Synthesis, molecular structure, and reactivity of indenylrhodium complexes containing diphenylcarbene as ligand

Article abstract of DOI:10.1021/om000188v

(η⁵-Indenyl)rhodium(I) complexes of the general composition [(η⁵-C₉H₇)Rh(=CPh₂)(L)] (L = SbiPr₃ (6), PiPr₃ (7), PPh₃ (8), P/PrPh₂ (9), PiPr₂Ph (10)) were prepared from the square-planar precursors frans-[RhCl(=CPh₂)(L)₂] (1-5) and C₉H₇K in THF. Treatment of 6-10 with carbon monoxide resulted in an unusual migratory insertion of the carbene ligand into one of the C-H bonds of the five-membered ring of the indenyl unit to give the compounds [{η⁵-C₉H₆(CHPh₂)}Rh(CO)(L)] (12-16) in 78-87% yield. The X-ray crystal structure analyses of 6 and 13 revealed that in both complexes the slip distortion from a η⁵ to a η³ coordination mode of the indenyl ligand is nearly the same, independent of the bulky CHPh₂ group in the ring-substituted species.

Full text of DOI:10.1021/om000188v

Organometallics 2000, 19, 3109-3114
3109
Syn th esis, Molecu la r Str u ctu r e, a n d Rea ctivity of
In d en ylr h od iu m Com p lexes Con ta in in g Dip h en ylca r ben e
a s Liga n d †
Elke Bleuel, Olaf Gevert, Matthias Laubender, and Helmut Werner*
Institut fu¨r Anorganische Chemie, Universita¨t Wu¨rzburg, Am Hubland,
D-97074 Wu¨rzburg, Germany
Received February 28, 2000
(η5-Indenyl)rhodium(I) complexes of the general composition [(η5-C9H7)Rh(dCPh2)(L)] (L
) SbiPr3 (6), PiPr3 (7), PPh3 (8), PiPrPh2 (9), PiPr2Ph (10)) were prepared from the square-
planar precursors trans-[RhCl(dCPh2)(L)2] (1-5) and C9H7K in THF. Treatment of 6-10
with carbon monoxide resulted in an unusual migratory insertion of the carbene ligand into
one of the C-H bonds of the five-membered ring of the indenyl unit to give the compounds
[{η5-C9H6(CHPh2)}Rh(CO)(L)] (12-16) in 78-87% yield. The X-ray crystal structure analyses
of 6 and 13 revealed that in both complexes the slip distortion from a η5 to a η3 coordination
mode of the indenyl ligand is nearly the same, independent of the bulky CHPh2 group in
the ring-substituted species.
Sch em e 1
In tr od u ction
Recently, we described a simple and very efficient
synthesis of square-planar (carbene)rhodium(I) com-
plexes of the general composition trans-[RhCl(dCRR′)-
(L)2], in which the ligands L could be tertiary phos-
phines, arsines, or stibines.1,2 The key to success was
the use of the bis(stibine) compound trans-[RhCl(C2H4)-
(SbiPr3)2] as the starting material, which reacts with a
variety of diazoalkanes RR′CN2 to give the complexes
trans-[RhCl(dCRR′)(SbiPr3)2] in excellent yield. The two
triisopropylstibine ligands can be easily displaced by
several phosphines and arsines without cleavage of the
rhodium-carbene bond. The square-planar compounds
trans-[RhCl(dCRR′)(L)2] also undergo ligand substitu-
tion reactions with various anionic nucleophiles, which
led not only to the structurally related derivatives trans-
[RhX(dCRR′)(L)2] with X ) F, Br, OPh, OC(O)R, OS-
(O)2CF3 etc.1,3 but, by using NaC5H5 or LiC5H4SiMe3 as
the substrates, also to the cyclopentadienyl complexes
[(η5-C5H5)Rh(dCRR′)(L)] and [(η5-C5H4SiMe3)Rh(dCRR′)-
(L)], respectively.1,4
type [(η5-C9H7)Rh(dCPh2)(L)]. In this paper we describe
the synthesis of a series of corresponding tertiary
phosphine and stibine complexes and the molecular
structure of the compound with L ) SbiPr3 and report
on the reactivity of the molecules [(η5-C9H7)Rh(dCPh2)-
(ER3)] (E ) P, Sb) toward CO, which leads to an unusual
migratory insertion of the carbene ligand into a C-H
bond of the indenyl ring. Some preliminary results have
already been communicated.7
Taking into account that η5-indenyl transition-metal
complexes are sometimes more reactive toward nucleo-
philes than their η5-cyclopentadienyl analogues,5,6 we
set out to prepare half-sandwich type compounds of the
† Dedicated to Professor Fred Basolo on the occasion of his 80th
birthday.
Resu lts a n d Discu ssion
(1) Schwab, P.; Mahr, N.; Wolf, J .; Werner, H. Angew. Chem. 1993,
105, 1498-1500; Angew. Chem., Int. Ed. Engl. 1993, 32, 1480-1482.
(2) Werner, H.; Schwab, P.; Bleuel, E.; Mahr, N.; Steinert, P.; Wolf,
J . Chem. Eur. J . 1997, 3, 1375-1384.
(3) Bleuel, E. Ph.D. Thesis, Universita¨t Wu¨rzburg, 2000.
(4) Bleuel, E.; Werner, H. C.R. Acad. Sci. Paris, Ser. IIc 1999, 341-
349.
(5) (a) Rerek, M. E.; J i, L.-N.; Basolo, F. J . Chem. Soc., Chem.
Commun. 1983, 1208-1209. (b) Basolo, F. Polyhedron 1990, 9, 1503-
1535. (c) Kakkar, A. K.; Taylor, N. J .; Marder, T. B.; Shen, J . K.;
Hallinan, N.; Basolo, F. Inorg. Chim. Acta 1992, 198-200, 219-231.
(6) Bleuel, E.; Laubender, M.; Weberndo¨rfer, B.; Werner, H. Angew.
Chem. 1999, 111, 222-225; Angew. Chem., Int. Ed. Engl. 1999, 38,
156-159.
1. P r ep a r a tion of (η5-In d en yl)(ca r ben e)r h od iu m -
(I) Com p lexes. The square-planar (diphenylcarbene)-
rhodium(I) compounds 1-5 react with C9H7K in THF
at room temperature to give the η5-indenyl complexes
6-10 in 62-87% yield (Scheme 1). After chromato-
graphic workup, the analytically pure products were
(7) Bleuel, E.; Laubender, M.; Weberndo¨rfer, B.; Werner, H. 7th
International Conference on the Chemistry of the Platinum Group
Metals; Nottingham, U.K., 1999; Abstracts, p 30.
10.1021/om000188v CCC: $19.00 © 2000 American Chemical Society
Publication on Web 07/08/2000

3110 Organometallics, Vol. 19, No. 16, 2000
Bleuel et al.
Sch em e 2
high degree of back-bonding between the metal and the
carbene ligand. The slip-fold parameter ∆,9 which
results from the difference between the distances Rh-
C20, Rh-C24 and Rh-C21, Rh-C23, is 0.213 Å and is
thus nearly the same as in [(η5-C9H7)Rh(C2H4)2] (0.161
Å) and [(η5-C9H7)Rh(PMe3)2] (0.201 Å).10 The parameter
∆, together with the hinge angle HA (6.3°) and the fold
angle FA (8.9°), indicates that in 6 a significant slippage
of the indenyl moiety from a η5 to a η3 bonding mode
occurred.
F igu r e 1. ORTEP drawing of 6.
Ta ble 1. Selected Bon d Dista n ces a n d An gles w ith
Esd ’s for Com p ou n d 6
Bond Distances (Å)
2. CO-In itia ted Migr a tor y In ser tion Rea ction s.
In the context of our studies on the reactivity of half-
sandwich complexes of the general type [(η5-C5H5)M-
(PR3)(L)] (M ) Co, Rh, Ir),11 we recently observed that,
upon treatment of [(η5-C5H5)Rh(dCPh2)(PiPr3)] with HX
(X ) Cl, CF3CO2), instead of the expected addition of
the electrophile to the rhodium-carbon double bond a
migratory insertion of the carbene ligand into one of the
C-H bonds of the cyclopentadienyl ring occurs.12 The
analogous reaction of the related η5-indenyl complex 7
with HCl is less straightforward. If an equimolar
amount of HCl is added to a solution of 7 in benzene,
Rh-C1
Rh-Sb
1.885(7)
2.559(7)
2.45(1)
Rh-C22
Rh-C23
Rh-C24
2.199(8)
2.274(8)
2.46(1)
Rh-C20
Rh-C21
2.210(8)
Bond Angles (deg)
96.7(2)
127.0(4)
C1-Rh-Sb
Rh-C1-C30
Rh-C1-C40
C30-C1-C40
120.5(5)
112.2(5)
obtained as deeply colored solids which are only mod-
erately air-sensitive and readily soluble in common
organic solvents. The 13C NMR spectra of the η5-indenyl
compounds display a resonance for the carbene carbon
atom in the low-field region at δ 281-289, which
compared with the square-planar precursors 1-5 are
shifted upfield by 26-37 ppm. The signals for the
bridging carbon atoms C8 and C9 appear at δ 117-120,
indicating that the indenyl ligand is coordinated in a
η5 fashion. For compounds in which a η3 bonding mode
predominates, the corresponding resonances are usually
observed at somewhat lower fields.8 In the case of the
phosphine derivatives 7-10, the signals of the carbon
atoms C1, C3, C8, and C9 appear as doublets of doublets
due to 13C-31P and 13C-103Rh coupling, whereas the
resonance for C2 is a doublet with J (RhC) ) 5.0-6.1
1
the formation of a new compound is observed, the H
NMR spectrum of which displays a signal in the hydride
region at δ -12.70. Since the 31P NMR spectrum of the
solution exhibits a doublet resonance at δ 77.6 with a
31P-103Rh coupling of 145.7 Hz that is typical for a
(triisopropylphosphine)rhodium(III) species,13 we as-
sume that the product of the reaction of 7 with HCl is
the chloro hydrido compound 11 (Scheme 2). If the
insertion of the carbene would occur adjacent to the
benzene ring, diastereomers could be produced. How-
ever, we found no evidence for this. In contrast to the
cyclopentadienyl analogue [{η5-C5H4(CHPh2)}RhHCl-
(PiPr3)],12 the substituted indenyl complex is quite
labile; therefore, attempts to isolate 11 failed. Addition
of an excess of HCl did not yield the supposedly more
stable dichlororhodium(III) derivative [{η5-C9H6(CHPh2)}-
RhCl2(PiPr3)] but led to a mixture of products which
could not be separated by fractional crystallization or
chromatographic techniques.
1
Hz. Characteristic features of the H NMR spectra of
7-10 are the multiplet for the ring proton H2 at δ 4.9-
5.2 and the doublet of doublets for the adjacent protons
H1 and H3 at δ 5.1-5.8, which seems to be a quartet
due to almost identical 1H-1H and H-103Rh couplings.
1
The molecular structure of compound 6 is shown in
Figure 1, and bond distances and angles are given in
Table 1. The molecule possesses the expected two-legged
piano-stool configuration with a Rh-Sb distance (2.559-
(7) Å) that differs only slightly from the Rh-Sb bond
lengths in the square-planar complex 1 (2.5843(5) and
2.5633(5) Å). Similarly to 1, also the Rh-C1 distance is
rather short (1.885(7) Å), which points to a relatively
(9) Faller, J . W.; Crabtree, R. H.; Habib, A. Organometallics 1985,
4, 929-935.
(10) Marder, T. B.; Calabrese, J . C.; Roe, D. C.; Tulip, T. H.
Organometallics 1987, 6, 2012-2014.
(11) Werner, H. Angew. Chem. 1983, 95, 932-954; Angew. Chem.,
Int. Ed. Engl. 1983, 22, 927-959.
(12) Herber, U.; Bleuel, E.; Gevert, O.; Laubender, M.; Werner, H.
Organometallics 1998, 17, 10-12.
(8) (a) Baker, R. T.; Tulip, T. H. Organometallics 1986, 5, 839-845.
(b) O’Connor, J . M.; Casey, C. P. Chem. Rev. 1987, 87, 307-318.
(13) (a) Schwab, P. Ph.D. Thesis, Universita¨t Wu¨rzburg, 1994. (b)
Werner, H. J . Organomet. Chem. 1995, 500, 331-336.

Indenylrhodium Complexes with Diphenylcarbene
Organometallics, Vol. 19, No. 16, 2000 3111
Sch em e 3
Quite unexpectedly, a migratory insertion of the CPh2
ligand not only of 7 but also of 6 and 8-10 can be
initiated by carbon monoxide (Scheme 3). Passing a slow
stream of CO through a solution of the η5-indenyl
complex in pentane at -78 °C leads, upon warming to
room temperature, to a change of color from dark green
to yellow and gives, after removal of the solvent and
recrystallization from pentane, the complexes 12-16 as
yellow, moderately air sensitive solids in 78-87% yield.
The IR spectra of 12-16 show a strong ν(CO) band at
1
1930-1980 cm-1, while the H NMR spectra display as
F igu r e 2. ORTEP drawing of 13.
a typical feature a resonance at δ 5.6-6.1 for the
methine proton of the CHPh2 unit. The two nonequiva-
lent protons H2 and H3 of the five-membered ring give
rise to two separate signals, indicating that the insertion
of the carbene ligand took place into one of the C-H
bonds next to the bridging carbon atoms C8 and C9. With
regard to the mechanism of the migratory insertion, we
assume that the initial step consists of a bimolecular
process leading to a 1:1 adduct of the starting material
and CO. This 20-electron intermediate could afford via
a ring slippage an isomer with an η3-indenyl ligand and
an 18-electron configuration at rhodium which finally
would yield the isolated product.
To confirm the structural proposal for the insertion
products, an X-ray crystal structure analysis of 13 was
carried out. The ORTEP plot (Figure 2) illustrates the
unsymmetrical substitution of the five-membered ring
of the indenyl ligand. The CHPh2 moiety is pointing
away from the triisopropylphosphine, which minimizes
the steric repulsion between the two bulky moieties. The
plane [P, Rh, C20] lies almost exactly perpendicular to
the plane defined by the carbon atoms C1, C2, C3, C4,
and C9, the dihedral angle being 88.6(1)°. The bond
lengths Rh-C4 and Rh-C9 (see Table 2) are ca. 0.2 Å
larger than those between the metal center and C1, C2,
and C3, which confirms the slip distortion of the indenyl
ligand. The slip-fold parameter ∆ (0.196 Å), the hinge
angle HA (9.5(3)°), and the fold angle FA (10.6(3)°) are
similar to those of the nonsubstituted complex 6, which
means that the substituent CHPh2 has no influence on
the slippage from a η5 to a η3 coordination mode.
The influence of CO on the migratory insertion of the
diphenylcarbene ligand seems rather unique. We at-
tempted to generate the trimethylphosphine complex
[{η5-C9H6(CHPh2)}Rh(PMe3)(SbiPr3)] by treatment of 6
with PMe3 but, apart from small amounts of the
substitution product [(η5-C9H7)Rh(dCPh2)(PMe3)]
Ta ble 2. Selected Bon d Dista n ces a n d An gles w ith
Esd ’s for Com p ou n d 13
Bond Distances (Å)
Rh-P
2.2714(7)
1.816(3)
1.156(3)
2.254(2)
Rh-C2
Rh-C3
Rh-C4
Rh-C9
2.244(2)
2.238(2)
2.426(2)
2.458(2)
Rh-C20
C20-O
Rh-C1
Bond Angles (deg)
P-Rh-C20
Rh-C20-O
C2-C3-C30
88.91(8)
178.1(2)
126.8(2)
C4-C3-C30
C40-C30-C50
124.1(2)
111.1(2)
(δ(31P) -12.7, d, J (RhP) ) 255.8 Hz), mainly observed
decomposition. It should be noted, however, that the
reaction of [(η5-C5H5)Rh(dCPh2)(PiPr3)] with PF3 led to
the migration of the diphenylcarbene ligand to the ring
and afforded the insertion product [{η5-C5H4(CHPh2)}-
Rh(PF3)(PiPr3)].12
Con clu sion s
The present investigations have shown that the
analogous (η5-cyclopentadienyl)- and (η5-indenyl)rhod-
ium(I) compounds [(η5-C5H5)Rh(dCPh2)(PiPr3)] and [(η5-
C9H7)Rh(dCPh2)(PiPr3)] (7) behave completely differ-
ently toward carbon monoxide. While the η5-cyclo-
pentadienyl derivative upon treatment with CO affords
exclusively the substitution product [(η5-C5H5)Rh(CO)-
(PiPr3)] and diphenylketene,1,2 the η5-indenyl complex
7 reacts with CO by migratory insertion of the carbene
ligand into one C-H bond of the indenyl unit to give
the ring-substituted compound [{η5-C9H6(CHPh2)}Rh-
(CO)(PiPr3)] in excellent yield. A striking difference in
the reactivity toward CO has also been observed for the
corresponding triisopropylstibine complexes [(η5-C5H5)-
Rh(dCPh2)(SbiPr3)] and [(η5-C9H7)Rh(dCPh2)(SbiPr3)]
(6), respectively. Treatment of the η5-cyclopentadienyl

3112 Organometallics, Vol. 19, No. 16, 2000
Bleuel et al.
163.6 (d, J (RhC) ) 1.2 Hz, ipso-C of C6H5), 128.3, 127.4, 127.0,
125.9 (all s, C6H5), 122.3, 121.8 (both s, C4-7), 118.4 (s, C8,9),
88.9 (d, J (RhC) ) 6.1 Hz, C2), 75.5 (br dd, J (RhC) ) J (PC) )
3.7 Hz, C1,3), 26.5 (d, J (PC) ) 18.3 Hz, PCHCH3), 19.8 (s,
PCHCH3). 31P NMR (81.0 MHz, C6D6): δ 57.3 (d, J (RhP) )
245.6 Hz). Anal. Calcd for C31H38PRh (544.5): C, 68.38; H, 7.03;
Rh, 18.90. Found: C, 68.13; H, 7.35; Rh, 18.41.
P r ep a r a t ion of [(η5-C9H 7)R h (dCP h 2)(P P h 3)] (8). This
was prepared as described for 6, from 3 (99 mg, 0.12 mmol)
and C9H7K (93 mg, 0.60 mmol) in THF (10 mL) at room
temperature: blue green crystals; yield 48 mg (62%); mp 40
°C dec. 1H NMR (200 MHz, C6D6): δ 7.44-6.74 (br m, 29H,
C6H5 and H4-7), 5.61 (dt, J (HH) ) J (RhH) ) 2.6 Hz, 1H, H2),
4.92 (m, 2H, H1,3). 13C NMR (100.6 MHz, C6D6): δ 163.0 (d,
J (RhC) ) 2.0 Hz, ipso-C of C6H5), 134.1 (d, J (PC) ) 20.1 Hz,
meta-C of C6H5P), 128.8, 128.7, 127.8, 127.3, 126.8, 125.6 (all
s, C6H5), 122.7, 119.5 (both s, C4-7), 119.1 (s, C8,9), 90.6 (d,
J (RhC) ) 5.0 Hz, C2), 78.7 (dd, J (RhC) ) 5.0, J (PC) ) 3.0 Hz,
C1,3); the signal of RhdC could not be exactly located. 31P NMR
(81.0 MHz, C6D6): δ 48.7 (d, J (RhP) ) 264.5 Hz). Anal. Calcd
for C40H32PRh (646.6): C, 74.31; H, 4.99. Found: C, 74.32; H,
5.00.
P r epar ation of [(η5-C9H7)Rh (dCP h 2)(P iP r P h 2)] (9). This
was prepared as described for 6, from 4 (221 mg, 0.29 mmol)
and C9H7K (224 mg, 1.45 mmol) in THF (10 mL) at room
temperature. For column chromatography, ether was used as
the eluant: dark green crystals; yield 126 mg (71%); mp 40
°C dec. 1H NMR (400 MHz, C6D6): δ 7.39-6.95 (br m, 24H,
C6H5 and H4-7), 5.15 (br dt, J (HH) ) J (RhH) ) 2.0 Hz, 1H,
H2), 4.98 (m, 2H, H1,3), 1.23 (m, 1H, PCHCH3), 1.06 (dd, J (PH)
) 16.0, J (HH) ) 7.2 Hz, 3H, PCHCH3), 0.45 (dd, J (PH) ) 15.6,
J (HH) ) 6.8 Hz, 3H, PCHCH3). 13C NMR (100.6 MHz, C6D6):
δ 284.4 (dd, J (RhC) ) 48.8, J (PC) ) 13.6 Hz, RhdC), 162.9
(d, J (RhC) ) 2.0 Hz, ipso-C of C6H5), 136.4 (d, J (PC) ) 35.2
Hz, ipso-C of C6H5P), 133.8 (d, J (PC) ) 11.1 Hz, meta-C of
C6H5P), 131.2 (d, J (PC) ) 9.1 Hz, ortho-C of C6H5P), 130.3,
129.0, 127.7, 127.6, 127.0, 125.8 (all s, C6H5), 122.7, 119.4 (both
s, C4-7), 119.9 (s, C8,9), 91.1 (d, J (RhC) ) 5.0 Hz, C2), 78.0 (dd,
J (RhC) ) J (PC) ) 3.5 Hz, C1,3), 22.7 (br s, PCHCH3), 17.9 (s,
PCHCH3). 31P NMR (162.0 MHz, C6D6): δ 53.3 (d, J (RhP) )
260.5 Hz). Anal. Calcd for C37H34PRh (612.6): C, 72.55; H, 5.59.
Found: C, 72.09; H, 5.97.
F igu r e 3.
compound with carbon monoxide leads to the formation
of [(η5-C5H5)Rh(dCPh2)(CO)] and uncoordinated
SbiPr3,13 while the reaction of 6, similar to that of 7,
with CO yields the insertion product [{η5-C9H6(CHPh2)}-
Rh(CO)(SbiPr3)] (12).
Therefore, the final conclusion is that structurally
related η5-cyclopentadienyl and η5-indenyl transition-
metal complexes differ not only in the rate of ligand
substitution processes5 but also in the course of the
reactions with Lewis bases. It is conceivable that in both
cases the reason is the same and lies in the slip
distortion of the more unsymmetrical indenyl moiety.
Exp er im en ta l Section
Gen er a l Con sid er a tion s. All experiments were carried out
under an atmosphere of argon by Schlenk techniques. Solvents
were dried by known procedures and distilled before use. The
starting materials 1-5 were prepared as described in the
literature.1,2
P h ysica l Mea su r em en ts. NMR spectra were recorded at
room temperature on Bruker AC 200 and Bruker AMX 400
instruments. Chemical shifts are expressed in ppm downfield
from SiMe4 (1H and 13C) and (85%) H3PO4 (31P). Abbreviations
used: s, singlet; d, doublet; q, quartet; sept, septet; m,
multiplet; br, broadened signal. Coupling constants J are given
in hertz. Melting points were measured by DTA. For assign-
ment of indenyl protons and carbon atoms see Figure 3.
P r ep a r a tion of [(η5-C9H7)Rh (dCP h 2)(SbiP r 3)] (6). A
solution of 1 (161 mg, 0.20 mmol) in THF (10 mL) was treated
at -78 °C with C9H7K (154 mg, 1.00 mmol) and then slowly
warmed to room temperature. After the mixture was stirred
for 30 min, the solvent was evaporated in vacuo, and the dark
green residue was extracted with pentane (30 mL). The extract
was concentrated to ca. 2 mL and then chromatographed on
Al2O3 (neutral, activity grade V, height of column 4 cm). With
pentane, a dark green fraction was eluted, which was brought
to dryness in vacuo. The residue was recrystallized from
pentane (3 mL) at -78 °C to give dark green crystals, which
were separated from the mother liquor, washed twice with
pentane (2 mL, -30 °C), and dried: yield 103 mg (81%); mp
62 °C dec. 1H NMR (400 MHz, C6D6): δ 7.28-6.97 (br m, 14H,
C6H5 and H4-7), 5.37 (m, 3H, H1-3), 1.44 (sept, J (HH) ) 7.3
Hz, 3H, SbCHCH3), 1.02 (d, J (HH) ) 7.3 Hz, 18H, SbCHCH3).
13C NMR (100.6 MHz, C6D6): δ 281.2 (d, J (RhC) ) 46.3 Hz,
RhdC), 164.8 (s, ipso-C of C6H5), 128.3, 127.4, 126.6, 125.5
(all s, C6H5), 122.1, 119.4 (both s, C4-7), 117.7 (s, C8,9), 85.0 (d,
J (RhC) ) 5.5 Hz, C2), 73.0 (d, J (RhC) ) 3.8 Hz, C1,3), 21.5 (s,
SbCHCH3), 18.3 (d, J (RhC) ) 3.9 Hz, SbCHCH3). Anal. Calcd
for C31H38RhSb (635.3): C, 58.61; H, 6.03. Found: C, 58.35;
H, 6.05.
P r ep a r a tion of [(η5-C9H7)Rh (dCP h 2)(P iP r 2P h )] (10).
This was prepared as described for 6, from 5 (232 mg, 0.33
mmol) and C9H7K (258 mg, 1.67 mmol) in THF (10 mL) at
room temperature. For column chromatography, ether was
used as the eluant: dark green crystals; yield 150 mg (78%);
1
mp 70 °C dec. H NMR (400 MHz, C6D6): δ 7.25-6.80 (br m,
19H, C6H5 and H4-7), 5.70 (dt, J (HH) ) J (RhH) ) 2.4 Hz, 1H,
H2), 5.11 (m, 2H, H1,3), 1.57 (m, 2H, PCHCH3), 0.66 (dd, J (PH)
) 13.2, J (HH) ) 6.8 Hz, 6H, PCHCH3), 0.62 (dd, J (PH) ) 15.4,
J (HH) ) 7.2 Hz, 6H, PCHCH3). 13C NMR (100.6 MHz, C6D6):
δ 289.3 (dd, J (RhC) ) 49.3, J (PC) ) 13.1 Hz, RhdC), 163.1
(br s, ipso-C of C6H5), 134.3 (d, J (PC) ) 10.1 Hz, meta-C of
C6H5P), 133.1 (d, J (PC) ) 31.2 Hz, ipso-C of C6H5P), 129.3 (d,
J (PC) ) 0.2 Hz, ortho-C of C6H5P), 127.3, 127.2, 127.1, 127.0,
126.0 (all s, C6H5), 122.4, 121.8 (both s, C4-7), 118.8 (s, C8,9),
89.9 (d, J (RhC) ) 5.2 Hz, C2), 76.2 (br dd, J (RhC) ) J (PC) )
3.6 Hz, C1,3), 23.5 (dd, J (PC) ) 22.9, J (RhC) ) 2.0 Hz,
PCHCH3), 18.8 (br s, PCHCH3), 17.5 (s, PCHCH3). 31P NMR
(162.0 MHz, C6D6): δ 53.9 (d, J (RhP) ) 256.6 Hz). MS (FAB):
m/z 578 (M+), 463 (M+ - C9H7), 384 (M+ - PiPr2Ph). Anal.
Calcd for C34H36PRh (578.5): C, 70.59; H, 6.27. Found: C,
70.17; H, 6.32.
P r ep a r a tion of [(η5-C9H7)Rh (dCP h 2)(P iP r 3)] (7). This
was prepared as described for 6, from 2 (99 mg, 0.16 mmol)
and C9H7K (123 mg, 0.80 mmol) in THF (5 mL): dark green
crystals; yield 75 mg (87%); mp 75 °C dec. 1H NMR (200 MHz,
C6D6): δ 7.37-7.02 (br m, 14H, C6H5 and H4-7), 5.75 (dt, J (HH)
) J (RhH) ) 2.6 Hz, 1H, H2), 5.20 (m, 2H, H1,3), 1.52 (dsept,
J (PH) ) 13.3, J (HH) ) 7.1 Hz, 3H, PCHCH3), 0.87 (dd, J (PH)
) 13.3, J (HH) ) 7.1 Hz, 18H, PCHCH3). 13C NMR (50.3 MHz,
C6D6): δ 285.0 (dd, J (RhC) ) 50.8, J (PC) ) 12.8 Hz, RhdC),
P r epar ation of [{η5-C9H6(CHP h 2)}Rh (CO)(SbiP r 3)] (12).
A slow stream of CO was passed for 30 s through a solution of
6 (58 mg, 0.09 mmol) in pentane (10 mL) at -78 °C. Warming
of the solution to room temperature was accompanied by a
change of color from dark green via violet and red to yellow.
The solvent was removed in vacuo, and the residue was
dissolved in pentane (3 mL) which was saturated with CO.

Indenylrhodium Complexes with Diphenylcarbene
Organometallics, Vol. 19, No. 16, 2000 3113
384 (M+ - CO - PiPr3), 291 (M+ - C9H6(CHPh2)). Anal. Calcd
for C32H38OPRh (572.5): C, 67.13; H, 6.69; Rh, 17.97. Found:
C, 66.84; H, 6.90; Rh, 18.60.
Ta ble 3. Cr ysta llogr a p h ic Da ta for 6 a n d 13
formula
C31H38RhSb (6)
C32H38OPRh (13) +
1/2C6H14
615.59
P r ep a r a tion of [{η5-C9H6(CHP h 2)}Rh (CO)(P P h 3)] (14).
This was prepared as described for 12, from 8 (72 mg, 0.11
mmol) and CO: orange-yellow crystals; yield 65 mg (87%); mp
fw
635.27
cryst size, mm3
cryst syst
space group
cell dimens determn
0.5 × 0.43 × 0.3
monoclinic
P21/n (No. 14)
25 rflns,
12° < θ < 18°
17.66(5)
9.73(3)
18.06(5)
90
115.6(1)
90
2800(2)
4
0.5 × 0.4 × 0.4
triclinic
P1h (No. 2)
25 rflns,
10° < θ < 15°
9.4450(6)
11.505(1)
14.9591(5)
101.660(6)
99.720(4)
99.542(6)
1535.1(2)
2
68 °C dec. IR (C6H6): ν(CO) 1948 cm-1 1H NMR (400 MHz,
.
C6D6): δ 7.61 (m, 2H, C6H5), 7.42-6.50 (br m, 27H, C6H5 and
H4-7), 5.91 (m, 2H, CHPh2 and H2), 4.48 (m, 1H, H3). 13C NMR
(100.6 MHz, C6D6): δ 195.4 (dd, J (RhC) ) 90.1, J (PC) ) 22.4
Hz, Rh-CO), 144.0, 143.8 (both s, ipso-C of C6H5), 136.7 (d,
J (PC) ) 44.8 Hz, ipso-C of C6H5P), 134.1 (d, J (PC) ) 12.4 Hz,
meta-C of C6H5P), 132.4 (d, J (PC) ) 9.5 Hz, ortho-C of C6H5P),
130.3, 128.9, 128.6, 128.4, 128.2, 128.1 (all s, C6H5), 129.8 (d,
J (PC) ) 2.9 Hz, para-C of C6H5P), 123.0, 122.7 (both s, C4,7),
118.5 (s, C8 or C9), 117.9, 117.5 (both s, C5,6), 116.8 (s, C8 or
C9), 99.0 (dd, J (RhC) ) 5.7, J (PC) ) 1.9 Hz, CHPh2), 98.7 (dd,
J (RhC) ) 13.4, J (PC) ) 3.8 Hz, C1), 76.6 (br s, C2), 50.8 (br s,
C3). 31P NMR (162.0 MHz, C6D6): δ 47.9 (d, J (RhP) ) 201.8
Hz). Anal. Calcd for C41H32OPRh (674.6): C, 73.00; H, 4.78.
Found: C, 72.54; H, 5.04.
P r ep a r a t ion of [{η5-C9H 6(CH P h 2)}R h (CO)(P iP r P h 2)]
(15). This was prepared as described for 12, from 9 (85 mg,
0.14 mmol) and CO: orange-yellow crystals; yield 75 mg (84%);
mp 41 °C dec. IR (C6H6): ν(CO) 1943 cm-1. 1H NMR (400 MHz,
C6D6): δ 7.65 (m, 2H, C6H5), 7.43-6.66 (br m, 22H, C6H5 and
H4-7), 5.94 (br s, 1H, CHPh2), 5.85 (m, 1H, H2), 4.44 (m, 1H,
H3), 2.24 (m, 1H, PCHCH3), 0.85 (dd, J (PH) ) 17.0, J (HH) )
7.0 Hz, 3H, PCHCH3), 0.81 (dd, J (PH) ) 15.8, J (HH) ) 7.0
Hz, 3H, PCHCH3). 13C NMR (100.6 MHz, C6D6): δ 196.0 (dd,
J (RhC) ) 89.5, J (PC) ) 21.4 Hz, Rh-CO), 144.5, 144.1 (both
s, ipso-C of C6H5), 137.4 (d, J (PC) ) 39.7 Hz, ipso-C of C6H5P),
133.5 (d, J (PC) ) 10.5 Hz, meta-C of C6H5P), 130.7, 129.8,
128.9, 128.6, 128.3, 128.1, 128.0 (all s, C6H5), 126.5 (d, J (PC)
) 9.5 Hz, ortho-C of C6H5P), 123.1, 122.3 (both s, C4,7), 118.7
(s, C8 or C9), 117.9, 117.4 (both s, C5,6), 117.0 (s, C8 or C9), 98.7
(dd, J (RhC) ) 5.7, J (PC) ) 1.9 Hz, CHPh2), 98.6 (dd, J (RhC)
) 13.2, J (PC) ) 4.1 Hz, C1), 75.6 (br s, C2), 50.9 (br s, C3), 29.2
(d, J (PC) ) 29.5 Hz, PCHCH3), 19.4, 19.2 (both d, J (PC) ) 4.1
Hz, PCHCH3). 31P NMR (162.0 MHz, C6D6): δ 58.3 (d, J (RhP)
) 201.8 Hz). Anal. Calcd for C38H34OPRh (640.6): C, 71.25;
H, 5.35. Found: C, 71.13; H, 5.17.
P r ep a r a t ion of [{η5-C9H 6(CH P h 2)}R h (CO)(P iP r 2P h )]
(16). This was prepared as described for 12, from 10 (61 mg,
0.11 mmol) and CO: orange-yellow crystals; yield 55 mg (86%);
mp 78 °C dec. IR (C6H6): ν(CO) 1945 cm-1. 1H NMR (200 MHz,
C6D6): δ 7.68 (m, 2H, C6H5), 7.34 (m, 2H, ortho H of C6H5P),
7.24-6.92 (br m, 15H, C6H5 and H4-7), 6.07 (d, J (RhH) ) 3.2
Hz, 1H, CHPh2), 5.80 (m, 1H, H2), 4.64 (m, 1H, H3), 1.95 (m,
2H, PCHCH3), 0.79 (dd, J (PH) ) 16.7, J (HH) ) 6.8 Hz, 3H,
PCHCH3), 0.69 (dd, J (PH) ) 16.9, J (HH) ) 6.8 Hz, 3H,
PCHCH3), 0.66 (dd, J (PH) ) 17.2, J (HH) ) 6.8 Hz, 3H,
PCHCH3), 0.62 (dd, J (PH) ) 17.6, J (HH) ) 6.8 Hz, 3H,
PCHCH3). 13C NMR (100.6 MHz, C6D6): δ 195.0 (dd, J (RhC)
) 89.0, J (PC) ) 21.9 Hz, Rh-CO), 144.4, 143.8 (both s, ipso-C
of C6H5), 134.5 (d, J (PC) ) 10.2 Hz, meta-C of C6H5P), 130.4,
128.9, 128.7, 128.6, 128.1, 126.5 (all s, C6H5), 129.9 (d, J (PC)
) 2.0 Hz, para-C of C6H5P), 127.5 (d, J (PC) ) 9.2 Hz, ortho-C
of C6H5P), 123.5, 121.3 (both s, C4,7), 119.2 (s, C5 or C6), 118.7
(br s, C8,9), 117.4 (s, C5 or C6), 98.5 (dd, J (RhC) ) 5.1, J (PC) )
2.0 Hz, CHPh2), 98.3 (dd, J (RhC) ) 13.2, J (PC) ) 4.1 Hz, C1),
73.5 (d, J (RhC) ) 4.1 Hz, C2), 51.0 (d, J (RhC) ) 2.0 Hz, C3),
26.1 (br d, J (PC) ) 19.3 Hz, PCHCH3), 25.9 (br d, J (PC) )
17.3 Hz, PCHCH3), 18.5, 18.4 (both d, J (PC) ) 6.1 Hz,
PCHCH3), 17.8, 17.3 (both br s, PCHCH3); signal of ipso-C of
C6H5P could not be exactly located. 31P NMR (162.0 MHz,
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
d
calcd, g cm-3
1.508
1.332
temp, K
223(2)
1.571
ω/θ
48
173(2)
0.627
ω/θ
48
5149
4820 (R(int) )
0.0166)
µ, mm-1
scan method
2θ(max), deg
total no. of rflns
no. of unique rflns
3142
2986 (R(int) )
0.0328)
2406
no. of obsd rflns
(I > 2σ(I))
no. of rflns used for
refinement
4573
2984
4820
no. of params refined
final R indices
(I > 2σ(I))
298
354
R1 ) 0.0304,
wR2 ) 0.0676a
R1 ) 0.0493,
wR2 ) 0.0772a
R1 ) 0.0265,
wR2 ) 0.0637a
R1 ) 0.0283,
wR2 ) 0.0653
0.730/-0.705
R indices (all data)
resid electron density, 0.519/-0.535
e Å-3
a
2
2
w-1 ) [σ2Fo + (0.0427P)2 + 0.7682P] (6) and w-1 ) [σ2Fo
+
2
(0.0270P)2 + 2.0493P] (13), where P ) (Fo + 2Fc2)/3.
After the solution was stored for 3 days at -18 °C, yellow
crystals precipitated which were separated from the mother
liquor, washed with a small amount of pentane (-10 °C), and
dried: yield 47 mg (78%); mp 42 °C dec. IR (C6H6): ν(CO) 1930
cm-1. 1H NMR (400 MHz, C6D6): δ 7.23-6.70 (br m, 14H, C6H5
and H4-7), 5.58 (br s, 1H, CHPh2), 5.52 (m, 1H, H2), 5.11 (d,
J (RhH) ) 3.0 Hz, 1H, H3), 2.08 (m, 3H, SbCHCH3), 1.34 (m,
18H, SbCHCH3). 13C NMR (100.6 MHz, C6D6): δ 190.8 (d,
J (RhC) ) 86.5 Hz, Rh-CO), 147.0, 144.9 (both s, ipso-C of
C6H5), 132.1, 131.8, 130.7, 128.7, 128.1, 125.0 (all s, C6H5),
124.1, 121.2 (both s, C4,7), 119.4 (s, C5 or C6), 118.3 (s, C8 or
C9), 118.2 (s, C5 or C6), 117.3 (s, C8 or C9), 102.6 (d, J (RhC) )
3.0 Hz, C1), 98.9 (d, J (RhC) ) 6.1 Hz, CHPh2), 71.7 (d, J (RhC)
) 4.1 Hz, C2), 50.3 (br s, C3), 22.0 (s, SbCHCH3), 21.3 (s,
SbCHCH3). Anal. Calcd for C32H38ORhSb (663.3): C, 57.94;
H, 5.77. Found: C, 57.78; H, 5.59.
P r ep a r a tion of [{η5-C9H6(CHP h 2)}Rh (CO)(P iP r 3)] (13).
This was prepared as described for 12, from 7 (98 mg, 0.18
mmol) and CO: orange-yellow solid; yield 81 mg (79%); mp
56 °C dec. IR (hexane): ν(CO) 1944 cm-1. 1H NMR (400 MHz,
C6D6): δ 7.69 (m, 2H, C6H5), 7.24-6.89 (br m, 12H, C6H5 and
H4-7), 6.06 (d, J (RhH) ) 3.2 Hz, 1H, CHPh2), 5.83 (m, 1H, H2),
4.82 (d, J (RhH) ) 3.2 Hz, 1H, H3), 1.72 (br sept, J (HH) ) 7.2
Hz, 3H, PCHCH3), 0.84 (dd, J (PH) ) 14.4, J (HH) ) 7.2 Hz,
9H, PCHCH3), 0.81 (dd, J (PH) ) 14.0, J (HH) ) 7.2 Hz, 9H,
PCHCH3). 13C NMR (100.6 MHz, C6D6): δ 196.0 (dd, J (RhC)
) 89.0, J (PC) ) 21.6 Hz, Rh-CO), 144.3, 144.0 (both s, ipso-C
of C6H5), 130.4, 128.9, 128.5, 128.1, 126.5, 126.4 (all s, C6H5),
122.9, 121.2 (both s, C4,7), 119.3 (s, C8 or C9), 118.6 (s, C5 or
C6), 117.6 (s, C8 or C9), 117.3 (s, C5 or C6), 98.5 (dd, J (RhC) )
5.2, J (PC) ) 1.7 Hz, CHPh2), 97.3 (dd, J (RhC) ) 13.0, J (PC)
) 3.8 Hz, C1), 72.3 (d, J (RhC) ) 3.3 Hz, C2), 51.0 (d, J (RhC) )
1.5 Hz, C3), 28.0 (d, J (PC) ) 21.2 Hz, PCHCH3), 19.8, 19.7
(both s, PCHCH3). 31P NMR (162.0 MHz, C6D6): δ 74.3 (d,
J (RhP) ) 194.7 Hz). MS (FAB): m/z 572 (M+), 544 (M+ - CO),
C6D6): δ 67.8 (d, J (RhP) ) 201.7 Hz). Anal. Calcd for C35H36
OPRh (606.6): C, 69.31; H, 5.98; C, 69.61; H 6.33.
-
X-r a y Str u ctu r a l Deter m in a tion of Com p ou n d s 6 a n d
13. Single crystals of 6 were grown from pentane at -18 °C
and those of 13 from hexane (saturated with CO) at -18 °C.

3114 Organometallics, Vol. 19, No. 16, 2000
Bleuel et al.
Crystal data collection parameters are summarized in Table
3. Intensity data were corrected by Lorentz and polarization
effects, and an empirical absorption correction was applied in
each case (minimum transmission 83.47% (6) and 96.35% (13)).
The structure of 6 was solved by the Patterson method
(SHELXS-86)14 and that of 13 by direct methods (SHELXS-
86). Atomic coordinates and the anisotropic thermal param-
eters of non-hydrogen atoms were refined by full-matrix least
squares on F2 (SHELXL-93).15 In 13, half of a molecule of
hexane was found in the asymmetric unit and refined aniso-
tropically with restraints on the anisotropic displacement
parameters and interatomic distances. The center of the
central C-C bond lies on the crystallographic center of
symmetry. The positions of all hydrogen atoms in 6 and 13
were calculated according to ideal geometry and were refined
by using the riding method, except for H6 of 13, which was
found and refined isotropically.
Ack n ow led gm en t. We gratefully acknowledge fi-
nancial support from the Deutsche Forschungsgemein-
schaft (Grant No. SFB 347), the Fonds der Chemischen
Industrie, and BASF AG. Moreover, we also thank R.
Schedl and C. P. Kneis (DTA and elemental analysis),
M.-L. Scha¨fer and Dr. W. Buchner (NMR spectra), and
Dr. G. Lange and Mr. F. Dadrich (mass spectra).
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 6 and 13.
This material is available free of charge via the Internet at
http://pubs.acs.org.
(14) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467-473.
(15) Sheldrick, G. M. SHELXL-93; University of Go¨ttingen, Go¨ttin-
gen, Germany, 1993.
OM000188V