Nortricyclyl- And Norbornenyl-acylrhodium complexes from the reaction of norbornadiene rhodium(i) complexes with o-(diphenylphosphanyl)-benzaldehyde

Article abstract of DOI:10.1002/ejic.200400935

[{Rh(Nbd)Cl)₂] (Nbd = norbomadiene) reacts with o-(diphenylphosphane)benzaldehyde in benzene solution to give the rhodium(III) complex [Rh(Cl)(C₇H₉){o-PPh₂(C ₆H₄CO)}]_n (1), where C₇H ₉ is a nortricyclyl (Ntyl) group. Complex 1 reacts with various bidentate N-donors, such as biacetyldihydrazone, 2,2′-bipyridine, 8-aminoquinoline, 2-(aminomethyl)-pyridine, or pyridine, to afford nortricyclyl [Rh(Cl){o-PPh₂(C₆H₄CO)}(Ntyl)(NN)] complexes. The presence of the nortricyclyl group and the structure of the complexes have been confirmed by NMR spectroscopy and, in one case, by single-crystal X-ray diffraction. Nortricyclyl complexes containing bidentate N-donors are also formed by the reaction in benzene of PPh₂(o-C₆H ₄CHO) with the corresponding [Rh(Cl)(Nbd)(NN)] compounds prepared in situ . (Rh(Cl)-(Nbd)(bipy)| prepared in situ reacts with PPh₂(o-C₆H₄CH O) in methanol to give the complex [Rh(Cl){o-PPh₂(C₆H₄CO)}(C ₇H₉(bipy)], where C₇H₉ is a norbomenyl (Nbyl) group. This compound has been fully characterized by NMR spectroscopy. A proposal for the selective production of the norbomenyl and the nortricydyl derivatives is presented. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200400935

FULL PAPER
Nortricyclyl- and Norbornenyl-Acylrhodium Complexes from the Reaction of
Norbornadiene Rhodium(
I
) Complexes with o-(Diphenylphosphanyl)-
benzaldehyde
Rachad El Mail,[a] María Angeles Garralda,*[a] Ricardo Hernández,[a] Lourdes Ibarlucea,[a]
Elena Pinilla,[b] María Rosario Torres,[b] and Malkoa Zarandona[a]
Keywords: Rhodium complexes / Aldehydes / Insertion and rearrangement of norbornadiene / N ligands
[{Rh(Nbd)Cl}2] (Nbd = norbornadiene) reacts with o-(di-
phenylphosphane)benzaldehyde in benzene solution to give
the rhodium(III) complex [Rh(Cl)(C7H9){o-PPh2(C6H4CO)}]n
taining bidentate N-donors are also formed by the reaction
in benzene of PPh2(o-C6H4CHO) with the corresponding
[Rh(Cl)(Nbd)(NN)] compounds prepared “in situ”. [Rh(Cl)-
(1), where C7H9 is a nortricyclyl (Ntyl) group. Complex 1 re- (Nbd)(bipy)] prepared “in situ” reacts with PPh2(o-
acts with various bidentate N-donors, such as biacetyldihyd-
razone, 2,2Ј-bipyridine, 8-aminoquinoline, 2-(aminomethyl)-
pyridine, or pyridine, to afford nortricyclyl [Rh(Cl){o-
PPh2(C6H4CO)}(Ntyl)(NN)] complexes. The presence of the
nortricyclyl group and the structure of the complexes have
been confirmed by NMR spectroscopy and, in one case, by
single-crystal X-ray diffraction. Nortricyclyl complexes con-
C6H4CHO) in methanol to give the complex [Rh(Cl){o-
PPh2(C6H4CO)}(C7H9)(bipy)], where C7H9 is a norbornenyl
(Nbyl) group. This compound has been fully characterized by
NMR spectroscopy. A proposal for the selective production of
the norbornenyl and the nortricyclyl derivatives is presented.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
oxygen and carbon (π complex) as in [Co(C5Me5){η3-
PPh2(o-C6H4CHO)}][16] or [W(CO)2{η3-PPh2(o-C6H4-
CHO)}].[14b]
Introduction
C–H bond cleavage in aldehydes, promoted by transition
metal complexes, is an active area of research.[1] Rhodium
and iridium compounds add, oxidatively, aldehyde C–H
bonds to afford acylhydride derivatives;[2] such species are
involved in catalytic processes such as aldehyde decarbon-
ylation or alkene hydroacylation.[3] o-(Diphenylphosphanyl)-
benzaldehyde [PPh2(o-C6H4CHO)] promotes the chelate-as-
sisted oxidative addition of aldehyde to rhodium(i)[4] iridi-
um(i)[5] platinum(0)[6] or cobalt(i),[7] yielding cis acylhydride
complexes that contain acylphosphane chelates PPh2(o-
C6H4CO). Ruthenium and osmium clusters also undergo
oxidative addition to afford compounds with bridging acyl
and hydride ligands.[8] PPh2(o-C6H4CHO) is also a versatile
ligand that can coordinate to transition metal atoms: (i) as a
monodentate P-donor towards rhodium(i),[9] iridium(iii),[10]
palladium(ii),[11] platinum(ii),[12] ruthenium(ii),[13] or tung-
sten(0);[14] (ii) as chelating phosphane-aldehyde ligand with
the aldehyde portion bonded through oxygen (σ complex)
as in [Ru(η6-arene)Cl{κ2-PPh2(o-C6H4CHO)}][SbF6][13] or
[Re(Cl)(CO)3{κ2-PPh2(o-C6H4CHO)}][15] or through both
1,5-Cyclooctadiene (Cod) rhodium or iridium complexes
react with PPh2(o-C6H4CHO) to undergo chelate-assisted
oxidative addition, affording different types of complexes.
[{Rh(Cod)Cl}2] reacts through diolefin displacement to
give a hydride, [Rh(Cl)(H){PPh2(o-C6H4CO)}{κ2-PPh2(o-
C6H4CHO)}],[17] while the cationic complex [Rh(Cod)2]-
ClO4 affords cyclooctenyl derivative [Rh(η3-C8H13)-
{PPh2(o-C6H4CO)}{κ2-PPh2(o-C6H4CHO)}]ClO4, due to
hydride formation being followed by insertion of the diole-
fin into the Rh–H bond.[18] [{Ir(Cod)Cl}2] gives the 1,5-
cyclooctadiene complex [Ir(Cl)(H){PPh2(o-C6H4CO)}-
(Cod)] – a proposed model intermediate in the hydroacyl-
ation of olefins,[5] which reacts with PPh2(o-C6H4CHO) to
give hydridoirida-β-diketones, most likely via iridium(v) in-
termediates formed by oxidative addition of aldehyde to
IrIII species.[19] Recently, the reaction of [(η5-C5Me5)-
M(Cl)(μ-Cl)]2 (M = Rh, Ir) with PPh2(o-C6H4CHO) to af-
ford [(η5-C5Me5)M(Cl)(PPh2(o-C6H4CO))] with HCl loss
has been reported.[20]
We report here on the reactions of norbornadiene-con-
taining rhodium(i) complexes with PPh2(o-C6H4CHO).
[a] Facultad de Química de San Sebastián, Universidad del País
Vasco,
Apdo. 1072, 20080 San Sebastián, Spain
E-mail: qppgahum@sq.ehu.es
Results and Discussion
[{Rh(Nbd)Cl}2] (Nbd = norbornadiene) reacts with o-
(diphenylphosphane)benzaldehyde in benzene solution to
[b] Departamento de Química Inorgánica, Laboratorio de Difrac-
ción de Rayos X, Facultad de Ciencias Químicas, Universidad
Complutense,
28040 Madrid, Spain
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M. A. Garralda et al.
FULL PAPER
afford a yellow rhodium(iii) complex, which according to tricyclyl [Rh(Cl){o-PPh2(C6H4CO)}(Ntyl)(NN)] complexes
its elemental analysis corresponds to [Rh(Cl)(C7H9){o- [NN = biacetyldihydrazone (bdh), 2; 2,2Ј-bipyridine (bipy),
PPh2(C6H4CO)}]n 1 (see i in Scheme 1). Its IR spectrum 3; 8-aminoquinoline (aqui), 4; 2-aminomethylpyridine
shows a strong band at 1637 cm–1 due to bonded acyl (ampy), 5; pyridine (py), 6] (see ii in Scheme 1). In all cases,
groups. The FAB spectrum shows [M–Cl]+ and [M–Cl– a single complex is obtained, as indicated by NMR spec-
(C7H9)]+ peaks for 1 (n = 3) at 1525 (47%) and 1432 (20%), troscopy. The 31P{1H} NMR spectra show only one doub-
respectively, suggesting a trinuclear structure. The four reso- let at low field (68–73 ppm), with JRh,P of 170–183 Hz,
nances in the 70–74 ppm region of the 31P{1H} NMR spec- which is consistent with phosphorus atoms trans to nitro-
trum are of almost equal intensity as doublets, due to coup- gen.[4d] A doublet of doublets in the low-field region of the
ling with rhodium (JRh,P = ca. 200 Hz). The 1H NMR spec- 13C{1H} NMR spectra (ca. 240 ppm) is due to the bonded
trum also shows four almost equal doublets in the 2.4– acyl group, with JRh,C around 37 Hz and JP,C of ca. 4 Hz.
2.9 ppm region, complex multiplets in the 1.41–0.22 ppm Nortricyclyl group assignments have been made using 2D
region and no resonances in the olefinic region. On these NMR techniques (Experimental section). The 1H NMR
spectroscopic grounds, we believe 1 contains a nortricyclyl spectra show a doublet of doublets (1.4–2.4 ppm) for the
group formed by the oxidative addition of aldehyde to rho- Ntyl-CH bonded to rhodium, due to coupling with rho-
dium to give an acylhydridenorbornadiene complex, fol- dium (ca. 10 Hz) and with a cis phosphorus (JP,H = ca.
lowed by hydrogen transfer with a concurrent double bond 2 Hz). Two doublets for each Ntyl-CH2 group, three triplets
shift to form the nortricyclyl group. This last type of step due to the Ntyl-cyclopropyl fragment and a broad singlet
has been suggested in the rhodium-catalyzed amination of due to another Ntyl-CH are also observed. 13C{1H} NMR
norbornadiene[21] and, recently, the formation of rhodi- spectra show, at ca. 40 ppm, the resonance due to the nor-
um(iii) complexes containing a nortricyclyl bonded group tricyclyl carbon atom bonded to rhodium as either a doub-
and using norbornadiene rhodium(i) compounds as starting let due to rhodium coupling (JRh,C = ca. 25 Hz) or as a
material has been reported.[22]
doublet of doublets if additional splitting by a cis phospho-
rus atom is observed (JP,C = ca. 6 Hz). Complex 2 contains
a diimino-coordinated dihydrazone and shows two well-
separated resonances for the pendant amino groups at δ =
5.65 and 7.78 ppm, respectively. The low-field resonance is
most likely due to hydrogen bond formation. Complexes 4
and 5, containing bonded amino groups, show the expected
displacement of the corresponding amino resonance
towards lower field on coordination. Only one isomer is
formed, containing the amino group trans to the phos-
phane. Were the amino group cis to the phosphane, ring
current effects originated by its aromatic rings would shift
the signals towards higher field.[4d]
An X-ray diffraction study of 2 confirms the presence of
the nortricyclyl group and the structure. There appears to
be only two previous, recent, structural reports of a nor-
tricyclyl unit bonded to rhodium.[22] The crystal consists of
Scheme 1. Formation of nortricyclyl derivatives in benzene.
The complexity of the NMR spectra indicates the pres- [Rh(Cl){o-PPh2(C6H4CO)}(C7H9)(H2NN=C(CH3)C(CH3)=
ence of several isomers. On raising the temperature to NNH2)] neutral molecules and chloroform solvent mole-
+60 °C, the proton resonances at δ = 2.89, 2.71 and cules. Figure 1 shows an ORTEP view of the complex with
2.46 ppm, and also three of the four resonances in the the atomic numbering scheme, together with selected bond
31P{1H} NMR spectrum, decrease markedly, while the pro- lengths and angles. The rhodium atom is coordinated in a
ton resonance at δ = 2.80 ppm and the doublet at δ31P slightly distorted octahedral fashion due to the presence of
71.52 ppm increase in intensity. These observations, along two bidentate ligands. The maxima deviations of 15.3 and
with the FAB data, suggest that 1 contains a mixture of two 14.3° correspond to the angles N3–Rh–N2 and C8–Rh–P
trinuclear isomers, one with equivalent phosphorus atoms for the bidentate ligands. The nortricyclyl unit and the chlo-
and equivalent nortricyclyl groups and the other with three rine atom occupy axial positions. The equatorial plane,
inequivalent phosphorus atoms and three inequivalent nor- formed by the P, C8, N2 and N3 atoms of the two metall-
tricyclyl groups. At higher temperatures, or longer periods ocycles, shows a maximum least-squares deviation of
in solution, the complex decomposes and, consequently, we 0.09(1) Å for C8, with the rhodium atom 0.022(1) Å out of
could not obtain either a single isomer or single crystals for this plane. Rh–N2 [2.10(1) Å] trans to phosphorus is
X-ray diffraction analysis. The reaction of 1 with several N- slightly shorter than Rh–N3 [2.16(1) Å] trans to acyl, re-
donor ligands confirmed the formation of the nortricyclyl flecting the stronger trans influence of the acyl ligands. Rh–
(Ntyl) group.
C1 [2.12(1) Å] is similar to those recently reported in nor-
Complex 1 reacts with bidentate N-donors, such as di- tricyclylrhodium compounds[22] and longer than Rh–C8
imines or amino-imines, or with pyridine, to afford nor- [2.00(1) Å], which is as expected.[4b] The difference between
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Nortricyclyl- and Norbornenyl-Acylrhodium Complexes
FULL PAPER
Figure 1. ORTEP view of complex 2, showing the atomic numbering (30% probability ellipsoids); solvent molecules, some carbon atoms
and all hydrogen atoms but four have been omitted for clarity; selected bond lengths [Å] and angles [°]: Rh–C(1) 2.12(2), Rh–C(8),
2.00(2), Rh–N(2) 2.10(1), Rh–N(3) 2.16(1), Rh–P 2.273(3), Rh–Cl(1) 2.525(3), O(1)–C(8) 1.21(1); C(8)–Rh–C(1) 97.8(5), C(8)–Rh–N(2)
97.9(4), C(1)–Rh–N(2) 89.2(4), C(8)–Rh–N(3) 170.7(4), C(1)–Rh–N(3) 87.8(4), N(2)–Rh–N(3) 74.7(4), C(8)–Rh–P(1) 83.2(3), C(1)–Rh–
P(1) 90.1(3), N(2)–Rh–P 178.8(3), N(3)–Rh–P 104.3(3), C(8)–Rh–Cl(1) 85.2(3), C(1)–Rh–Cl(1) 174.2(4), N(2)–Rh–Cl(1) 85.5(3), N(3)–
Rh–Cl(1) 88.6(3), P(1)–Rh–Cl(1) 95.2(1).
Figure 2. PLUTO view of the “dimer units” showing the hydrogen bonds for 2.
the Rh–C distances may be viewed as a consequence of the Table 1. Hydrogen bond geometry [Å] and angles [°] for [Rh(Cl)-
different hybridization, i.e. sp3 for C1 and sp2 for C8,[4b,23]
and also of C8 being part of a five-membered metallocycle.
{o-PPh2(C6H4CO)}(C7H9)(H2NN=C(CH3)C(CH3)=NNH2)]·
3CHCl3 (2).[a]
D–H---A
d(D–H) d(H---A) ϽDHA
d(D---A)
Complex 2 bears hydrogen bonds through both pendant
amino groups of the bdh ligand. One NH2 group (N1)
binds the oxygen atom of the acyl group (O1) intramolecu- N1–H1A---Cl1Ј
N1–H1B---O1
0.860
0.860
0.860
0.860
0.860
2.050
2.549
2.846
2.743
2.856
142.54
148.37
133.72
145.15
123.46
2.78(1)
3.31(1)
3.50(1)
3.48(1)
3.41(1)
N1–H1B---Cl9ЈЈ
larly (Figure 1) and a solvent molecule through H1B in a
N4–H4A---Cl7ЈЈЈ
bifurcated way. The H1A atom binds to the Cl1Ј atom of
N4–H4B---Cl5ЈЈЈ
the centrosymmetric molecule to give dimers (Figure 2).
[a] (Ј) Cl1 [–x +1, –y + 1, –z]; (ЈЈ) [x, y, z – 1]; (ЈЈЈ) [–x + 1, –y +
1, –z + 1].
The other NH2 group (N4) forms hydrogen bonds with two
chlorine atoms of two other molecules of solvent. Table 1
lists the hydrogen bond geometry.
Complexes 2–5 are also formed, though impure (Experi-
Coordinated norbornadiene in transition metal com-
mental section), in the reaction of the corresponding com- plexes is hydrogenated by both 1,2- and 1,4-addition to give
plexes [Rh(Cl)(Nbd)(NN)][24] (NN = bdh, bipy, aqui, norbornene and nortricyclene, respectively. The products
ampy), prepared “in situ”, with stoichiometric 1:1 amounts obtained depend markedly on the starting materials and/or
of PPh2(o-C6H4CHO) in benzene (see iii in Scheme 1).
reaction conditions.[25]
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When [Rh(Cl)(Nbd)(bipy)], prepared “in situ”, is treated
with PPh2(o-C6H4CHO) in methanol, oxidative addition of
aldehyde to rhodium followed by insertion of norbornadi-
ene into the Rh–H bond also occurs, but in this case the
norbornenyl (Nbyl) derivative [Rh(Cl){o-PPh2(C6H4CO)}-
Nbyl)(bipy)] (7), an isomer of 3, is obtained [Equa-
tion (1)].
NMR spectroscopy, including 2D experiments, allows
complete characterization of complex 7. The presence of
two doublets of doublets at δ = 5.06 and 4.89 ppm in the
1H NMR spectrum, which correlate with two resonances at
δ = 134.0 and 134.2 ppm, respectively, in the 13C{1H} NMR
spectrum, is indicative of a non-coordinated olefin. The
norbornenyl-CH group bonded to rhodium shows a mul-
tiplet at δH = 1.75 ppm and a doublet of doublets at δ13C
= 29.9 ppm due to coupling with rhodium and with a cis
Scheme 2. Proposal for the selective production of nortricyclyl and
norbornenyl derivatives.
The reaction of other [Rh(Cl)(Nbd)(NN)] complexes
prepared “in situ” (NN = bdh, aqui, ampy; N = py) with
PPh2(o-C6H4CHO) in methanol gave complex mixtures of
products. Decomposition products were formed in the reac-
tion of [{Rh(Nbd)Cl}2] with o-(diphenylphosphane)benzal-
dehyde in methanol.
1
phosphorus atom. Other H and 13C{1H} assignments are
given in the Experimental section. The spectroscopic fea-
tures of the acylphosphane chelate in 7 are similar to those
in 3: δ13C=O = 238.5 (dd, JRh,C = 32.4 Hz, JP,C = 6.0 Hz)
ppm and δ31P = 71.1 (d, JRh,P = 171 Hz) ppm for 7, and
δ13C=O = 235.8 (d, JRh,C = 38.3 Hz) ppm and δ31P = 72.8
(d, JRh,P = 176 Hz) ppm for 3 in [D6]DMSO. Therefore, 7
has the structural features shown in Equation (1), with the
phosphorus atom and the acyl group trans to nitrogen, as
in 3.
These results show that the solvent plays an important
role in the reaction of [Rh(Cl)(Nbd)(bipy)] with PPh2(o-
C6H4CHO). Different paths lead to different isomers (3 and
7). Complex 3 remains unchanged in methanol and com-
plex 7 is recovered unaltered from benzene. Scheme 2 pres-
ents a proposal for the selective production of the norbor-
nenyl and nortricyclyl derivatives. The rhodium(i) starting
material is a saturated species that requires ligand dissoci-
ation to undergo oxidative addition. In methanol, dissoci-
ation of chlorine to give an unsaturated cationic complex is
Conclusions
Norbornadiene rhodium(i) complexes react with o-(di-
phenylphosphane)benzaldehyde to undergo chelate-assisted
oxidative addition followed by hydrogen transfer to norbor-
nadiene, giving acylalkylrhodium(iii) derivatives. Nortricy-
clyl and the norbornenyl isomers have been obtained selec-
tively by using the appropriate solvent. We propose that, in
benzene, hydrogen transfer occurs with concurrent double
bond shift to form a nortricyclyl group because the norbor-
nadiene is bonded as a diolefin. In an ionising solvent such
as methanol, hydrogen transfer to the norbornadiene coor-
dinated as monoolefin can yield a norbornenyl group.
Experimental Section
General Procedures: The metal complexes were prepared at room
feasible. Chelate-assisted oxidative addition can then occur temperature under nitrogen by standard Schlenk techniques.
[{Rh(Nbd)Cl}2][26] and o-(diphenylphosphane)benzaldehyde[27]
with opening of the diolefinic chelate to give a hydride-
were prepared according to reported procedures. Microanalyses
monoolefin species that can afford the norbornenyl deriva-
were carried out with a Leco CHNS-932 microanalyser. IR spectra
tive. Related [Rh(Cl)(Cod)(bipy)] undergoes the chelate-as-
were recorded with a Nicolet FTIR 740 spectrophotometer in the
sisted oxidative addition of PPh2(o-C6H4CHO) with diole-
range 4000–400 cm–1 using KBr pellets. NMR spectra were re-
fin displacement.[4c] Coordination of the norbornadiene as
corded with Bruker Avance DPX 300 or Bruker Avance 500 spec-
a diolefin is, most likely, a requirement for the hydrogen
transfer with concurrent double bond shift to occur. In ben-
zene, dissociation of 2,2Ј-bipyidine from the neutral penta-
coordinate complex may allow the formation of a hydride-
diolefin species that affords the nortricyclyl isomer.
trometers, 1H and 13C{1H} (TMS internal standard), 31P{1H}
(H3PO4 external standard) and 2D spectra were measured as
CDCl3 or [D6]DMSO solutions. Mass spectra were recorded on a
VG Autospec, by liquid secondary ion (LSI) MS, using nitrobenzyl
alcohol as matrix and a caesium gun (Universidad de Zaragoza).
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Nortricyclyl- and Norbornenyl-Acylrhodium Complexes
FULL PAPER
Preparation of [Rh(Cl)(Nortricyclyl){PPh2(o-C6H4CO)}]n (1): A
stoichiometric amount of PPh2(o-C6H4CHO) (0.12 mmol) was
added to a benzene solution of [{Rh(Nbd)Cl}2] (0.06 mmol). Sub-
sequent stirring for 60 min at room temperature gave a yellow solid
that was filtered off, washed with benzene and vacuum dried (yield
m/z = 629 [M–Cl]+. C35H31ClN2OPRh: C 63.22, H 4.70, N 4.21;
found C 62.96, H 4.76, N 3.85.
Data for 5: Yield 40%. IR: ν = 3345 (m), 3323 (m), 3261 (m, NH ),
˜
2
1603(s, C=O) cm–1. 1H NMR (CDCl3): δ = 5.32 (m, 1 H, ampy-
CH2), 4.64 (br. s, 1 H, NH2), 4.44 (m, 1 H, ampy-CH2), 4.32 (br s,
66%). IR: ν(C=O) = 1637(s) cm–1. 1H NMR (CDCl ): δ = 2.89 (d,
˜
3
1 H, NH2), 1.71 (d, JRh,H = 12.9 Hz, 1 H, HC–Rh), 1.58 (t, JHH
=
JRh,H = 11.5 Hz), 2.71 (d, JRh,H = 11.1 Hz), 2.46 (d, JRh,H = 9.1 Hz)
and 2.80 (d, JRh,H = 9.1 Hz) ppm, HC–Rh. 31P{1H} NMR
(CDCl3): δ = 73.1 (d, JRh,P = 209 Hz), 72.9 (d, JRh,P = 211 Hz),
71.8 (d, JRh,P = 203 Hz) and 71.5 (d, JRh,P = 208 Hz) ppm. FAB
MS calcd. for [C26H23ClOPRh]3: 1560; observed 1525 [M–Cl]+,
1432 [M–Cl–(C7H9)]+. C26H23ClOPRh: calcd. C 59.96, H 4.45;
found C 59.66, H 4.29.
4.7 Hz, 1 H, Ntyl-CHcyclopropyl–CHRh), 1.25 (d, Jgem = 10.3 Hz, 1
H, Ntyl-CH2), 1.02 (t, JHH = 4.3 Hz, 1 H, Ntyl-CHcyclopropyl), 0.81
(m, 4 H, Ntyl-CH + 2 Ntyl-CH2 + Ntyl-CHcyclopropyl), 0.46 (d, Jgem
= 9.4 Hz, 1 H, Ntyl-CH2) ppm. 13C{1H} NMR (CDCl3): δ = 240.7
(dd, JRh,C = 37.3, JP,C = 4.0 Hz, 1C, C=O), 38.8 (dd, JRh,C = 25.2,
JP,C = 6.9 Hz, 1C, HC–Rh), 37.2 (1C, Ntyl-CH), 34.5, 32.9 (2C,
Ntyl-CH2), 19.2 (1C, Ntyl-CHcyclopropyl–CHRh), 12.7, 12.5 (2C,
Ntyl-CHcyclopropyl) ppm. 31P{1H} NMR (CDCl3): δ = 68.3 (d, JRh,P
= 177 Hz) ppm. FAB MS: calcd. C32H31ClN2OPRh 628; m/z = 593
[M–Cl]+. C32H31ClN2OPRh·0.3C6H6: C 62.23, H 5.07, N 4.29;
found C 62.45, H 5.03, N 4.87.
Preparation of [Rh(Cl)(Nortricyclyl)(PPh2(o-C6H4CO))(NN)] (2–6):
A stoichiometric amount of the corresponding bidentate N-ligand
(0.06 mmol) or of pyridine (0.12 mmol) was added to a benzene
suspension of 1 (0.06 mmol). Subsequent stirring for 60 min at
room temperature afforded yellow solids that were filtered off,
washed with benzene and vacuum-dried.
Data for 6: Yield 55%. IR: ν = 1609 (s, C=O) cm–1. 1H NMR
˜
(CDCl3): δ = 2.45 (dd, JRh,H = 10.3, JP,H = 3.3 Hz, 1 H, HC–Rh),
1.25 (d, Jgem = 9.9 Hz, 1 H, Ntyl-CH2), 0.78 (br. s, 1 H, Ntyl-CH),
0.67 (d, Jgem = 9.9 Hz, 1 H, Ntyl-CH2), 0.63 (d, Jgem = 9.5 Hz, 1 H,
Data for 2: Yield 65%. IR: ν = 3389 (s), 3271 (s), 3138 (s, NH ),
˜
2
1600 (s, C=O), 1590 (s, C=N) cm–1. H NMR (CDCl3): δ = 7.78,
1
Ntyl-CH2), 0.60 (m, 2 H, Ntyl-CHcyclopropyl + Ntyl-CHcyclopropyl
–
5.65 (br s, 4 H, NH2), 2.24, 2.15 (s, 6 H, CH3), 1.85 (d, Jgem
=
CHRh), 0.50 (t, JHH = 4.7 Hz, 1 H, Ntyl-CHcyclopropyl), 0.27 (d,
Jgem = 9.5 Hz, 1 H, Ntyl-CH2) ppm. 13C{1H} NMR (CDCl3): δ =
240.0 (dd, JRh,C = 39.1, JP,C = 3.0 Hz, 1C, C=O), 38.1 (dd, JRh,C
= 25.5, JP,C = 6.3 Hz, 1C, HC–Rh), 36.9 (1C, Ntyl-CH), 34.5, 32.6
(2C, Ntyl-CH2), 19.8 (1C, Ntyl-CHcyclopropyl–CHRh), 14.2, 12.4
(2C, Ntyl-CHcyclopropyl) ppm. 31P{1H} NMR (CDCl3): δ = 72.2 (d,
JRh,P = 183 Hz) ppm. C36H33ClN2OPRh: C 63.68, H 4.90, N 4.13;
found C 63.02, H 4.96, N 4.07.
9.5 Hz, 1 H, Ntyl-CH2), 1.41 (dd, JRh,H = 12.8, JP,H = 2.1 Hz, 1
H, HC–Rh), 0.85 (t, JH,H = 4.5 Hz, 1 H, Ntyl-CHcyclopropyl), 0.74
(d, Jgem = 9.5 Hz, 1 H, Ntyl-CH2), 0.69 (m, 1 H, Ntyl-CH), 0.54
(d, Jgem = 9.1 Hz, 1 H, Ntyl-CH2), 0.53 (s, 1 H, Ntyl-CHcyclopropyl),
0.23 (t, JH,H = 5.2 Hz, 1 H, Ntyl-CHcyclopropyl–CHRh), –0.08 (d,
Jgem = 9.1 Hz, 1 H, Ntyl-CH2) ppm. 13C{1H} NMR (CDCl3): δ =
240.7 (dd, JRh,C = 33.2, JP,C = 5.9 Hz, 1C, C=O), 149.9, 145.2 (2C,
C=N), 39.8 (d, JRh,C = 22.4 Hz, 1C, HC–Rh), 38.0 (1C, Ntyl-CH),
33.9, 32.0 (2C, Ntyl-CH2), 17.0 (1C, Ntyl-CHcyclopropyl–CHRh),
14.5 (1C, CH3), 12.9 (2C, CH3 + Ntyl-CHcyclopropyl), 11.4 (1C,
Ntyl-CHcyclopropyl) ppm. 31P{1H} NMR (CDCl3): δ = 71.4 (d, JRh,P
= 172 Hz) ppm. FAB MS: calcd. C30H33ClN4OPRh 634, m/z = 599
[M–Cl]+. C30H33ClN4OPRh·0.3C6H6: C 58.01, H 5.33, N 8.51;
found: C 57.76, H 5.24, N 7.98%.
Reaction of “[Rh(Cl)(Nbd)(bdh)]” with PPh2(o-C6H4CHO) in Ben-
zene: A stoichiometric amount of bdh (13.7 mg, 0.12 mmol) was
added to
a benzene solution of [{Rh(Nbd)Cl}2] (27.6 mg,
0.06 mmol), affording a red suspension of [Rh(Cl)(Nbd)(bdh)].
Subsequent addition of PPh2(o-C6H4CHO) (34.8 mg, 0.12 mmol)
and stirring for 60 min at room temperature gave a yellow solid
that was filtered off, washed with benzene and vacuum dried (yield:
62 mg). According to NMR spectra, the solid contains complex 2
as the main product (up to 87%). Small amounts of hydrides (up
to 13%), products of diolefin displacement, were also observed.
Data for 3: Yield 60%. IR: ν = 1624 (s, C=O) cm–1. 1H NMR
˜
(CDCl3): δ = 1.95 (d, Jgem = 9.9 Hz, 1 H, Ntyl-CH2), 1.36 (dd,
JRh,H = 12.0, JP,H = 2.1 Hz, 1 H, HC–Rh), 0.87 (br s, 1 H, Ntyl-
CH), 0.65 (d, Jgem = 9.9 Hz, 1 H, Ntyl-CH2), 0.47 (d, Jgem = 9.5 Hz,
1 H, Ntyl-CH2), 0.27 (t, JH,H = 5.4 Hz, 1 H, Ntyl-CHcyclopropyl),
Preparation of [Rh(Cl)(Norbornenyl)(PPh2(o-C6H4CO))(bipy)] (7):
A stoichiometric amount of 2,2Ј-bipyridine (0.12 mmol) and an ex-
cess of PPh2(o-C6H4CHO) (0.24 mmol) were added to a MeOH
suspension of [{Rh(Nbd)Cl}2] (0.06 mmol). Subsequent stirring for
60 min at room temperature gave a yellow solid that was filtered
0.13 (t, JH,H = 4.9 Hz, 1 H, Ntyl-CHcyclopropyl), –0.10 (d, Jgem
=
9.5 Hz, 1 H, Ntyl-CH2), –0.49 (t, JH,H = 5.0 Hz, 1 H, Ntyl-
CHcyclopropyl–CHRh) ppm. 13C{1H} NMR (CDCl3): δ = 40.6 (dd,
JRh,C = 26.9, JP,C = 5.2 Hz, 1C, HC–Rh), 38.0 (1C, Ntyl-CH), 34.3,
31.5 (2C, Ntyl-CH2), 17.8 (1C, Ntyl-CHcyclopropyl–CHRh), 12.8,
12.2 (2C, Ntyl-CHcyclopropyl) ppm. 31P{1H} NMR (CDCl3): δ =
72.8 (d, JRh,P = 175 Hz) ppm. FAB MS: calcd. C36H31ClN2OPRh
676; m/z = 641 [M–Cl]+. C36H31ClN2OPRh: calcd. C 63.87, H
4.62, N 4.14; found: C 63.68, H 4.70, N 3.75.
off, washed with methanol and vacuum dried (yield: 46%). IR: ν
˜
= 1624 (s, C=O) cm–1. 1H NMR ([D6]DMSO): δ = 5.06 (dd, JH3,H2
= 5.36, JH1,H2 = 2.89 Hz, 1 H, Nbyl-H2), 4.89 (dd, JH4,H3
=
2.48 Hz, 1 H, Nbyl-H3), 2.40 (s, 1 H, Nbyl-H4), 1.83 (s, 1 H, Nbyl-
H1), 1.75 (m, 1 H, Nbyl-H5), 0.61, 0.15 (d, Jgem = 7.23 Hz, 2 H,
Nbyl-H7), –0.09, –0.57 (m, 2 H, Nbyl-H6) ppm. 13C{1H} NMR
([D6]DMSO): δ = 238.5 (dd, JRh,C = 32.4, JP,C = 6.0 Hz, 1C, C=O),
134.2 (1C, Nbyl-C3), 134.0 (1C, Nbyl-C2), 50.9 (1C, Nbyl-C7), 50.1
(1C, Nbyl-C4), 40.8 (1C, Nbyl-C1), 30.9 (1C, Nbyl-C6), 29.9 (dd,
JRh,C = 28.8, JP,C = 4.4 Hz, 1C, Nbyl-C5) ppm. 31P{1H} NMR
([D6]DMSO): δ = 71.1 (d, JRh,P 171 Hz) ppm. FAB MS: calcd.
C36H31ClN2OPRh 676; m/z (%) = 676 [M]+ (6), 641 [M–Cl]+ (87).
C36H31ClN2OPRh·MeOH: C 62.68, H 4.98, N 3.95; found C 62.60,
H 4.90, N 3.84.
Data for 4: Yield 30%. IR: ν = 3257 (m), 3205 (m, NH ), 1601 (s,
˜
2
C=O) cm–1. 1H NMR (CDCl3): δ = 6.10, 5.72 (m, 2 H, NH2), 1.86
(dd, JRh,H = 12.4, JP,H = 2.9 Hz, 1 H, HC–Rh), 1.63 (t, JHH
=
5.0 Hz, 1 H, Ntyl-CHcyclopropyl–CHRh), 1.45 (d, Jgem = 10.3 Hz, 1
H, Ntyl-CH2), 1.17 (t, JHH = 4.7 Hz, 1 H, Ntyl-CHcyclopropyl), 0.85
(m, 3 H, Ntyl-CH + Ntyl-CH2 + Ntyl-CHcyclopropyl), 0.76, 0.38 (d,
Jgem = 9.3 Hz, 2 H, Ntyl-CH2) ppm. 13C{1H} NMR (CDCl3): δ =
239.36 (dd, JRh,C = 36.1, JP,C = 4.4 Hz, 1C, C=O), 39.1 (dd, JRh,C
= 25.1, JP,C = 6.6 Hz, 1C, HC–Rh), 37.1 (1C, Ntyl-CH), 34.3, 33.0
(2C, Ntyl-CH2), 19.1 (1C, Ntyl-CHcyclopropyl–CHRh), 12.6, 12.3 X-ray Crystal Structure Determination of 2: Single crystals of com-
(2C, Ntyl-CHcyclopropyl) ppm. 31P{1H} NMR (CDCl3): δ = 68.5 (d, plex 2, suitable for X-ray diffraction, were successfully grown by
JRh,P = 183 Hz) ppm. FAB MS: calcd. C35H31ClN2OPRh 664;
www.eurjic.org
allowing slow diffusion of diethyl ether onto chloroform solutions.
1675
Eur. J. Inorg. Chem. 2005, 1671–1677
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

M. A. Garralda et al.
FULL PAPER
A yellow crystal was epoxy coated and mounted on a Bruker Smart
CCD diffractometer using graphite monochromated Mo-Kα radia-
tion (λ = 0.71073 Å) operating at 50 kV and 20 mA. Data were
collected over a hemisphere of the reciprocal space by combination
of three exposure sets. Each exposure of 10 s covered 0.3 in ω. The
first 50 frames were recollected at the end of the data collection to
monitor crystal decay after X-ray exposition. Several crystals were
tried and the best data collection showed a decay of 18% in the
intensities of standard reflections. Fundamental crystal data for the
crystal given are summarized in Table 2. The structure was solved
by Direct methods and conventional Fourier techniques. Refine-
ment was done by full-matrix least-squares on F2 (SHELX-97).[28]
After three cycles of isotropic refinement of all atoms in the Rh
complex, extra electron density was found and was attributed to
three molecules of chloroform. All non-hydrogen atoms have been
refined anisotropically, except the solvent molecules. All hydrogen
atoms were calculated at geometrical positions. It was impossible
to locate the hydrogen atoms of the NH2 groups in a Fourier syn-
thesis. The presence of three CHCl3 molecules of crystallization is
probably the source of the problems encountered during the data
collection. All these atoms were refined only isotropically and with
geometrical restraints and variable common carbon–chlorine dis-
tances. Despite these problems, the atoms of the rhodium complex
refined well – as can be judged from the reasonable deviation in
distances and angles, their thermal parameters and the quality-of-
fit indicator. The high values of largest residual peak and hole in
the final Fourier difference map and the largest shift/esd ratio were
associated with the chlorine atoms of the solvent molecules.
Acknowledgments
Partial financial supports by AECI (Project 119/03/P), Diputación
Foral de Guipuzcoa/EU, MCYT (Project BQU2002–0129) and
UPV are gratefully acknowledged.
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=
NNH2)]·
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Empirical formula
Formula mass
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C33H36Cl10N4OPRh
993.04
293(2)
0.71073
triclinic
¯
P1
11.517(1)
13.481(1)
15.338(1)
76.606(2)
74.156(2)
73.004(2)
2160.9(3)
2
1.082
0.40×0.27×0.18
1.40 to 28.78
(–15, –18, –20 to 12, 10, 20)
18
β [°]
γ [°]
Volume [Å3]
Z
Absorption coefficient (mm–1)
Crystal size (mm3)
θ range for data collection [°]
Index ranges
Decay [%]
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)][a]
wR2 indices (all data)[b]
13935
9835 [R(int.) = 0.0601]
9835/9/393
1.068
0.1164 (4539 observed)
0.3785
Largest diff. peak and hole [e Å–3] 2.825 and –1.551
[a] Σ[|Fo| – |Fc|]/Σ|Fo|. [b] {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
2
2 2
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CCDC-253669 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
1676
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 1671–1677

Nortricyclyl- and Norbornenyl-Acylrhodium Complexes
FULL PAPER
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Received: November 04, 2004
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