Cationic and neutral diphenyldiazomethanerhodium(I) complexes as catalytically active species in the C-C coupling reaction of olefins and diphenyldiazomethane

Article abstract of DOI:10.1002/1521-3765(20000818)6:16<3052::AID-CHEM3052>3.0.CO;2-C

Cationic rhodium(I) complexes cis-[Rh(acetone)₂(L)(L')]⁺ (2: L=L'=C₈H₁₄; 3: L=C₈H₁₄; L'=PiPr₃; 4: L= L'=PiPr₃), prepared from [{RhCl-(C₈H₁₄)

Full text of DOI:10.1002/1521-3765(20000818)6:16<3052::AID-CHEM3052>3.0.CO;2-C

FULL PAPER
Cationic and Neutral Diphenyldiazomethanerhodium(i) Complexes as
À
Catalytically Active Species in the C C Coupling Reaction of Olefins and
Diphenyldiazomethane
[
a]
[a]
[a]
[a]
[b]
Helmut Werner,* Michael E. Schneider, Marco Bosch, Justin Wolf, Jan H. Teuben,
[
c]
[d]
Auke Meetsma, and Sergei I. Troyanov
Dedicated to Professor Günter Wilke on the occasion of his 75th birthday
Abstract: Cationic rhodium(i) complexes
around the rhodium(i) center. Treatment
of 4 with Ph CN in the molar ratio of 1:1
(possibly resting states) in the CÀC
coupling process. The lability of 8 and
9 is illustrated by the reactions with
‡
cis-[Rh(acetone) (L)(L')] (2: L ˆ L' ˆ
2
2
2
C H ; 3: L ˆ C H ; L' ˆ PiPr ; 4: L ˆ
and 1:2 gave the complexes trans-[Rh-
8
14
8
14
3
1
L' ˆ PiPr ), prepared from [{RhCl-
(PiPr ) (acetone)(h -N CPh )]PF
(8)
pyridine and NaX (X ˆ Cl, Br, I, N )
3
3
2
2
2
6
3
1
(
C H ) } ] and isolated as PF salts,
and trans-[Rh(PiPr ) (h -N CPh ) ]PF
6
which afford the mono(diphenyldiazo-
8
14
2
2
6
3
2
2
2
2
catalyze the CÀC coupling reaction of
(9), of which 8 was characterized by
X-ray crystallography. Since 8 and 9 not
only react with ethene but also catalyze
the reaction of C H and free Ph CN ,
methane)rhodium(i) compounds trans-
1
diphenyldiazomethane with ethene, pro-
pene, and styrene. In most cases, a
mixture of isomeric olefins and cyclo-
propanes were obtained which are for-
mally built up by one equivalent of
RCHˆCH2 (R ˆ H, Me, Ph) and one
[Rh(PiPr ) (py)(h -N CPh )]PF (10) and
3
2
2
2
6
1
trans-[RhX(h -N CPh )(PiPr ) ]
(11 ±
2
2
3 2
14), respectively. The catalytic activity
of the neutral complexes 11 ± 14 is some-
what less than that of the cationic
species 8, 9 and decreases in the order
Cl > Br> I > N3.
2
4
2
2
they can be regarded as intermediates
Keywords: acetone complexes
CÀC coupling ´ N ligands ´ Pligands
rhodium
´
equivalent of CPh . The efficiency and
2
selectivity of the catalyst depends sig-
nificantly on the coordination sphere
´
Introduction
as the monomeric ethene derivative trans-[RhCl(C
H )-
2 4
(
PiPr ) ] react with diphenyldiazomethane to afford the
3
2
During studies directed to the synthesis of carbenerhodium(i)
square-planar diazoalkane compound trans-[RhCl(N CPh )-
2 2
[1]
complexes of the general composition trans-[RhCl(ˆCR )-
(PiPr ) ]. Moreover, we discovered that various rhodium(i)
2
3 2
(
PiPr ) ], we observed that the dimer [{RhCl(PiPr ) } ] as well
complexes including [{RhCl(PiPr ) } ] and [{RhCl(C H ) } ]
3 2 2 2 4 2 2
3
2
3
2
2
catalyze the reaction of ethene and diphenyldiazomethane to
[
a] Prof. Dr. H. Werner, Dr. M. E. Schneider, Dipl.-Chem. M. Bosch,
Dr. J. Wolf
give almost selectively 1,1-diphenylprop-1-ene Ph CˆCH-
2
Me.[
1, 2]
The formation of this trisubstituted olefin can be
Institut für Anorganische Chemie der Universität Würzburg
Am Hubland, 97074 Würzburg (Germany)
Fax : (‡49) 931-888-4605
formally understood as the coupling of two carbene fragments
:CPh and :CHMe, of which the latter is generated from the
2
E-mail: helmut.werner@mail.uni-wuerzburg.de
isomeric ethene. Besides Ph CˆCHMe, there were only traces
2
[
b] Prof. Dr. J. H. Teuben
of 1,1-diphenylcyclopropane detected which was surprising
insofar as it was well known that dinuclear bis(carboxylato)-
rhodium(ii) compounds such as [Rh (m-O CMe) ] and
Groningen Center for Catalysis and Synthesis
Department of Chemistry of the University of Groningen
Nijenborgh 4, 9747 AG Groningen (The Netherlands)
E-mail: teuben@chem.rug.nl
2
2
4
derivatives thereof are effective catalysts for the synthesis
[
3]
[
c] Drs. A. Meetsma
of cyclopropanes from olefins and diazoalkanes. In the
context of these investigations we also found that, if the
anionic ligand in the chlororhodium(i) complexes is substi-
tuted by acetate, benzoate, or acetylacetonate, the catalytic
Department of Chemical Physics of the University of Groningen
Nijenborgh 4, 9747 AG Groningen (The Netherlands)
E-mail: a.meetsma@fwn.rug.nl
[
d] Dr. S. I. Troyanov
activity decreases and besides Ph CˆCHMe and cyclo-1,1-
2
Institut für Chemie der Humboldt Universität Berlin
Hessische Strasse 1-2, 10115 Berlin (Germany)
E-mail: sergej ˆ troyanov@rz.hu-berlin.de
C H Ph , a third isomer CH ˆCHCHPh is formed from C H
3
4
2
2
2
2
4
[4]
and Ph CN .
2
2
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Chem. Eur. J. 2000, 6, No. 16

3
052±3059
Because of this apparent influence of the anionic ligand on
both the reactivity and the selectivity, we became interested to
find out whether cationic rhodium(i) complexes also catalyze
the reaction of olefins (not only ethene) and diphenyldiazo-
methane and what the products of these CÀC coupling
processes are. Here we report on the preparation of a series of
compounds of the general composition cis-[Rh(acetone) (L)-
2
(
L')]PF , on the synthesis of cationic as well as neutral
6
rhodium(i) complexes containing Ph CN as a ligand, and on
2
2
the catalytic activity of these species in CÀC coupling
reactions. Some preliminary results have already been com-
municated.[
5]
Results and Discussion
Scheme 1. Preparation of the cationic bis(acetone)rhodium(i) complexes
± 4 from the bis(cyclooctene) complex 1.
Cationic bis(acetone)rhodium(i) complexes: From earlier
work it was already known that the dimeric diolefinrho-
2
dium(i) complexes [{RhCl(diolefin)} ] (diolefin ˆ norborna-
2
diene, cycloocta-1,5-diene) react with AgPF in a coordinating
(Figure 1) which reveals that the coordination sphere around
the rhodium center is distorted square-planar. The cyclo-
octene as well as the acetone ligands are in cis disposition, the
distances Rh(1)ÀO(1) and Rh(1)ÀO(2) (2.138(4) and
2.126(4) Š) being somewhat longer than the RhÀO distance
6
solvent such as acetone or THF to give the compounds
[
6]
[
Rh(S) (diolefin) ]PF (S ˆ acetone, THF). The ªsilver-salt-
2
2
6
methodº had also been used in our laboratory for the
preparation of the bis(cyclooctene) derivative 2 (Scheme 1)
which contains four labile monodentate ligands. These are
easily displaced by a bidentate donor such as iPr PCH -
2
2
2
CH OMe to produce [Rh(k -O,P-iPr PCH CH OMe) ]PF in
2
2
2
2
2
6
a good yield.[
7]
In order to confirm the supposed stereochemistry of the
cation of 2, an X-ray crystal structure analysis was carried out
Abstract in German: Die kationischen Rhodium(i)-Komplexe
‡
cis-[Rh(acetone) (L)(L')] (2: L ˆ L' ˆ C H ; 3: L ˆ C H ;
2
8
14
8
14
L' ˆ PiPr ; 4: L ˆ L' ˆ PiPr ), die aus [{RhCl(C H ) } ]
3
3
8
14 2 2
hergestellt und als PF -Salze isoliert wurden, katalysieren die
6
C-C-Kupplungsreaktion von Diphenyldiazomethan mit Ethen,
Propen und Styrol. In den meisten Fällen wird ein Gemisch
isomerer Olefine und Cyclopropane erhalten, die sich formal
aus einem ¾quivalent RCHˆCH (R ˆ H, Me, Ph) und einem
2
¾
quivalent CPh zusammensetzen. Die Effektivität und die
Figure 1. Molecular structure of 2 (anionic ligand omitted for clarity).
Principal bond lengths [Š] and angles [8] with estimated standard devia-
tions in parentheses: Rh(1)ÀO(1) 2.138(4), Rh(1)ÀO(2) 2.126(4),
Rh(1)ÀC(1) 2.126(5), Rh(1)ÀC(2) 2.122(5), Rh(1)ÀC(9) 2.113(5),
Rh(1)ÀC(10) 2.148(5), C(1)ÀC(2) 1.394(7), C(9)ÀC(10) 1.393(7),
O(1)ÀC(17) 1.232(7), O(2)ÀC(20) 1.240(7); O(1)-Rh(1)-O(2) 83.87(14),
2
Selektivität des Katalysators hängen entscheidend von der
Koordinationssphäre des Rhodium(i)-Zentrums ab. Die Um-
setzungen von 4 mit Ph CN im Molverhältnis 1:1 und 1:2
2
2
1
liefern
die
Komplexe
trans-[Rh(PiPr ) (acetone)(h -
3
1
2
N CPh )]PF (8) und trans-[Rh(PiPr ) (h -N CPh ) ]PF
Rh(1)-O(1)-C(17) 126.8(4), Rh(1)-O(2)-C(20) 127.3(4).
2
2
6
3
2
2
2
2
6
(
9), von denen 8 durch eine Kristallstrukturanalyse charak-
terisiert wurde. Da die Verbindungen 8 und 9 nicht nur mit
(
(
2.078(2) Š) in the cation trans-[Rh(ˆCˆCˆCPh )(acetone)-
Ethen reagieren, sondern auch die Reaktion von C H mit
2
2
4
‡
[8]
PiPr ) ] . The coordinated CÀC bonds of the C H ligands
3
2
8
14
freiem Ph CN katalysieren, können sie als Zwischenstufen
2
2
are significantly elongated compared with the free olefin
indicating a relative high degree of back bonding from the
metal to the olefin. The bond angles Rh(1)-O(1)-C(17) and
Rh(1)-O(2)-C(20) are 126.8(4)8 and 127.3(4)8, respectively,
which indicates that the acetone ligands are coordinated
through one of the lone pairs of electrons on the oxygen atom.
(
möglicherweise als ¹resting stateª) in dem C-C-Kupplungs-
prozess angesehen werden. Die Labilität von 8 und 9 zeigt sich
bei den Reaktionen mit Pyridin und NaX (X ˆ Cl, Br, I, N ),
3
die zu den Mono(diphenyldiazomethan)rhodium(i)-Verbin-
1
dungen trans-[Rh(PiPr ) (py)(h -N CPh )]PF (10) und
trans-[RhX(h -N CPh )(PiPr ) ] (11 ± 14) führen. Die kataly-
tische Aktivität der Neutralkomplexen 11 ± 14 ist etwas gerin-
ger als diejenige der kationischen Spezies 8, 9 und nimmt in der
Reihenfolge Cl > Br > I > N ab.
3
2
2
2
6
1
2
2
3 2
Upon treatment of 2 with PiPr in diethyl ether a replace-
3
ment of one cyclooctene ligand occurs and the PF salt of the
6
cationic monophosphane complex 3 is formed. The compo-
sition of the yellow crystalline solid is supported both by the
3
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3053

H. Werner et al.
FULL PAPER
elemental analysis and the spectroscopic data. The IR
than metathesis products is generated. Moreover, in the
5
spectrum of 3 displays two CˆO stretching frequencies at
first case the metallacyclobutane complex [(h -C H )-
5
5
À1
2
1
701 and 1658 cm in agreement with a cis disposition of the
Ti(CH CH CHtBu)(k -O,P-OCH CH PPh )] could be isolat-
2 2 2 2 2
two acetone units. We note that the reaction of 2 with two
equivalents of triisopropylphosphane generates the bis(phos-
phane) compound 4 which in contrast to 3 is a violet, quite air-
sensitive solid.[ The presence of 1:1 electrolytes has been
confirmed for 3 as well as for 4 by conductivity measurements.
ed and charaterized.
The cationic complexes not only catalyze the reaction of
Ph CN with ethene but also that of diphenyldiazomethane
2
2
8]
with substituted olefins such as propene and styrene. With
CH ˆCHCH and Ph CN as starting materials and catalytic
2
3
2
2
amounts of 2 ± 4 (in THF at 408C) a mixture of four isomers
(6a ± 6d) is formed (Scheme 3). In each case the dominating
Catalytic activity of compounds
2
± 4: As has been described for
the neutral complexes trans-
2
[
RhCl(C H )(PiPr ) ], [Rh(h -
2
4
3 2
O CR)(PiPr ) ],
[Rh(acac)-
2
3 2
(
PiPr ) ],
[{RhCl(C H ) } ],
3
2
2
4 2 2
and [{RhCl(PiPr ) } ], the cat-
3
2 2
ionic compounds 2 ± 4 also cata-
lyze the CÀC coupling reaction
of ethene and diphenyldiazo-
methane. The most noteworthy
feature is that both the activity
and the selectivity significantly
depends on the coordination
sphere around the rhodium(i)
center (see Scheme 2). If one
cyclooctene ligand in 2 is dis-
Scheme 2. Results of the cata-
lytic reaction of ethene and
Ph
as catalyst (T.O.N. ˆ turnover
number ˆ [(mmol product)/
mmol catalyst)]; ratio of 5a
and 5b in%).
2 2
CN with compounds 2 ± 4
placed by PiPr , the activity
3
Scheme 3. Results of the catalytic reaction of propene and Ph
compounds 2 ± 4 as catalyst (T.O.N. ˆ turnover numberˆ [(mmol product)/
mmol catalyst)]; ratio of 6a, 6b, 6c, and 6d in%).
2 2
CN with
increases while the amount of
1,1-diphenylcyclopropane (5a)
compared to 1,1-diphenylprop-
(
(
1-ene (5b) decreases. In contrast, substitution of both olefinic
ligands by triisopropylphosphane leads to a significant
decrease in activity but also to a tremendous increase in
selectivity, the cyclopropanation product 5a being almost
exclusively formed.
species is the trisubstituted cyclopropane 6a; the relative
amount of this CÀC coupling product decreases with the
increasing number of phosphane ligands at the rhodium
center. This result is in contrast to the C H /Ph CN system
2
4
2
2
The mechanism of the reaction of ethene and diphenyldi-
azomethane in the presence of 2, 3, or 4 as catalyst is not clear
as yet. We assume that in the initial stage of the catalytic
process both C H and Ph CN are coordinated to rhodium
where the opposite trend is observed.
A decrease in selectivity is also observed for the rhodium-
catalyzed reaction of diphenyldiazomethane with styrene.
With the phosphane-free compound 2 as the catalyst, the
isomeric olefins 7b ± 7d are generated in nearly equal
amounts; in this case (Scheme 4) the trisubstituted cyclo-
2
4
2
2
and that, after elimination of N , a four-membered RhC cycle
2
3
is formed. The next step could be the opening of the
metallacyclobutane ring to give a chainlike cationic inter-
‡
mediate RhCH CH CPh bearing the positive charge at the
2
2
2
trisubstituted terminal carbon atom. Reductive elimination
and ring closure should yield the cyclopropane 5a. Regarding
the formation of the olefinic isomer 5b, it is conceivable that
the postulated metallacyclobutane reacts by b-H shift to
afford a p-allyl(hydrido)rhodium(iii) intermediate [L RhH-
3
3
‡
(
h -CH CHCPh )] which, by reductive coupling of the
2 2
hydrido ligand and the CH carbon atom of the allyl unit,
2
generates Ph CˆCHMe (5b).
2
Interestingly, no formation of CH ˆCPh , which would be
2
2
the result of a retro-[2‡2] cycloaddition of the postulated
metallacyclobutane, is observed. This finding, however, does
not exclude the possibility of a metallacyclic intermediate.
Recent studies on the reactivity of ethene toward carbene
5
2
titanium complexes [(h -C H )Ti(k -O,P-OCH CH PPh )-
5
5
2
2
2
2 2
Scheme 4. Results of the catalytic reaction of styrene and Ph CN with
[
9]
5
(
(
ˆCHtBu)]
and [{h -C H (CH ) NtBu-k-N}Ti(ˆCHtBu)-
5
4
2
2
compounds 2 ± 4 as catalyst (T.O.N. ˆ turnover numberˆ [(mmol product)/
[
10]
PMe )] have shown that a mixture of CÀC coupling rather
(mmol catalyst)]; ratio of 7a, 7b, 7c, and 7d in%).
3
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Chem. Eur. J. 2000, 6, No. 16

Diphenyldiazomethanerhodium(i) Complexes
3052±3059
propane 7a is the minor product. In contrast to 2, the
bis(phosphane) complex 4 is somewhat more selective and
converts one third of the starting materials PhCHˆCH and
2
Ph CN to 1,1,2-triphenylcyclopropane and two thirds to a 2:1
2
2
mixture of the olefins 7c and 7d. In our opinion, there is no
rationale at the moment which could explain the influence of
the coordination sphere around the metal center on the
catalytic activity of the cationic species. Importantly, however,
the selectivity of the CÀC coupling process critically depends
on the type of ligands bonded to rhodium(i); apparently the
presence of the sterically demanding triisopropylphosphanes
seems to disfavor a high degree of selectivity.
Isolation of possible intermediates: In order to prove whether
the proposed catalytic cycles for the reactions of ethene and
its derivatives with diphenyldiazomethane involve the for-
mation of Rh(N CPh ) species as intermediates, the reactivity
2
2
of the cationic complexes toward Ph CN has been inves-
2
2
tigated. The bis(cyclooctene) compound 2 is rather inert
toward the diazoalkane; after stirring a suspension of the
starting materials in diethyl ether for 30 min no reaction was
observed.
The monophosphane complex behaves differently. Addi-
Scheme 5. Preparation of the cationic diphenyldiazomethanerhodium(i)
complexes 8 ± 10 from the bis(acetone) complex 4.
tion of one equivalent of Ph CN to a suspension of 3 in ether
2
2
leads, even at À788C, to a smooth change of color of the
solution from red to off-white. While the remaining redbrown
3
1
Despite the lability of 8 in solution, we were able to grow
single crystals by slow diffusion of ether into a saturated
solution of 8 in acetone. The result of the X-ray crystal
structure analysis is shown in Figure 2. The coordination
solid was shown by PNMR spectroscopy to be the
unchanged starting material 3, the solution contained the
ketazine Ph CˆNÀNˆCPh (confirmed by GC/MS) which is
2
2
probably generated by a metal-catalyzed conversion of
Ph CN . We note that Lemenovskii and co-workers have
2
2
already reported that the reactions of the trishydrides
[
(C H ) MH ] (M ˆ Nb, Ta) with diaryldiazomethanes
5
5
2
3
RR'CN2 afford the corresponding ketazines RR'CˆNÀNˆ
CRR', in this case probably via the monohydrido compounds
1
[11]
[
(C H ) MH(h -N CRR')] as intermediates.
5 5 2 2
Stable cationic diphenyldiazomethanerhodium(i) com-
plexes are formed from the bis(acetone)rhodium(i) derivative
as the starting material. Treatment of a suspension of 4 in
4
ether with either one or two equivalents of Ph CN at À788C
2
2
leads to a stepwise substitution of the ketonic ligands and
gives the compounds 8 and 9 in about 80% yield (Scheme 5).
Both 8 and 9 are dark green, moderately air-sensitive solids,
the composition of which has been confirmed by elemental
3
1
analyses and conductivity measurements. The PNMR
3
1
103
spectra of 8 and 9 display a doublet with a P ± Rh coupling
constant of 122.1 Hz (8) and 116.2 Hz (9) indicating that, in
contrast to the starting material 4, the two phosphane ligands
Figure 2. Molecular structure of 8 (anionic ligand omitted for clarity).
Principal bond lengths [Š] and angles [8] with estimated standard
deviations in parentheses: Rh(1)ÀP(1) 2.3546(8), Rh(1)ÀP(2) 2.3693(8),
are in trans disposition.[ In the C NMR spectra of 8 and 9,
7, 8]
13
Rh(1) O(1) 2.039(2), Rh(1) N(1) 1.869(3), N(1) N(2) 1.157(4),
À
À
À
the resonance for the diazoalkane carbon atom Ph CN
N(2)ÀC(19) 1.312(4), O(1)ÀC(32) 1.237(4); P(1)-Rh(1)-P(2) 170.88(3),
2
2
P(1)-Rh(1)-O(1) 90.36(6), P(1)-Rh(1)-N(1) 91.71(8), P(2)-Rh(1)-O(1)
appears at d ˆ 84.5 (8) and d ˆ 83.3 (9) as a broad singlet,
the broadening probably being due to the quadrupol moment
of the nitrogen atoms. Regarding the stability of the mono-
substitution product 8 it should be mentioned that in solution
8
9.47(6), P(2)-Rh(1)-N(1) 87.29(8), O(1)-Rh(1)-N(1) 172.21(10), Rh(1)-
O(1)-C(32) 140.1(2), Rh(1)-N(1)-N(2) 161.0(2), N(1)-N(2)-C(19) 171.6(3).
3
1
a partial disproportionation of 8 to 4 and 9 occurs. The
P
geometry around the metal center is slightly distorted square-
planar with bond angles P(1)-Rh(1)-P(2) and O(1)-Rh(1)-
N(1) of 170.88(3)8 and 172.21(10)8, respectively. The Rh(1)-
N(1)-N(2) chain is considerably bent, the bond angle being
NMR spectrum of 8 in [D ]acetone shows, besides the doublet
6
at d ˆ 40.2, two other doublets at d ˆ 60.3 (for 4) and d ˆ 46.5
(
for 9) with the intensity ratio of approximately 4:1:1.
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3055

H. Werner et al.
FULL PAPER
about 108 smaller than in the octahedral cationic tungsten com-
diazoalkane complexes 11 ± 14 in good to excellent yield
(Scheme 6). Similarly to the chloro derivative 11, which was
previously prepared from [RhCl(PiPr ) ] or trans-[RhCl-
‡
[12]
pound [WBr(N CMe )(dppe) ] (dppe ˆ 1,2-C H (PPh ) ).
2
2
2
2
4
2 2
The more remarkable fact, however, is that the N(1)-N(2)-
C(19) angle is nearly linear (171.6(3)8) which is unusual
compared to other N-bonded diazoalkane metal complexes.[
Since the size of the bond angle N-N-C in compounds
3
2 2
[1, 2a]
(C H )(PiPr ) ] and Ph CN ,
the related compounds 12 ±
2
4
3
2
2
2
13]
14 are also dark green solids which are quite stable and
1
n‡
[
L M(h -N CRR')] should depend on the degree of d ! p*
n
2
metal-to-ligand back bonding, gaining a maximum at an N-N-
C angle of 1208, we assume that in 8 the diphenyldiazo-
methane behaves predominantly as a s-donor ligand. An
analogous conclusion has been drawn in the case of trans-
RhCl{h -N C(C H ) CO}(PiPr ) ] and some other [M(h -
N CR )] complexes.
1
[14]
1
[
2 6 4 2 3 2
[
15, 16]
2
2
Regarding the distances in 8, the N(1)ÀN(2) and
N(2)ÀC(19) bond lengths are rather short (1.157(4) and
1
(
.312(4) Š) and quite similar to those in free diazomethane
1.12 and 1.32 Š).[ This similarity supports the proposal that
13]
the s-donor character of the diphenyldiazomethane ligand in
8
dominates. The Rh(1)ÀN(1) distance (1.869(3) Š) is rather
short and comparable to the RhÀN bond length in the square-
planar dinitrogenrhodium(i) complex trans-[RhCl(N )-
2
[17]
(
PiPr ) ].
Scheme 6. Preparation of the neutral diphenyldiazomethanerhodium(i)
complexes 11 ± 14 from the cationic compounds 8 or 9 as the precursors.
3
2
Both the cationic compounds 8 and 9 are quite labile and
react smoothly with pyridine to give the monosubstituted
product 10 (see Scheme 5). While in the reaction of 8 with
pyridine the acetone ligand is replaced, treatment of 9 with
pyridine leads to the formation of N2 and the ketazine
Ph CˆNÀNˆCPh as the by-products. Compound 10 is a
neither on heating nor photolysis eliminate N to give trans-
2
[19]
[
RhX( CPh )(PiPr ) ].
ˆ
Characteristic spectroscopic fea-
2 3 2
tures of 12 ± 14 are the N N stretching frequency for the
À
À1
2
2
diphenyldiazomethane ligand at 1940 ± 1955 cm in the IR
green, moderately air-sensitive solid, the composition of
which has been confirmed by analytical and spectroscopic
and the singlet resonance for the Ph CN carbon atom at d ˆ
2
2
13
7
8.3 ± 79.4 in the C NMR spectrum. For 14, the n(N ) band
3
data. The appearance of a doublet of virtual triplets for the
À1
appears at 2038 cm .
1
PCHCH protons in the H NMR spectrum and of a sharp
3
The catalytic activity of the neutral compounds 11 ± 14 in
the reaction of C H and Ph CN is somewhat less than that of
31
103
doublet with a P ± Rh coupling constant of 126.7 Hz in the
PNMR spectrum are indicative for the trans disposition of
2
4
2
2
31
the cationic species 8 and 9 (for details see Experimental
Section). The turnover number (in methylcyclohexane at
the phosphane ligands. The structural proposal for 10 is
somewhat reminiscent to that for the amine complexes
4
08C) decreases in the order Cl > Br> I> N . A more note-
3
[
Rh(PNP)(HNR )]PF [PNP ˆ 2,6-NC H (CH PPh ) ] which
2
6
5
3
2
2
2
worthy observation is that a significant difference exists in the
selectivity between 11 on one side and 12 ± 14 on the other.
While upon treatment of ethene with diphenyldiazomethane
in the presence of 11 as the catalyst almost exclusively the
trisubstituted olefin 5b is formed, the analogous reaction of
C H and Ph CN with 12, 13, or 14 as the catalyst yield a
are formed upon treatment of the ethene derivative
[18]
[Rh(PNP)(C H )]PF with secondary amines.
2 4 6
To find out whether the isolated compounds 8 and 9 could
play a role in the above-mentioned catalytic process between
C H and Ph CN , both diazoalkane complexes were treated
2
4
2
2
2
4
2
2
with ethene. In THF at 408C, the major organic product is the
cyclopropane derivative 5a. Whereas in the case of 8, only
mixture 5a and 5b in the ratio of 19:81 (12), 8:92 (13), and
9:61 (14), respectively. These data confirm (as mentioned above)
3
traces of 5b (<1%) are formed, the reaction of 9 with C H
2
4
that the ligands coordinated to rhodium(i) as the active center
play a crucial role for the C C coupling process, even minor
differences in the electron density at rhodium are possibly
responsible for the preference for one or the other route.
yields a mixture of 5a to 5b in the ratio of about 9:1. Since
almost identical results regarding the product distribution are
À
obtained for the catalytic reaction of C H and free Ph CN ,
2
4
2
2
we conclude that 8 and 9 can be regarded as intermediates
possibly resting states) in the catalytic cycle. For 9, the
(
turnover number (in THF at 408C) for the formation of the
CÀC coupling product 5a of 33 is very similar to that with 4 as
Experimental Section
the catalyst.
All experiments were carried out under an atmosphere of argon by Schlenk
techniques. The commercially available starting materials ethene, propene
Neutral diphenyldiazomethanerhodium(i) complexes: The
pronounced lability of the cations of 8 and 9 prompted us to
study also the reactivity of these species toward halide and
azide anions. Both compounds 8 and 9 react smoothly with
and styrene were used without purification. PiPr
3
was a commercial
8
14 2 2
H ) ]
(1)[ , cis-
20]
product from Strem Chemicals. The complexes [RhCl(C
2 8 14 2 6 2 3 2 6
Rh(acetone) (C H ) ]PF (PiPr ) ]PF (4)
(2),[ and cis-[Rh(acetone)
7, 8]
[8]
[
were prepared as described in the literature. NMR spectra were recorded,
unless stated otherwise, at room temperature on Bruker AC 200 and
Bruker AMX 400 instruments. Abbreviations used: s, singlet; d, doublet; q,
NaX (X ˆ Cl, Br, I, N ) in ether to afford the neutral
3
3056
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Chem. Eur. J. 2000, 6, No. 16

Diphenyldiazomethanerhodium(i) Complexes
3052±3059
quartet; sept, septet; m, multiplet; br, broadened signal; dvt, doublet of
(2  2 mL) and pentane (3  2 mL) and dried in vacuo. Yield ˆ 56 mg,
3
5
2
4
2
À1
À1
virtual triplets; N ˆ J(P,H)‡ J(P,H) or J(P,C)‡ J(P,C), respectively.
Conductivity measurements were carried out in nitromethane with a
Schott Konduktometer CG 851. Melting and decomposition points were
measured by DTA. IR spectra were recorded on a Bruker IFS 25 FT/IR
spectrometer, and GC/MS analyses were carried out on a Hewlett Packard
G1800A GCD system equipped with a capillary column (HP5, 25 m) and
HP-Chemstation software.
91%; m.p. 648C (decomp); conductivity L ˆ 87 cm W mol
. IR
): nÄ ˆ 1984 (NˆN) cm ; 1H NMR (200 MHz, [D
À1
(CH
2
Cl
2
6
]acetone): d ˆ
), 7.63
), 7.27 (m, 6H;
), 1.28 (dvt, N ˆ 13.4 Hz,
]acetone,
), 129.9,
), 66.0 (s, CN ),
5 5 5 5
9.03 (m, 2H; ortho H of NC H ), 7.96 (m, 1H; para H of NC H
(m, 2H; meta H of NC H ), 7.47 (m, 4H; ortho H of C H
5 5 6 5
para and meta H of C
6
H
5
), 1.86 (m, 6H; PCHCH
3
3
13
J(H,H) ˆ 7.3 Hz, 36H; PCHCH
3
); C NMR (50.3 MHz, [D
6
À358C): d ˆ 154.7 (s, ortho C of NC
5
H
5
), 139.0 (s, para C of NC
5 5
H
1
2
27.5, 127.2, 126.5 (all s, C
6
H
5
), 126.8 (s, meta C of NC
5
H
5
2
cis-[Rh(acetone)
.20 mmol) in diethyl ether (4 mL) was treated at À788C with PiPr
39 mL, 0.20 mmol) and stirred for 10 min. The solvent was removed, the
residue was washed with diethyl ether (2 Â 10 mL) and pentane (3 Â
0 mL) and dried in vacuo. The resulting brown powder was recrystallized
2 8 3 6
(C H14)(PiPr )]PF (3): A suspension of 2 (119 mg,
3
1
4.1 (vt, N ˆ 19.0 Hz; PCHCH
3
), 19.8 (s, PCHCH
]acetone): d ˆ 38.0 (d, J(Rh,P) ˆ 126.7 Hz), À142.7 (sept, J(F,P) ˆ
3
); PNMR (81.0 MHz,
0
3
1
1
[
D
6
(
7
07.0 Hz); elemental analysis (%) for C36
57 6 3 3
H F N P Rh (841.7): calcd: C
5
1.37, H 6.83, N 4.99; found: C 51.23, H 6.86, N 4.85.
1
by slow diffusion of diethyl ether (10 mL) into a solution of acetone (1 mL)
which afforded a yellow solid. The precipitation was completed by addition
of pentane (10 mL). The solvent was decanted, and the yellow solid was
washed with pentane (10 mL) and dried. Yield ˆ 99 mg, 78%; m.p. 618C
trans-[RhCl(h
1
-N CPh )(PiPr ) ] (11): suspension of 8 (66 mg,
A
2
2
3 2
0.08 mmol) or 9 (77 mg, 0.08 mmol) in diethyl ether (10 mL) was treated
with an excess of NaCl (50 mg, 0.86 mmol) and was stirred for 3 h at room
temperature. The solvent was removed in vacuo and the residue extracted
with hexane (20 mL). The extract was evaporated to dryness in vacuo to
give a dark green solid which was washed with cold methanol (2 Â 1 mL)
and dried in vacuo. Yield ˆ 29 mg, 68%. Compound 11 was charaterized by
2
À1
À1
(
decomp); conductivity L ˆ 125 cm W mol ; IR (CH
2
Cl
]acetone): d ˆ 2.21 (m,
of acetone), 1.93 (m, 3H; PCHCH ),
2
): nÄ ˆ 1701, 1658
À1
1
(
2
CˆO), 1354 cm (CˆC); H NMR (400 MHz, [D
6
H; CH of C
8
H
14), 2.09 (s, 12H; CH
3
3
3
[1, 2a]
1
.60, 1.49, 1.36 (all m, 12H; CH
2
of C
8
H
14), 1.38 (dd, J(P,H)ˆ 13.6 Hz,
comparison of the spectroscopic data with those of an authentic sample.
3
); 13C NMR (100.6 MHz, [D
J(H,H) ˆ 7.2 Hz, 18H; PCHCH
3
6
]acetone):
1
trans-[RhBr(h -N
2
CPh
2
)(PiPr
3
)
2
] (12): This was prepared as described for
1
2
d ˆ 206.6 (s, C ˆ O), 62.5 (dd, J(Rh,C) ˆ 16.2 Hz, J(P,C)ˆ 1.6 Hz; CH of
1
1, using 8 (66 mg, 0.08 mmol) and NaBr (80 mg, 0.78 mmol) as starting
C
8
H
14), 30.6 (s, CH
3
of acetone), 30.2, 28.7, 26.9 (all s, CH
2
of C
8
H
14), 23.2 (d,
materials. Dark green solid; yield ˆ 33 mg, 71%; m.p. 518C (decomp). IR
1
31
J (P,C)ˆ 25.2 Hz; PCHCH
3
1
), 20.0 (s, PCHCH
3
); PNMR (162.0 MHz,
À1
1
(
(
KBr): nÄ ˆ 1943 (NˆN) cm ; H NMR (200 MHz, [D
m, 4H; ortho H of C ), 7.19 (m, 4H; meta H of C
), 2.42 (m, 6H; PCHCH
6
]benzene): d ˆ 7.41
1
[
D
6
]acetone): d ˆ 63.1 (d, J(Rh,P) ˆ 188.1 Hz), À144.2 (sept, J(F,P) ˆ
6
H
5
6
H
5
), 6.89 (m, 2H; para
7
07.4 Hz); elemental analysis (%) for C23
H
47
F
6
O
2
P
2
Rh (634.5): calcd: C
3
H of C
6
H
5
3
), 1.27 (dvt, N ˆ 13.2 Hz, J(H,H) ˆ
4
3.54, H 7.47; found: C 43.91, H 7.71.
1
3
6
1
.9 Hz, 36H; PCHCH
28.3, 125.4, 124.5 (all s, C
3
); C NMR (50.3 MHz, [D
), 79.1 (s, CN
), 24.1 (vt, N ˆ 18.5 Hz;
); 31PNMR (81.0 MHz, [D
]benzene): d ˆ 40.9
Rh
6
]benzene): d ˆ 128.9,
1
trans-[Rh(PiPr
3
)
2
(acetone)(h -N
2
CPh
2
)]PF
6
(8): A solution of 4 (260 mg,
6
H
5
2
0
.38 mmol) in acetone (5 mL) was treated at À788C with one equivalent of
PCHCH
(
3
), 20.1 (s, PCHCH
3
6
a 0.5m solution of Ph CN (0.76 mL, 0.38 mmol) in methylcyclohexane. A
2
2
1
d, J(Rh,P) ˆ 119.1 Hz); elemental analysis (%) for C31
2 2
H52BrN P
change of color from violet to dark green occurred. After the reaction
mixture was warmed to room temperature and stirred for 1 h, a dark green
solid precipitated. The solvent was decanted, the dark green precipitate was
washed with diethyl ether (3 Â 5 mL) and pentane (2 Â 5 mL), and dried.
Yield ˆ 284 mg, 91%; m.p. 578C (decomp); conductivity L ˆ
(
697.5): calcd: C 54.79, H 7.51, N 4.02; found: C 54.38, H 7.67, N 4.08.
1
trans-[RhI(h -N
2
CPh
2
)(PiPr
3
)
2
] (13): This was prepared as described for
1
1, using 8 (66 mg, 0.08 mmol) and NaI (120 mg, 0.80 mmol) as starting
materials. Dark green solid; yield ˆ 43 mg, 87%; m.p. 488C (decomp); IR
À1
1
2
À1
À1
À1
1
(CH
.39 (m, 4H; ortho H of C
para H of C ), 2.52 (m, 6H; PCHCH
6.9 Hz, 36H; PCHCH
128.3, 125.3, 124.7 (all s, C
2
Cl
2
): nÄ ˆ 2032 (NˆN) cm
;
H NMR (200 MHz, [D
6
]benzene): d ˆ
1
(
05 cm W mol
200 MHz, [D
]acetone): d ˆ 7.53 (m, 4H; ortho H of C
meta and para H of C ), 2.06 (m, 6H; PCHCH ), 2.05 (s, 6H; CH
3
;
IR (CH
2
Cl
2
): nÄ ˆ 1956 (NˆN) cm
), 7.34 (m, 6H;
of
;
H NMR
7
6
H
5
), 7.17 (m, 4H; meta H of C
6
H
5
), 6.90 (m, 2H;
6
6 5
H
3
H
5
3
6
H
5
3
), 1.26 (dvt, N ˆ 13.2 Hz, J(H,H) ˆ
6
1
3
3
3
); C NMR (50.3 MHz, [D
), 79.4 (s, CN
), 25.2 (vt, N ˆ 18.8 Hz;
); 31PNMR (81.0 MHz, [D
]benzene): d ˆ 40.8
Rh
6
]benzene): d ˆ 129.0,
acetone), 1.34 (dvt, N ˆ 13.1 Hz, J(H,H) ˆ 6.6 Hz, 36H; PCHCH
3
);
1
3
6
H
5
2
C NMR (50.3 MHz, [D
27.6, 127.1, 126.3 (all s, C
vt, N ˆ 19.6 Hz; PCHCH
6
]acetone, À358C): d ˆ 206.6 (s, CˆO), 130.2,
PCHCH
3
), 20.4 (s, PCHCH
3
6
1
(
6 5 2 3
H ), 84.5 (s, CN ), 30.6 (s, CH of acetone), 23.5
1
3
1
(d, J(Rh,P) ˆ 116.2 Hz); elemental analysis (%) for
31 2 2
C H52IN P
3
), 19.5 (s, PCHCH
3
); PNMR (81.0 MHz,
1
1
(744.5): calcd: C 50.01, H 7.04, N 3.76; found: C 49.30, H 6.78, N 4.10.
[
D
6
]acetone): d ˆ 40.2 (d, J(Rh,P) ˆ 122.1 Hz), À142.8 (sept, J(F,P) ˆ
7
09.2 Hz); elemental analysis (%) for C34
H
58
F
6
N
2
O
1
P
3
Rh (820.5): calcd:
trans-[Rh(N )(h -N CPh )(PiPr ) ] (14): This was prepared as described
1
3
2
2
3 2
C 49.76, H 7.12, N 3.41; found: C 49.50, H 6.80, N 3.29.
for 11, using 8 (66 mg, 0.08 mmol) and NaN (52 mg, 0.80 mmol) as starting
3
1
materials. Dark green solid; yield ˆ 31 mg, 56%; m.p. 588C (decomp); IR
trans-[Rh(PiPr
3
)
2
(h -N
2
CPh
2
)
2
]PF
6
(9): A solution of 4 (358 mg,
À1
1
(hexane): nÄ ˆ 2038 (N
ˆ
N of N ), 1948 (NˆN of N CPh ) cm ; H NMR
3
2
2
0
.52 mmol) in acetone (5 mL) was treated at room temperature with a
.0 m solution of Ph CN (1.31 mL, 1.31 mmol) in methylcyclohexane. The
resulting dark green solution was stirred for 3 min, and then hexane
20 mL) was added. A dark green precipitate was formed, which was
1
2
2
(200 MHz, [D
para H of C
6
]benzene): d ˆ 7.34 (m, 4H; ortho H of C
6 5
H ), 7.19 (m, 4H;
), 2.12 (m, 6H; PCHCH
6
H
5
), 6.87 (m, 2H; para H of C
6
H
5
3
),
3
13
(
1.20 (dvt, N ˆ 13.6 Hz, J(H,H) ˆ 6.9 Hz, 36H; PCHCH
3
); C NMR
separated from the mother liquor, washed with hexane (portions of 20 mL)
until the hexane solution was colorless. The residue was dried, then
dissolved in acetone (0.5 mL) and the solution layered with diethyl ether
(50.3 MHz, [D
), 78.3 (s, CN
PNMR (81.0 MHz, [D
elemental analysis (%) for C31
10.62; found: C 56.21, H 8.07, N 10.06.
6
]benzene): d ˆ 129.9, 129.0, 128.3, 125.1, 124.6 (all s,
), 24.0 (vt, N ˆ 17.6 Hz; PCHCH ), 19.7 (s, PCHCH );
]benzene): d ˆ 44.3 (d, J(Rh,P) ˆ 123.5 Hz);
Rh (659.7): calcd: C 56.44, H 7.95, N
C
6
H
5
2
3
3
3
1
1
6
(
10 mL). The resulting dark green microcrystalline solid was separated,
52 5 2
H N P
washed with pentane (2  2 mL) and dried in vacuo. Yield ˆ 380 mg, 76%;
2
À1
À1
m.p. 628C (decomp); conductivity L ˆ 102 cm W mol ; IR (CH
2 2
Cl ):
2
2
2 4
Catalytic reactions of Ph CN and C H with 2 ± 4, 8, and 9 as catalyst: In a
À1
1
nÄ ˆ 1948 (NˆN) cm
;
H NMR (200 MHz, [D
]acetone): d ˆ 7.54 (d,
6
typical experiment, a solution of the catalyst (10 ± 20 mg, ca. 0.04 mmol) in
3
J(H,H) ˆ 7.7 Hz, 8 H ; ortho H of C
6
H
5
), 7.37 (m, 12H; meta and para H
À1
THF (6 mL) was treated dropwise (ca. 10 mLh ) at 408C with a 0.1m
3
of C
6
H
5
), 2.03 (m, 6H; PCHCH
3
), 1.26 (dvt, N ˆ 14.3 Hz, J(H,H) ˆ 6.9 Hz,
solution of diphenyldiazomethane in methylcyclohexane/THF (1:4). While
adding the substrate, a slow stream of ethene was passed through the
solution. The catalytic reaction was finished when the violet color of the
diazoalkane solution did not disappear on further addition to the reaction
mixture. The solvent was removed in vacuo, and the oily residue was
1
3
3
6H; PCHCH
3
); C NMR (50.3 MHz, [D
8
]THF, À358C): d ˆ 130.5, 129.4,
1
28.0, 127.5 (all s, C
6
H
5
), 83.3 (s, CN
2
), 24.8 (vt, N ˆ 19.4 Hz; PCHCH
3
), 19.6
3
1
1
(
s, PCHCH
3
); PNMR (81.0 MHz, [D
6
]acetone): d ˆ 46.5 (d, J(Rh,P) ˆ
1
1
16.2 Hz), À142.7 (sept, J(F,P) ˆ 707.3 Hz); elemental analysis (%) for
C
44
H
62
F
6
N
4
P
3
Rh (956.8): calcd: C 55.23, H 6.53, N 5.86; found: C 55.19, H
dissolved in hexane (5 mL). In order to destroy excess Ph
the catalyst from the reaction products, the mixture was filtered through
Al (neutral, activity grade III, height of column 7 cm). After evapo-
2 2
CN and separate
6
.60, N 5.54.
1
trans-[Rh(PiPr
3
)
2
(py)(h -N
2
CPh
2
)]PF
6
(10): A suspension of 8 (61 mg,
2 3
O
0
.07 mmol) or 9 (67 mg, 0.07 mmol) in diethyl ether (10 mL) was treated at
ration of the solvent, a colorless oil consisting of a mixture of 5a and 5b was
isolated from the eluate. The ratio of the products, diphenylcyclopropane
(5a) and 1,1-diphenylpropene (5b), was determined by integration of
room temperature with an excess of pyridine (0.5 mL, 6.2 mmol). After the
mixture was stirred for 15 min, a brownish-green suspension was formed.
The solvent was decanted, the solid green residue washed with diethyl ether
1
characteristic signals in the H NMR spectra and by GC/MS analysis. The
Chem. Eur. J. 2000, 6, No. 16
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
0947-6539/00/0616-3057 $ 17.50+.50/0
3057

H. Werner et al.
FULL PAPER
using the program DIRDIF.[ All structures were refined by full matrix
24]
results with 2 ± 4 as the catalyst are summarized in Scheme 2. With 8 and 9
as the catalyst, the ratio of 5a to 5b is >99:1 and the turnover numbers are
2
[25]
least-squares procedures on F with SHELX93. The asymmetric unit of 2
1
7 (with 8) and 33 (with 9).
Catalytic reactions of Ph CN
analogous manner to the catalytic reaction of Ph
contains four formula units, each consisting of two moieties; a cationic
±
rhodium complex and a PF
6
counterion. For 2 a weak hydrogen bonding
2
2
and propene with 2 ± 4 as catalyst: In an
CN with ethene by using
between the methyl groups of the coordinated actone and fluor atoms of
2
2
±
[26]
6
the PF anions is observed. For 8 the positional and anisotropic thermal
propene as the olefinic substrate. After evaporation of the solvent of the
eluate, a colorless oil consisting of a mixture of 6a, 6b, E/Z 6c and 6d was
isolated. The results are summarized in Scheme 3.
displacement parameters for the non-hydrogen atoms were refined. A
subsequent difference Fourier synthesis resulted in the location of all
hydrogen atoms, of which the coordinates and the isotropic thermal
displacement parameters were refined. The methyl hydrogen atoms of the
acetone moiety were ultimately refined riding on their carrier atoms with
2 2
Catalytic reactions of Ph CN and styrene with 2 or 4 as catalyst: A solution
of 2 or 4 (10 ± 20 mg, ca. 0.04 mmol) and styrene (50 molar equivalents) in
THF (6 mL) was treated dropwise (ca. 10 mLh ) at 408C with a 0.1m
À1
3
their positions calculated by using sp hybridization at the C atom as
solution of diphenyldiazomethane in methylcyclohexane/THF (1:4). The
catalytic reaction was finished when the violet color of the diazoalkane
solution did not disappear on further addition to the reaction mixture.
Workup of the reaction mixture was carried out as described for the
catalytic reactions with ethene. After evaporation of the solvent of the
eluate, a colorless oil consisting of a mixture of 7a, 7b, 7c, and 7d was
isolated. The results are summarized in Scheme 4.
appropiate with Uiso ˆ 1.5  Uequiv of their parent atom, C(33) and C(34),
repectively. The methyl groups in both 2 and 8 were refined as rigid groups,
À
which were allowed to rotate free. The PF
6
ion in 8 is rotational disordered
over the F(1)-P(3)-F(2) axis. The site occupancy factor of the major
component was refined to a value of 0.69(2).
Catalytic reactions of Ph
2
CN
2
and C
2
H
4
with 12 ± 14 as catalyst: In an
Acknowledgement
analogous manner to the reactions with 2 ± 4 as catalyst, by using a solution
of 12, 13, or 14 (10 ± 20 mg, ca. 0.04 mmol) in methylcyclohexane (6 mL). A
mixture of 5a and 5b was obtained in the ratio of 19:81 (for 12), 8:92 (for
We thank the Deutsche Forschungsgemeinschaft (SFB 347) and the Fonds
der Chemischen Industrie for financial support, the latter in particular for a
Ph.D. grant to M. E. S. We are also grateful to Mrs. R. Schedl and Mr. C. P.
Kneis (DTA and elemental analysis), Mrs. M.-L. Schäfer and Dr. W.
Buchner (NMR spectra), and BASF AG for various gifts of chemicals. M.
B. gratefully acknowledges support from the European Union (SOK-
RATES program).
1
3) and 39:61 (for 14). The turnover numbers were 27 (for 12), 18 (for 13),
and 17 (for 14).
X-ray structural analysis of the compounds 2 and 8:[21] Single crystals of 2
and 8 were grown by slow diffusion of diethyl ether (10 mL) into a
saturated solution of 2 or 8 in acetone (1 mL). The yellow/orange (2) and
dark green (8) crystalline products were washed with pentane (2 Â 1 mL)
and dried under a stream of argon. Crystal data for the two structures are
represented in Table 1. The data for 2 and 8 were collected from a
glassfiber-mounted single crystal which was prepared under an inert
atmosphere and transferred into a cold nitrogen stream of the low
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[
22]
temperature unit mounted on a ENRAF-Nonius CAD-4F diffractom-
[
23]
eter with monochromated MoKa radiation (l ˆ 0.71073 Š). The struc-
tures were solved by Patterson methods and extension of the models were
accomplished by direct methods applied to difference structure factors
Ghosh, J. Am. Chem. Soc. 1993,
Table 1. Crystal structure data for 2 and 8.
1
15, 9968 ± 9978.
Compound
2[d]
8
[4] L. Brandt, A. Fries, N. Mahr, H.
Werner, J. Wolf in Selective Re-
actions of Metal-Activated Mole-
cules (Eds.: H. Werner, A. G.
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Braunschweig, 1992, p. 171 ± 174.
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International Symposium on Ho-
mogeneous Catalysis, Princeton,
formula
C
22
H
40
F
6
O
2
RhPC
34 58 6 2 3
H F N OP Rh
M
r
584.43
130
820.66
130
T [K]
cryst. size [mm ]
3
0.3 Â 0.3 Â 0.6
0.1 Â 0.1 Â 0.6
Å
space group
cell dimensions determination
a [pm]
b [pm]
c [pm]
a [8]
P1
P2 /n (no. 14)
1
24 rflns, 16.8 <q < 17.7
1282.4(1)
1289.5(1)
3153.1(1)
99.950(6)
90.888(4)
90.068(4)
5.1231(6)
8
1.515
0.789
2416
52
18648
18633
16207
1245
0.0478
0.1262
0.0565; 15.2674
0.96/ À 1.01
24 rflns, 16.2 <q < 17.9
[
1369.6(1)
1199.3(1)
2457.1(1)
±
102.41(1)
±
3.9417(5)
4
1.383
0.612
1712
54
8707
1
996.
[
6] a) J. R. Shapley, R. R. Schrock,
J. A. Osborn, J. Am. Chem. Soc.
1969, 91, 2816 ± 2817; b) R. R.
Schrock, J. A. Osborn, J. Am.
Chem. Soc. 1971, 93, 2397 ± 2407.
b [8]
g [8]
V [nm ]
3
Z
À3
1
calcd [Mgm
]
À1
[7] B. Windmüller, J. Wolf, H. Wern-
m [mm
F(000)
]
er, J. Organomet. Chem. 1995,
5
02, 147 ± 161.
2
q max [8]
[
[
8] B. Windmüller, O. Nürnberg, J.
Wolf, H. Werner, Eur. J. Inorg.
Chem. 1999, 613 ± 619.
9] J. A. van Doorn, H. van der
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4247; b) P. J. Sinnema, Disserta-
tion, Rijksuniversiteit Gronin-
gen, 1999.
no. meas. reflns.
no. unique reflns.
no. reflns. used
8573
7859
665
refined parameters
[
a]
R1 [I > 2s(I)]
0.0368
0.0880
0.0484; 1.5161
0.78/ À 0.65
[
b]
wR2 (all data)
g1; g2
resid. elec. 1 [10 epm
[
c]
À6
À3
]
2
2)2]/S[w(F
2
† ]}1/2. [c] w ˆ 1/[s (F
2
2
2
2
[
a] R1 ˆ S j jF
o
j À jF
c
j j/S j F
o
j . [b] wR2 ˆ {S[w(F
o
À F
c
o
o
† ‡ (g1 ” P) ‡ g2 ” P];
2
2
P ˆ (F
o
‡ 2F
c
†/3. [d] The asymmetric unit contains four independent molecules 2a ± d. In this table the formula
and M
r
represent one molecule only.
3058
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
0947-6539/00/0616-3058 $ 17.50+.50/0
Chem. Eur. J. 2000, 6, No. 16

Diphenyldiazomethanerhodium(i) Complexes
3052±3059
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free of charge on application to CCDC, 12 Union Road, Cambridge
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[
[
2
022 ± 2025.
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Received: February 2, 2000 [F2275]
Chem. Eur. J. 2000, 6, No. 16
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
0947-6539/00/0616-3059 $ 17.50+.50/0
3059