, 50.3
MHz): δ 183.2 (ddd, J (RhC) ) 48.1, J (PBC) ) 144.1, J (PAC) )
4.4 Hz, Rh-CO), 29.0 (t, J (PAC) ) J (PBC) ) 23.4 Hz, PCH2P),
28.2 (d, J (PC) ) 21.5 Hz, PCHCH3), 26.5 (d, J (PC) ) 19.0 Hz,
PCHCH3), 26.0 (d, J (PC) ) 25.0 Hz, PCHCH3), 25.8 (d, J (PC)
) 21.3 Hz, PCHCH3), 20.3, 19.7, 19.3, 19.2 (all s, PCHCH3),
18.3 (br s, PCHCH3), 17.1 (d, J (PC) ) 6.2 Hz, PCHCH3), 16.1
(d, J (PC) ) 4.4 Hz, PCHCH3). 31P NMR (CDCl3, 81.0 MHz):
δ 17.4 (dd, J (RhP) ) 95.2, J (PP) ) 62.5 Hz, PA), -12.2 (dd,
J (RhP) ) 85.3, J (PP) ) 62.5 Hz, PB).
Ack n ow led gm en t . We thank the Deutsche For-
schungsgemeinschaft (Grant SFB 347) and the Fonds
der Chemischen Industrie for financial support, the
latter in particular for a Ph.D. grant to M. M. Moreover,
D.S. and M.T. thank the Volkswagenstiftung and D.S.
wishes to thank axs-Analytical X-Ray Systems, Karlsru-
he, Germany, for support. We also gratefully acknowl-
edge support by Mrs. R. Schedl and Mr. C. P. Kneis
(elemental analysis and DTA), Mrs. M.-L. Scha¨fer and
Dr. W. Buchner (NMR spectra), BASF AG for various
gifts of chemicals, and in particular Mr. G. Canepa for
experimental assistance.
Cr ysta l Str u ctu r e Deter m in a tion of 16. Single crystals
were obtained by cooling a saturated solution of 16 in pentane
(from +25 to -25 °C). Data were collected at 133(2) K on a
Huber-Stoe-Siemens diffractometer with a CCD area detector
using an oil-coated shock-cooled crystal;31 monochromated Mo
KR (λ ) 0.710 73 Å) radiation was used. Crystal data:
monoclinic, space group P21/c, a ) 8.617(2) Å, b ) 14.089(3)
Å, c ) 17.177(3) Å, â ) 102.78(3)°, V ) 2033.7(7) Å3, Z ) 4,
Su p p or tin g In for m a tion Ava ila ble: Tables of crystal
data and refinement parameters, bond lengths and angles, and
positional and thermal parameters for 16 (5 pages). An X-ray
crystallographic file, in CIF format for 16, is available on the
Internet only. Ordering and access information is given on
any current masthead page.
Fcalcd ) 1.373 g/cm3, F(000) ) 880, µ(Mo KR) ) 0.995 mm-1
,
minimum/maximum transmission 0.636/0.865, crystal dimen-
sions 0.50 × 0.38 × 0.15 mm3, 4.86° e 2θ e 55.14°; 28 408
measured reflections of which 4697 were independent (Rint
)
0.0296) and employed in the structure refinement (218 pa-
rameters, 6 restraints). R1 ) 0.0215 [I > 2σ(I)], wR2 ) 0.0465
(all data);32 minimum/maximum residual electron density
0.379/-0.355 e Å-3. The hydrogen atoms of the allyl ligand
OM980062M
(32) R1 ) ∑||Fo| - |Fc||/∑|Fo|; wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]}1/2
,
with w ) 1/σ2[(Fo2) + (0.0128P)2 + 1.282P] where P ) (Fo + 2Fc2)/3.
(33) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(34) Sheldrick, G. M. SHELXL-97: program for crystal structure
refinement. Universita¨t Go¨ttingen, 1996.
2
(31) (a) Kottke, T.; Stalke, D. J . Appl. Crystallogr. 1993, 26, 615.
(b) Kottke, T.; Lagow, R.; Stalke, D. J . Appl. Crystallogr. 1996, 29,
465.