Formation of ruthenium-aminocarbene complexes from aldimines and aminals

Article abstract of DOI:10.1002/ejic.200200695

Specific pyridine-based aldimines and aminals act as chelating ligands towards the RuCpL and RuTpL (Tp = hydrido trispyrazolylborate) fragments giving κ²N,N′- coordinated cyclic imine complexes. Under particular conditions, as elucidated in this paper, these complexes rearrange into cyclic aminocarbene complexes. Thus, the reaction of [RuCp(L)(CH₃CN)₂] PF₆ (L = CH₃CN, PMe₃, SbPh₃) with 1 equiv. of py-N=CHR [R = Ph (phenyl), Fc (ferrocenyl), Np (naphthyl)] affords the cyclic aminocarbene complexes [RuCp(L)(=C(R)NH-py)]PF₆, whereas when L = PPh₃, PiPr₃, and CO the reaction stops at the stage of the imine complex [RuCp(L) (κ²N,N′-py-N=CHR)]PF₆. Analogously, [RuTp-(COD)Cl] (COD = 1,5-cyclooctadiene) also reacts readily with the imines py-N=CHR (R = Ph, pMeOC₆H₄, Np) at elevated temperatures to yield the aminocarbene complexes [RuTp{=C(R)NH-py}Cl]. This process may open a new synthetic route for obtaining carbene complexes. The mechanism of the imine-aminocarbene conversion was analyzed by DFT/B3LYP calculations. Accordingly, the operation of a direct 1,2 hydrogen shift can be ruled out; the reaction seems to involve hydrido iminoacyl intermediates resulting from C-H bond activation and deprotonation/protonation steps. Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200200695

FULL PAPER
Formation of Ruthenium؊Aminocarbene Complexes from Aldimines
and Aminals
Christina M. Standfest-Hauser,[a] Kurt Mereiter,[b] Roland Schmid,[a] and Karl Kirchner*[a]
Keywords: Carbenes / Density functional calculations / N ligands / Ruthenium
Specific pyridine-based aldimines and aminals act as chelat-
(COD)Cl] (COD = 1,5-cyclooctadiene) also reacts readily
ing ligands towards the RuCpL and RuTpL (Tp = hydrido with the imines py−N=CHR (R = Ph, pMeOC6H4, Np) at elev-
trispyrazolylborate) fragments giving κ2N,NЈ-coordinated
cyclic imine complexes. Under particular conditions, as
elucidated in this paper, these complexes rearrange into
cyclic aminocarbene complexes. Thus, the reaction of
[RuCp(L)(CH3CN)2]PF6 (L = CH3CN, PMe3, SbPh3) with 1
equiv. of py−N=CHR [R = Ph (phenyl), Fc (ferrocenyl), Np
ated temperatures to yield the aminocarbene complexes
[RuTp{=C(R)NH−py}Cl]. This process may open a new syn-
thetic route for obtaining carbene complexes. The mechan-
ism of the imine−aminocarbene conversion was analyzed by
DFT/B3LYP calculations. Accordingly, the operation of a dir-
ect 1,2 hydrogen shift can be ruled out; the reaction seems to
(naphthyl)] affords the cyclic aminocarbene complexes involve hydrido iminoacyl intermediates resulting from C−H
[RuCp(L)(=C(R)NH−py)]PF6, whereas when L = PPh3, PiPr3,
and CO the reaction stops at the stage of the imine complex
[RuCp(L)(κ2N,NЈ-py−N=CHR)]PF6. Analogously, [RuTp-
bond activation and deprotonation/protonation steps.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
(Ph)NHϪpy}]PF6 was obtained when CH3CN and PMe3
were employed, the reaction stops at the stage of the imine
complex [RuCp(L)(κ2N,NЈ-pyϪNϭCHR)]PF6 with L ϭ
PPh3 and CO. Similarly, [RuTp(COD)Cl] (Tp ϭ hydrido
trispyrazolylborate, COD ϭ 1,5-cyclooctadiene) reacts re-
adily with pyϪNϭCHPh at elevated temperatures to give
the aminocarbene complex [RuTp{ϭC(Ph)NHϪpy}Cl].
Our goal was to extend the scope of the above reactions
to better understand the reasons for the intriguing
imineϪaminocarbene conversion. Towards this goal, we
have used other imines with the general structure pyϪNϭ
CHR, viz. R ϭ ferrocenyl (Fc) and naphthyl (Np), and also
pyϪCH2ϪNϭCHPh. Furthermore, we also used pyridine-
based aminals which are known to be capable of forming
amino carbenes by CϪN and NϪH bond cleavage and am-
ine elimination.[4,5] We have included also PiPr3 and SbPh3
as co-ligands to see whether the ligand size changes the re-
action outcome. Finally, DFT/B3LYP calculations were
performed to back up the mechanistic suggestions.
It is highly fascinating to witness the vast and diversified
varieties of rearrangements within and between molecules
ligated to a transition metal center. In a recent communi-
cation,[1] we reported the conversion of an aldimine to an
amino carbene (Scheme 1, top). This conversion is anal-
ogous to the rearrangement of a coordinated olefin to a
carbene (Scheme 1, bottom).[2] Both of these processes in-
volve a formal 1,2 hydrogen shift whose intimate mecha-
nism remains unknown. For the olefinϪcarbene conver-
sion, the presence of a heteroatom X featuring a strong π-
donor group is of crucial importance. In fact, if X ϭ H,
alkyl, or aryl, the reverse process is more favorable.[3]
In
a
previous report,[1] we reacted the complex
[RuCp(L)(CH3CN)2]PF6, where L ϭ CH3CN, PMe3, PPh3,
or CO, with (E)-N-(phenylmethylene)-2-pyridine amine
(pyϪNϭCHPh). The outcome of the reaction varied with
the nature of the co-ligand L. Whereas [RuCp(L){ϭC-
[a]
Results and Discussion
Institute of Applied Synthetic Chemistry, Vienna University
of Technology,
Getreidemarkt 9, 1060 Vienna, Austria
Fax: (internat.) ϩ 43-1/58801-15499
E-mail: kkirch@mail.zserv.tuwien.ac.at
Synthesis and Characterization
Treatment of [RuCp(L)(CH3CN)2]PF6 [L ϭ CH3CN (1),
PMe3 (2a)] with 1 equiv. of pyϪNϭCHR [R ϭ Ph (phenyl),
Fc (ferrocenyl), Np (naphthyl)] afforded the aminocarbene
[b]
Institute of Chemical Technologies and Analytics, Vienna
University of Technology,
Getreidemarkt 9, 1060 Vienna, Austria
Eur. J. Inorg. Chem. 2003, 1883Ϫ1892
DOI: 10.1002/ejic.200200695
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C. M. Standfest-Hauser, K. Mereiter, R. Schmid, K. Kirchner
FULL PAPER
Scheme 1
complexes [RuCp(L){ϭC(R)NHϪpy}]PF6 (8a؊c, 9a؊c) in
All of the carbene complexes formed are air-stable, in
high yields (Scheme 2). A similar transformation between both solution and in the solid state, with the exception of
[RuCp(SbPh3)(CH3CN)2]PF6 (3) and pyϪNϭCHFc leads 8aϪc, and were characterized by 1H, 13C{1H}, and 31P{1H}
to the aminocarbene complex [RuCp(SbPh3){ϭC(Fc)- NMR spectroscopy and elemental analysis. In the 13C{1H}
NHϪpy}]PF6 (10). Analogously, [RuTp(COD)Cl] (5) also NMR spectra of 8؊10, the carbene moiety is identified by
readily reacts with the imines pyϪNϭCHR (R ϭ Ph, pMe- downfield signals in the range of δ ϭ 263.2 to 281.4 ppm.
OC6H4, Np) at elevated temperatures to yield the aminocar- Other spectral changes accompanying the transformation
bene complexes [RuTp{ϭC(R)NHϪpy}Cl] (11aϪc) to aminocarbene complexes include a characteristic broad
(Scheme 3). The ferrocenyl-based imine pyϪNϭCHFc was resonance between δ ϭ 11.8 and 13.2 ppm assignable to the
not stable under the reaction conditions. We note that no NH proton.
carbene complexes were obtained from 1؊3 by reaction
The solid-state structure of 11a was determined by single-
with monodentate aldimines RNϭCHRЈ (R ϭ Ph, iPr; crystal X-ray diffraction. An ORTEP diagram is depicted
RЈ ϭ Ph, iPr).
in Figure 1 with some bond lengths reported in the caption.
Scheme 2
Scheme 3
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Formation of RutheniumϪAminocarbene Complexes from Aldimines and Aminals
FULL PAPER
Figure 1. Structural view of 11a showing 20% thermal ellipsoids
Figure 3. Structural view of 7a showing 50% thermal ellipsoids
˚
(aromatic H atoms omitted); selected bond lengths (A) and angles
Ϫ
(aromatic H atoms and PF6 ions omitted for clarity); selected
(°): RuϪN(2) 2.210(3), RuϪN(4) 2.074(3), RuϪN(6) 2.048(3),
˚
bond lengths (A) and angles (°): RuϪC(1Ϫ5)av 2.201(2), RuϪC(18)
RuϪN(7) 2.046(3), RuϪCl 2.414(1), RuϪC(15) 1.915(3),
1.876(2), RuϪN(1) 2.125(2), RuϪN(2) 2.167(2), N(2)ϪC(11)
C(15)ϪRuϪN(7)
79.7(1),
92.2(1),
C(15)ϪRuϪN(6)
C(15)ϪRuϪN(2)
92.8(1),
176.6(1),
1.288(3),
C(18)ϪO
1.144(2),
N(1)ϪRuϪN(2)
62.8(1),
C(15)ϪRuϪN(4)
RuϪC(18)ϪO 171.6(1)
C(15)ϪRuϪCl 94.1(1)
Figure 4. Structural view of 7b showing 50% thermal ellipsoids
Ϫ
Figure 2. Structural view of 6b·(CH3)2CO showing 40% thermal
(aromatic H atoms and PF6 ions omitted for clarity); selected
ellipsoids [aromatic H atoms, PF6Ϫ and (CH3)2CO omitted for clar-
˚
bond lengths (A) and angles (°): RuϪC(1Ϫ5)av 2.174(11),
˚
ity]; selected bond lengths (A) and angles (°): RuϪC(1Ϫ5)av
RuϪC(22) 1.846 (10), RuϪN(1) 2.080(9), RuϪN(2) 2.133(8),
N(2)ϪC(11) 1.267(11), C(22)ϪO 1.139(11), N(1)ϪRuϪN(2)
60.3(3), RuϪC(22)ϪO 176.1(11)
2.186(2), RuϪP(1) 2.310(1), RuϪN(1) 2.104(1), RuϪN(2) 2.168(1),
N(2)ϪC(11) 1.294(2), N(1)ϪRuϪN(2) 62.2(1)
The coordination geometry is distorted octahedral with all complexes. Instead, and in keeping with previous results,[1]
angles at ruthenium between 79 and 98° and 172 and 176°. the complexes [RuCp(L)(κ2N,NЈ-pyϪNϭCHR)]PF6 (6aϪd,
The two RuϪN(Tp) bond lengths cis to the carbene moiety 7a,b) are obtained according to Scheme 2. In view of the
˚
are significantly shorter [RuϪN(4)
ϭ
2.074(3) A, strained four-membered NϪRuϪNϪC ring system, it is
˚
RuϪN(6) ϭ 2.048(3) A] than that trans to the carbene moi- noteworthy that no rearrangement to carbene complexes is
ety [RuϪN(2) ϭ 2.210(3) A]. The RuϪN(py) and RuϪCl observed, even at elevated temperature for 24 h. Complexes
bond lengths are 2.046(3) and 2.414(1) A. The RuϪC(15) 6 and 7 were characterized by NMR spectroscopy and el-
bond length is 1.915(3) A, which is similar to that in other emental analysis. In addition, the structures of 6b, 7a, and
˚
˚
˚
heteroatom-stabilized ruthenium carbene complexes (cf. 7b were determined by X-ray crystallography and are pre-
[1]
˚
1.959(1) A in 9a ). The C(15)ϪRuϪN(7) angle is 79.1(1)°. sented in Figure 2, Figure 3 and Figure 4. The overall struc-
If the ligand L in [RuCp(L)(CH3CN)2]PF6 is relatively tures are very similar and they can be described as three-
bulky, such as PPh3 or PiPr3, or if it is a relatively strong π legged piano stool conformations with the two N atoms of
acceptor, as in the case of CO, the reaction with pyϪNϭ the imine ligand and the PPh3 and CO ligands, respectively,
CHR does not result in the formation of aminocarbene as the legs. The NϪRuϪN angles in 6b, 7a, and 7b are
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C. M. Standfest-Hauser, K. Mereiter, R. Schmid, K. Kirchner
FULL PAPER
62.2(1), 62.8(1), and 60.3(3)°, respectively. The four-mem- with the two N atoms of the imine ligand and the N atom
bered NϪRuϪNϪC ring system is essentially planar with of the CH3CN ligand as the legs. It is worth noting that the
torsion angles of 2.5(1), Ϫ2.1(1), and Ϫ1.4(5)°.
NϪRuϪN angle [77.8(1)°] is considerably larger than those
Notwithstanding these stable structures, the relief of the in 6b, 7a, and 7b.
strain of the four-membered NϪRuϪNϪC ring might be a
factor that favors the rearrangement of the κ2NN imine
into the aminocarbene complex. In fact, the imine complex
derived from pyϪCH2ϪNϭCHR, rather than pyϪNϭ
CHR, that features a five-membered NϪRuϪNϪCϪC ring
instead of a four-membered one, does not convert into the
aminocarbene, even if kept for long times at elevated tem-
peratures. This lack of reactivity is the case for
[RuCp(CH3CN)(κ2N,NЈ-pyϪCH2ϪNϭCHPh)]PF6
(12)
and [RuTp(κ2N,NЈ-pyϪCH2ϪNϭCHPh)Cl] (13) that are
obtained from 1 and 5, respectively (Schemes 4 and 5). A
structural view of 12 is given in Figure 5 with selected bond
lengths reported in the caption. This complex can be de-
scribed in terms of a three-legged piano stool conformation
Figure 5. Structural view of 12 showing 50% thermal ellipsoids
Ϫ
(aromatic H atoms and PF6 ions omitted for clarity); selected
˚
bond lengths (A) and angles (°): RuϪC(1Ϫ5)av 2.153(3), RuϪN(1)
2.104(1), RuϪN(2) 2.117(1), RuϪN(3) 2.077(1), N(1)ϪRuϪN(2)
77.8(1), RuϪN(3)ϪC(19) 178.9(3)
The generality of cyclic aminocarbene construction is
further implied by the finding that aminals also react with
the RuCpL and RuTpL fragments to form the correspond-
ing aminocarbene complexes. In these reactions, the aminal
at first obviously transforms back into the starting aldim-
ines and amines. Thus, 1 and 2 react with N,NЈ-bis(2-pyri-
dyl)-1,1-propanediamine [pyϪNHCH(Et)NHϪpy] and
N,NЈ-bis(2-picolyl)-1,1-propanediamine [pyMe-NHCH(Et)-
NHϪpyMe] to form [RuCp(pyϪNH2){ϭC(NHϪpy)Et}]-
PF6 (14a), [RuCp(pyMe-NH2){ϭC(NHϪpyMe)Et}]PF6
(14b), and [RuCp(PMe3)(ϭC(NHϪpy)Et]PF6 (15) in high
yields (Scheme 6). Interestingly, with 2b the reaction does
not stop at the aminocarbene stage, but proceeds further to
give the olefin complex 16. Such a mode of rearrangement
is a common decomposition pathway of electron-deficient
carbene complexes.[3] A structural view of 16, determined
Scheme 4
Scheme 5
Scheme 6
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Formation of RutheniumϪAminocarbene Complexes from Aldimines and Aminals
FULL PAPER
pyMe to give [RuTp{ϭC(NHϪpyMe)Et}Cl] (17) as shown
in Scheme 7. These reactions involve both CϪH and CϪN
activation steps, which thereby release a 2-aminopyridine
molecule. It may be pertinent to note that 2b does not react
with pyϪNϭCHPh to form an aminocarbene complex or
a rearrangement product thereof.
Mechanistic Aspects
In the absence of detectable intermediate products on the
way from the κ2NN-imine to the aminocarbene complexes,
we performed DFT (B3LYP) calculations using pyϪNϭ
CH2 and HCN as model ligands. Along these lines, several
key intermediates can be proposed and these are depicted
in Scheme 8 (energy in kcal/mol). The overall reaction is
exothermic by 8.0 kcal/mol. The reliability of the compu-
tational method (details in the Exp. Sect.) is supported by
the good agreement between the calculated geometries of A
and F (Figure 7) with the X-ray structures for the related
complexes (6a, 6b, 7a, 7b, and 9a).
Figure 6. Structural view of 16 showing 20% thermal ellipsoids
Ϫ
(aromatic H atoms and PF6 ions omitted for clarity); selected
˚
bond lengths (A) and angles (°): RuϪC(1Ϫ5)av 2.224(4), RuϪP(1)
2.348(1), RuϪN(1) 2.122(1), RuϪC(11) 2.171(3), RuϪC(12)
1.272(3), C(11)ϪC(12) 1.383(5), N(1)ϪRuϪC(11) 76.1(1)
At first, the imine moiety of the κ2N,NЈ-pyϪNϭCH2
complex A becomes side-on coordinated (B). The endo-
thermic nature of this step (8.3 kcal/mol) points to the pref-
erence for end-on coordination, although the activation
barrier is relatively low (12.8 kcal/mol). Next, an agostic
CϪH bond is formed (C) that is energetically unfavorable
by 4.9 kcal/mol. In proceeding from A to C, a rotation
about the ϪNϭCH2 bond takes place that moves the
substituent (hydrogen in the model system) from a syn posi-
tion to an anti one, with respect to the metal center. Sub-
sequent CϪH bond activation leads eventually to the hyd-
rido iminoacyl intermediate D.[6Ϫ8] This process is slightly
Scheme 7
by X-ray crystallography, is shown in Figure 6 with selected endothermic by 1.2 kcal/mol and has a small activation bar-
bond lengths reported in the caption. Similarly, rier (2.3 kcal/mol). Such types of intermediates have been
[RuTp(COD)Cl] (5) reacts with pyMe-NHCH(Et)NH- suggested recently for the reaction of [RuHCl(PiPr3)2]2 also
Scheme 8
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C. M. Standfest-Hauser, K. Mereiter, R. Schmid, K. Kirchner
FULL PAPER
Figure 8. Optimized B3LYP geometries of the transition states
˚
Figure 7. Optimized B3LYP geometries of the equilibrium
TSAB, TSBC, TSCD, and TSCF (distances in A)
˚
structures A, B, C, D, and F (distances in A and angles in deg)
with imines, in which case, however, isocyanides are formed
and not aminocarbenes.[9]
hydration of carbonic acid[11] or the hydration of sulfur tri-
oxide.[12]
It appears that the step from C to D involving CϪH acti-
vation/oxidative addition, is particularly crucial to the over-
all imine-to-aminocarbene transformation. The reactivity of
the imine complex is arguably lessened in the case of steri-
cally demanding co-ligands like PPh3 in 2b and PiPr3 in 2c.
Note that the cone angle[10] increases in the order CH3CN
Conclusion
The factors that contribute to the present imine-to-amin-
Ͻ PMe3 Ͻ SbPh3 Ͻ PPh3 Ͻ PiPr3. Alternatively, the pres- ocarbene rearrangement are summarized as follows. (i) The
ence of a strongly π-accepting co-ligand, such as CO, in 4 reaction is chelate assisted with the presence of the pyridine
may prevent the oxidative addition step. The structures of moiety being essential for the coordination of the imine to
the entities AϪF as well as the corresponding transition the metal center. (ii) In the four-membered NϪRuϪNϪC
states TSABϪTSCF are shown in Figure 7 and Figure 8.
ring, the chelated imine ligand is under steric strain. (iii)
The mechanism that is least clear is that for the onward The five-membered ring system NϪRuϪCϪNϪC, arising
reaction from D to F. According to our DFT calculations, from the rearrangement, interacts with the planar pyridine
a direct 1,2 hydrogen shift has a barrier as high as 53.7 kcal/ ring and can be considered as a 10-π-electron metallacycle
mol and, thus, it is safe to exclude it. Alternative possibil- that benefits from aromatic stabilization. (iv) Heteroatom
ities include the intermediacy of a neutral imino acyl com- stabilization seems to be an important factor too. (v) The
plex E or, more appealingly, deprotonation/protonation as- co-ligand L should not be too bulky and only a moderate
sisted by adventitious water, counterion, or solvent. We π acceptor.
favor a hydrogen-transfer pathway based on the implication
The reaction of pyridine-based aldimines and aminals
of water as depicted in Scheme 9. Such a process, though with both RuCp and RuTp complexes could furnish
in need of verification, would be consistent with the proton- alternative and simple preparation methods for special car-
transfer catalysis of water molecules arranged in cyclic ag- bene complexes without the use, for example, of diazoal-
gregates that have been suggested, for example, for the de- kanes.
Scheme 9
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Formation of RutheniumϪAminocarbene Complexes from Aldimines and Aminals
FULL PAPER
[RuCp(PiPr3)(κ2N,NЈ-py؊N؍CHFc)]PF6 (6d): This compound
was prepared analogously to 6b by using 2c (50 mg, 0.090 mmol)
and pyϪNϭCHFc (26 mg, 0.090 mmol) as the starting materials.
Yield: 49 mg (71%). C30H40F6FeN2P2Ru (761.52): calcd. C 47.32,
H 5.29; found C 47.41, H 5.33. 1H NMR ([D6]acetone, 20 °C): δ ϭ
9.64 (s, 1 H, NϭCHFc), 8.64 (d, JH,H1 ϭ 5.03 Hz, 1 H, py6), 7.96
(t, JH,H ϭ 7.99 Hz, 1 H, py4), 7.66 (d, JH,H ϭ 8.45 Hz, 1 H, py3),
7.41 (dd, JH,H1 ϭ 7.54, JH,H2 ϭ 5.25 Hz, 1 H, py5), 5.31Ϫ5.22 (m,
1 H, FeCps), 5.09Ϫ5.01 (m, 1 H, FeCps), 5.00Ϫ4.90 (m, 2 H,
Experimental Section
General: All manipulations were performed under an inert atmos-
phere of argon by using Schlenk techniques. All chemicals were
standard reagent grade and used without further purification. The
solvents were purified according to standard procedures.[13] The
deuterated solvents were purchased from Aldrich and dried over 4-
˚
A
molecular sieves. [RuCp(CH3CN)3]PF6 (1),[14] [RuCp-
(PMe3)(CH3CN)2]PF6 (2a), [RuCp(PPh3)(CH3CN)2]PF6 (2b), and
[RuCp(PiPr3)(CH3CN)2]PF6 (2c),[15] [RuCp(SbPh3)(CH3CN)2]PF6
(3),[16] [RuCp(CO)(CH3CN)2]PF6 (4) and [RuTp(COD)Cl] (5),[17]
FeCps), 4.72 (s, 5 H, RuCp), 4.45 (s, 5 H, FeCp), 2.26 (m, JPH
ϭ
7.27 Hz, 3 H, CH), 1.14 (ddd, JH,H1 ϭ 12.90, JH,H2 ϭ 7.20, JH,H3 ϭ
2.43 Hz, 18 H, CH3) ppm. 13C{1H} NMR ([D6]acetone, 20 °C):
δ ϭ 170.1 (1C, py6), 165.5 (1C, py2), 153.0 (1C, NϭCHFc), 138.5
(1C, py4), 124.1 (1C, py3), 108.5 (1C, py5), 76.0 (1C, FeCps1), 74.9
(1C, FeCps), 74.6 (1C, FeCps), 73.2 (1C, FeCps), 72.9 (1C, FeCps),
[RuCp(PPh3)(κ2N,NЈ-pyϪNϭCHPh)]PF6
(6a),
[RuCp(CO)-
(κ2N,NЈ-pyϪNϭCHPh)]PF6 (7a), [RuCp(CH3CN){ϭC(Ph)NHϪ
py}]PF6 (8a), [RuCp(PMe3){ϭC(Ph)NHϪpy}]PF6 (9a), [RuTp-
{ϭC(Ph)NHϪpy}Cl]
(11a),
[RuCp(pyϪNH2){ϭ
71.7 (JC,P ϭ 1.35 Hz, 5C, RuCp), 70.4 (5C, FeCp), 26.8 (JC,P
ϭ
C(NHϪpy}Et)]PF6 (12a), [RuCp(PMe3){ϭC(NHϪpy)Et}]PF6
(13), and [RuCp(PPh3)(pyϪNHϪη2-CHϭCHMe)]PF6 (14)[1] were
prepared according to literature procedures. 1H, 13C{1H}, and
31P{1H} NMR spectra were recorded on a Bruker AVANCE-250
spectrometer and were referenced to SiMe4 and H3PO4 (85%),
18.9 Hz, 3C, P[CH(CH3)2]3), 19.5 [6C, P[CH(CH3)2]3] ppm.
31P{1H} NMR ([D6]acetone, 20 °C): δ ϭ 52.2 (PiPr3), Ϫ144.1
(1JPF ϭ 708.1 Hz, PF6).
[RuCp(CO)(κ2N,NЈ-py؊N؍CHFc)]PF6 (7b): This compound was
prepared analogously to 6b by using 4 (50 mg, 0.090 mmol) and
pyϪNϭCHFc (26 mg, 0.090 mmol) as the starting materials. Yield:
132 mg (89%). C22H19F6FeN2OPRu (629.29): calcd. C 41.99, H
3.04; found C 41.87; H 3.10. 1H NMR ([D6]acetone, 20 °C): δ ϭ
9.67 (s, 1 H, NϭCHFc), 8.53 (d, JH,H ϭ 5.18 Hz, 1 H, py6), 8.14
1
respectively. H and 13C{1H} NMR signal assignments were con-
firmed by 1H-COSY, 135-DEPT, and HMQC(1H-13C) experiments.
[RuCp(PPh3)(κ2N,NЈ-py؊N؍CHFc)]PF6 (6b): (E)-N-(Ferrocenyl-
methylene)-2-pyridineamine (pyϪNϭCHFc) (44 mg, 0.152 mmol)
was added to a solution of 2b (100 mg, 0.152 mmol) in CH2Cl2
(5 mL). After the mixture was stirred at room temperature for 9 h,
the solvent was evaporated under vacuum and the resulting red
solid was collected on a glass frit and washed twice with diethyl
ether (10 mL). Yield: 105 mg (80%). C39H34F6FeN2P2Ru (863.57):
(dt, JH,H1 ϭ 8.14, JH,H2 ϭ 1.27 Hz, 1 H, py4), 7.80 (d, JH,H
ϭ
8.38 Hz, 1 H, py3), 7.52 (dd, JH,H1 ϭ 7.54, JH,H2 ϭ 5.41 Hz, 1 H,
py5), 5.38 (s, 5 H, RuCp), 5.14Ϫ4.92 (m, 4 H, FeCps), 4.47 (s, 5 H,
FeCp) ppm. 13C{1H} NMR ([D6]acetone, 20 °C): δ ϭ 200.7 (1C,
CO), 171.0 (1C, py6), 166.0 (1C, py2), 152.7 (1C, NϭCHFc), 140.4
(1C, py4), 124.2 (1C, py3), 109.9 (1C, py5), 81.9 (1C, FeCps), 81.1
(5C, RuCp), 76.4 (1C, FeCps), 76.3 (1C, FeCps), 75.7 (1C, FeCps),
74.6 (1C, FeCps1), 71.0 (5C, FeCp) ppm.
1
calcd. C 54.24, H 3.97; found C 54.29; H 4.04. H NMR ([D6]ace-
tone, 20 °C): δ ϭ 9.20 (s, 1 H, NϭCHFc), 8.52 (d, JH,H ϭ 4.42 Hz,
1 H, py6), 7.77 (vt, JH,H ϭ 7.84 Hz, 1 H, py4), 7.55Ϫ7.15 (m, 17
H, PPh3, py3, py5), 5.26Ϫ5.17 (m, 1 H, FeCps), 5.06Ϫ4.99 (m, 1
H, FeCps), 4.97Ϫ4.87 (m, 2 H, FeCps), 4.69 (s, 5 H, RuCp), 4.26
(s, 5 H, FeCp) ppm. 13C{1H} NMR ([D6]acetone, 20 °C): δ ϭ 169.7
(1C, py6), 164.5 (1C, py2), 151.9 (JC,P ϭ 1.4 Hz, 1C, NϭCHFc),
[RuCp(CH3CN)(؍C(Fc)NH؊py)]PF6 (8b): Compound pyϪNϭ
CHFc (133 mg, 0.461 mmol) was added to a solution of 1 (200 mg,
0.461 mmol) in CH2Cl2 (7 mL). After the mixture was stirred at
room temperature for 24 h, the solvent was evaporated under vac-
uum and the resulting purple solid was collected on a glass frit
and washed twice with diethyl ether (10 mL). Yield: 152 mg (85%).
C23H22F6FeN3PRu (642.33): calcd. C 43.01, H 3.45; found C 43.11;
138.1 (1C, py4), 133.7 (JC,P ϭ 40.6 Hz, 3C, Ph1), 133.3 (JC,P
11.0 Hz, 6C, Ph2,6), 130.1 (JC,P ϭ 2.2 Hz, 3C, Ph4), 128.5 (JC,P
ϭ
ϭ
9.9 Hz, 6C, Ph3,5), 123.9 (1C, py3), 109.2 (1C, py5), 75.8 (1C,
FeCps1), 74.8 (1C, FeCps), 74.7 (1C, FeCps), 74.5 (5C, RuCp), 74.5
(1C, FeCps), 71.9 (1C, FeCps), 70.2 (5C, FeCp) ppm. 31P{1H}
1
H 3.47. H NMR ([D6]acetone, 20 °C): δ ϭ 11.90 (br. s, 1 H, NH),
NMR ([D6]acetone, 20 °C): δ ϭ 49.7 (PPh3), Ϫ144.2 (1JPF
719.5 Hz, PF6) ppm.
ϭ
9.10 (d, JH,H ϭ 5.63 Hz, 1 H, py6), 7.95 (ddd, JH,H1 ϭ 8.45, JH,H2 ϭ
7.23, JH,H3 ϭ 1.37 Hz, 1 H, py4), 7.72 (dd, JH,H1 ϭ 8.38, JH,H2
0.83 Hz, 1 H, py3), 7.22 (ddd, JH,H1 ϭ 7.23, JH,H2 ϭ 5.86, JH,H3
ϭ
ϭ
[RuCp(PPh3)(κ2N,NЈ-py؊N؍CHNp)]PF6 (6c): An NMR tube was
charged with 2b (50 mg, 0.080 mmol) and N-(naphthylmethylene)-
2-pyridine amine (pyϪNϭCHNp) (23 mg, 0.080 mmol), and when
they were dissolved in [D6]acetone (0.5 mL), the color changed
from yellow to dark red. After 12 h at room temperature NMR
spectra were taken indicating quantitative formation of 6c. 1H
NMR ([D6]acetone, 20 °C): δ ϭ 10.24 (s, 1 H, NϭCHNp), 9.27 (d,
1.29 Hz, 1 H, py5), 5.28Ϫ5.18 (m, 1 H, FeCps), 5.16Ϫ5.10 (m, 1
H, FeCps), 4.86 (s, 5 H, RuCp), 4.84Ϫ4.78 (m, 2 H, FeCps), 4.30
(s, 5 H, FeCp), 2.34 (s, 3 H, CH3CN) ppm. 13C{1H} NMR ([D6]a-
cetone, 20 °C): δ ϭ 264.6 (1C, RuϭC), 159.0 (1C, py2), 155.8 (1C,
py6), 138.7 (1C, py4), 127.2 (1C, CH3CN), 119.7 (1C, py3), 112.3
(1C, py5), 87.9 (1C, FeCps1), 80.7 (5C, RuCp), 75.1 (1C, FeCps),
74.2 (1C, FeCps), 73.8 (1C, FeCps), 70.3 (5C, FeCp), 68.2 (1C,
FeCps), 3.1 (1C, CH3CN) ppm.
J
H,H ϭ 7.31 Hz, 1 H, py6), 8.64 (td, JH,H1 ϭ 5.28, JH,H2 ϭ 0.80 Hz,
1 H, py4), 8.15Ϫ7.99 (m, 1 H, py3), 7.90Ϫ7.80 (m, 1 H, py5),
7.78Ϫ7.58 (m, 7 H, Np), 7.47Ϫ7.16 (m, 15 H, PPh3), 4.76 (d, [RuCp(CH3CN)(؍C(Np)NH؊py)]PF6 (8c): This compound was
H,H ϭ 0.16 Hz, 5 H, RuCp) ppm. 13C{1H} NMR ([D6]acetone, 20
prepared analogously to 8b by using 1 (100 mg, 0.230 mmol) and
°C): δ ϭ 162.9 (1C, py6), 164.0 (1C, py2), 152.1 (1C, NϭCHNp), pyϪNϭCHNp (64 mg, 0.276 mmol) as the starting materials.
138.4 (1C, py4), 136.9, 135.5, 134.0 (3C, Np), 133.3 (JC,P
Yield: 111 mg (83%). C23H20F6N3PRu (584.47): calcd. C 47.27, H
J
ϭ
1
41.5 Hz, 3C, Ph1), 133.2 (JC,P ϭ 11.5 Hz, 6C, Ph2,6), 132.3 (1C, 3.45; found C 47.33; H 3.40. H NMR ([D6]acetone, 20 °C): δ ϭ
Np), 130.2 (JC,P ϭ 2.2 Hz, 3C, Ph4), 129.3, 128.7 (2C, Np), 128.5 12.86 (s, 1 H, NH), 9.21 (ddd, JH,H1 ϭ 5.73, JH,H2 ϭ 1.54, JH,H3 ϭ
(JC,P ϭ 9.9 Hz, 6C, Ph3,5), 128.0, 127.1, 125.6, 124.8 (4C, Np), 0.75 Hz, 1 H, py6), 8.14Ϫ7.99 (m, 4 H, Np, py4), 7.94Ϫ7.85 (m, 1
122.2 (1C, py3), 110.2 (1C, py5), 75.3 (JC,P ϭ 2.1 Hz, 5C, RuCp) H, Np), 7.78Ϫ7.69 (m, 2 H, Np), 7.67 (d, JH,H ϭ 8.06 Hz, 1 H,
ppm. 31P{1H} NMR ([D6]acetone, 20 °C): δ ϭ 49.7 (PPh3), Ϫ144.1
(1JPF ϭ 719.5 Hz, PF6) ppm.
py3), 7.63Ϫ7.53 (m, 1 H, Np), 7.41 (ddd, JH,H1 ϭ 7.31, JH,H2
5.80, JH,H3 ϭ 1.38 Hz, 1 H, py5), 4.74 (s, 5 H, RuCp), 2.47 (s, 3 H,
ϭ
Eur. J. Inorg. Chem. 2003, 1883Ϫ1892
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1889

C. M. Standfest-Hauser, K. Mereiter, R. Schmid, K. Kirchner
C22H22BN8ClORu (561.81): calcd. C 47.04, H 3.95; found C, 47.11,
FULL PAPER
CH3CN) ppm. 13C{1H} NMR ([D6]acetone, 20 °C): δ ϭ 269.5 (1C,
RuϭC), 158.4 (1C, py2), 155.7 (1C, py6), 138.9 (1C, py4), 136.9, H 3.89. 1H NMR ([D6]DMSO, 20 °C): δ ϭ 13.17 (s, 1 H, NH),
135.1, 133.7, 129.8, 128.9, 128.6, 128.4, 126.5, 125.3, 125.1 (10C,
8.33 (d, JH,H ϭ 5.5 Hz, 1 H, py6), 8.11 (br. s, 1 H, Tp), 8.05 (d,
Np), 124.6 (1C, CH3CN), 120.5 (1C, py3), 113.2 (1C, py5), 82.1 JH,H ϭ 2.2 Hz, 1 H, Tp), 7.89 (d, JH,H ϭ 2.4 Hz, 1 H, Tp), 7.85
(5C, RuCp), 2.9 (1C, CH3CN) ppm.
(d, JH,H ϭ 2.2 Hz, 1 H, Tp), 7.83Ϫ7.68 (m, 2 H, py3,4), 7.16 (t,
JH,H ϭ 6.3 Hz, 1 H, py5), 6.77 (s, 4 H, Ph), 6.64 (br. s, 1 H, Tp),
6.50 (vt, 1 H, JH,H ϭ 1.8 Hz, Tp), 6.00 (vt, 1 H, JH,H ϭ 2.0 Hz,
Tp), 5.94 (vt, 1 H, JH,H ϭ 2.1 Hz, Tp), 5.88 (d, JH,H ϭ 1.6 Hz, 1
H, Tp), 3.71 (s, 3 H, OCH3) ppm. 13C{1H} NMR ([D6]DMSO, 20
°C): δ ϭ 276.9 (1C, RuϭC), 161.1 (1C, py2), 160.7 (1C, Ph4), 151.2
(1C, py6), 149.6 (1C, Ph1), 146.2 (1C, Tp), 143.0 (1C, Tp), 142.4
(1C, Tp), 137.2 (1C, Tp), 137.1 (1C, py4), 135.8 (1C, Tp), 135.5
(1C, Tp), 128.0 (2C, Ph3,5), 115.3 (1C, py5), 113.8 (1C, Ph2,6), 112.3
(1C, py3), 106.8 (2C, Tp), 105.9 (1C, Tp), 56.1 (1C, OCH3) ppm.
[RuCp(PMe3){؍C(Fc)NH؊py}]PF6 (9b): This compound was pre-
pared analogously to 8b by using 2a (50 mg, 0.107 mmol) and
pyϪNϭCHFc (31 mg, 0.107 mmol) as the starting materials. Yield:
68 mg (94%). C24H28F6FeN2P2Ru (677.36): calcd. C 42.56, H 4.17;
1
found C 42.61; H 4.19. H NMR ([D6]acetone, 20 °C): δ ϭ 11.89
(br. s, 1 H, NH), 8.97 (dd, JH,H1 ϭ 5.94, JH,H2 ϭ 0.69 Hz, 1 H,
py6), 7.88 (m, 1 H, py4), 7.76 (d, JH,H ϭ 8.07 Hz, 1 H, py3), 7.12
(ddd, JH,H1 ϭ 7.16, JH,H2 ϭ 5.79, JH,H3 ϭ 1.37 Hz, 1 H, py5),
5.20 (d, JPH ϭ 0.30 Hz, 5 H, RuCp), 5.15Ϫ5.05 (m, 1 H, FeCps),
4.94Ϫ4.87 (m, 1 H, FeCps), 4.83Ϫ4.74 (m, 2 H, FeCps), 4.33 (s, 5
H, FeCp), 1.09 (d, JPH ϭ 9.90 Hz, 9 H, PMe3) ppm. 13C{1H}
NMR ([D6]acetone, 20 °C): δ ϭ 263.2 (JC,P ϭ 12.1 Hz, 1C, Ruϭ
C), 157.9 (1C, py6), 155.7 (JC,P ϭ 1.9 Hz, 1C, py2), 137.5 (1C, py4),
119.2 (1C, py3), 113.0 (1C, py5), 88.0 (1C, FeCps1), 83.0 (5C,
RuCp), 76.8 (1C, FeCps), 73.7 (1C, FeCps), 73.0 (1C, FeCps), 70.6
(5C, FeCp), 66.9 (1C, FeCps), 17.5 (JC,P ϭ 31.8 Hz, 3C, PMe3)
ppm. 31P{1H} NMR ([D6]acetone, 20 °C): δ ϭ 6.2 (PMe3), Ϫ144.2
(1JPF ϭ 708.4 Hz, PF6) ppm.
[RuTp{؍C(Np)NH؊py}Cl] (11c): This compound was prepared
analogously to 11b by using 5 (100 mg, 0.218 mmol) and pyϪNϭ
CHNp (61 mg, 0.262 mmol) as the starting materials. Yield:
87.9 mg (69%). C25H22BN8ClRu (581.84): calcd. C 51.61, H 3.81;
1
found C 51.57, H 3.78. H NMR (CDCl3, 20 °C): δ ϭ 12.30 (s, 1
H, NH), 8.85Ϫ5.66 (m, 21 H, py2Ϫ6, Np, Tp) ppm. 13C{1H} NMR
(CDCl3, 20 °C): δ ϭ 281.4 (1C, RuϭC), 159.7 (1C, py2), 151.0 (1C,
py6), 142.2 (1C, Tp), 141.1(1C, Tp), 136.9 (1C, py4), 136.2 (1C,
Tp), 135.7 (1C, Tp), 135.4 (1C, Tp), 134.6 (1C, Tp), 129.1Ϫ124.8
(m, 10C, Np), 118.7 (1C, py5), 105.9 (1C, py3), 105.9 (3C, Tp) ppm.
[RuCp(PMe3){؍C(Np)NH؊py}]PF6 (9c): This compound was pre-
pared analogously to 8b by using 2a (50 mg, 0.107 mmol) and
pyϪNϭCHNp (25 mg, 0.107 mmol) as the starting materials.
Yield: 59 mg (91%). C24H17F6N2P2Ru (610.42): calcd. C 47.22, H
[RuCp(CH3CN)(κ2N,NЈ-py؊CH2؊N؍CHPh)]PF6 (12): This com-
pound was prepared analogously to 6b by using 1 (100 mg,
0.230 mmol) and N-(phenylmethylene)-2-picolylamine (pyϪCH2Ϫ
NϭCHPh) (50 mg, 0.253 mmol) as the starting materials. Yield:
90 mg (74%). C20H20F6N3PRu (548.44): calcd. C 43.80, H 3.68;
found C 43.85, H 3.71. 1H NMR ([D6]acetone, 20 °C): δ ϭ 9.19
(d, JH,H ϭ 5.05 Hz, 1 H, py6), 9.11 (d, JH,H ϭ 1.26 Hz, 1 H, Nϭ
CHPh), 8.50Ϫ8.48 (m, 2 H, py4, Ph), 7.98 (dt, JH,H1 ϭ 7.78,
JH,H2 ϭ 1.53 Hz, 1 H, py3), 7.68Ϫ7.56 (m, 4 H, Ph), 7.44 (vt, 1 H,
JH,H ϭ 6.56 Hz, py5), 5.62 (d, 1 H, JH,H1 ϭ 17.69 Hz, CH2), 5.43
(d, JH,H ϭ 17.69 Hz, 1 H, CH2), 4.28 (s, 5 H, Cp), 2.19 (s, 3 H,
CH3CN) ppm. 13C{1H} NMR ([D6]acetone, 20 °C): δ ϭ 173.0 (1C,
py6), 160.5 (1C, py2), 155.2 (1C, NϭCHPh), 137.7 (1C, py4), 134.3
(1C, Ph1), 132.5 (1C, Ph4), 130.2 (2C, Ph2,6), 128.8 (2C, Ph3,5),
125.9 (1C, CH3CN), 124.3 (1C, py3), 120.6 (1C, py5), 74.6 (1C,
CH2), 70.5 (5C, Cp), 2.7 (1C, CH3CN) ppm.
1
2.81; found C 47.17; H 2.78. H NMR ([D6]acetone, 20 °C): δ ϭ
12.66 (br. s, 1 H, NH), 9.08 (d, JH,H ϭ 5.79 Hz, 1 H, py6),
8.20Ϫ7.47 (m, 9 H, Np, py4, py3), 7.32 (ddd, JH,H1 ϭ 7.23, JH,H2 ϭ
5.86, JH,H3 ϭ 1.37 Hz, 1 H, py5), 4.94 (d, JPH ϭ 0.30 Hz, 5 H,
RuCp), 1.34 (d, JPH ϭ 9.90 Hz, 9 H, PMe3) ppm. 13C{1H} NMR
([D6]acetone, 20 °C): δ ϭ 268.8 (JC,P ϭ 9.7 Hz, 1C, RuϭC), 157.6
(1C, py2), 155.8 (1C, py6), 147.4 (1C, Np), 137.8 (1C, py4), 133.7
(1C, Np), 129.4 (1C, Np), 128.5 (2C, Np), 126.9 (1C, Np), 126.7
(1C, Npq), 126.5 (1C, Np), 125.3 (2C, Np), 119.9 (1C, py3), 113.6
(1C, py5), 84.1 (5C, RuCp), 17.5 (JC,P ϭ 32.3 Hz, 3C, PMe3) ppm.
31P{1H} NMR ([D6]acetone, 20 °C): δ ϭ 5.4 (PMe3), Ϫ144.2
(1JPF ϭ 719.5 Hz, PF6) ppm.
[RuTp(κ2N,NЈ-py؊CH2؊N؍CHPh)Cl] (13): This compound was
prepared analogously to 11b by using 5 (100 mg, 0.218 mmol) and
pyϪCH2ϪNϭCHPh (47 mg, 0.240 mmol) as the starting materials.
Yield: 87.9 mg (64%). C22H22BN8ClRu (545.81): calcd. C 48.41, H
[RuCp(SbPh3){؍C(Fc)NH؊py}]PF6 (10): This compound was pre-
pared analogously to 6b by using 3 (80 mg, 0.107 mmol) and
pyϪNϭCHFc (31 mg, 0.107 mmol) as the starting materials. Yield:
89 mg (87%). C39H34F6FeN2PSbRu (954.35): calcd. C 49.08, H
1
1
3.59; found C, 49.12, H 3.62. H NMR ([D6]acetone, 20 °C): δ ϭ
4.06; found C 48.49, H 4.13. H NMR (CDCl3, 20 °C): δ ϭ 9.05
11.76 (br. s, 1 H, NH), 9.19 (d, JH,H ϭ 5.18 Hz, 1 H, py6), 7.67 (dt,
JH,H1 ϭ 7.73, JH,H2 ϭ 0.91 Hz, 1 H, py4), 7.53Ϫ7.12 (m, 16 H,
(s, 1 H, NϭCH), 8.12 (d, JH,H ϭ 5.8 Hz, 1 H, py6), 7.89 (d, JH,H ϭ
2.4 Hz, 1 H, Tp), 7.83 (d, JH,H ϭ 1.9 Hz, 1 H, Tp), 7.73 (d, JH,H ϭ
2.2 Hz, 1 H, Tp), 7.61 (d, JH,H ϭ 1.4 Hz, 1 H, Tp), 7.57 (d, JH,H ϭ
2.2 Hz, 1 H, Tp), 7.4 Ϫ7.37 (m, 3 H, Ph), 7.33 (d, JH,H ϭ 2.1 Hz,
1 H, Tp), 7.23Ϫ7.13 (m, 2 H, Ph), 7.02 (t, JH,H ϭ 7.6 Hz, 1 H,
py4), 6.74 (t, JH,H ϭ 7.5 Hz, 1 H, py5), 6.61 (d, JH,H ϭ 14.9 Hz, 1
H, CH2), 6.44 (d, JH,H ϭ 7.9 Hz, 1 H, py3), 6.26 (vt, JH,H ϭ 2.1 Hz,
1 H, Tp), 6.03 (vt, JH,H ϭ 2.1 Hz, 1 H, Tp), 5.67 (vt, JH,H ϭ 2.0 Hz,
1 H, Tp), 5.23 (d, JH,H ϭ 16.0 Hz, 1 H, CH2) ppm. 13C{1H} NMR
SbPh3, py3), 6.98 (ddd, JH,H1 ϭ 6.62, JH,H2 ϭ 6.24, JH,H3
ϭ
0.46 Hz, 1 H, py5), 5.36 (s, 5 H, RuCp), 5.07Ϫ4.94 (m, 2 H, FeCps),
4.86Ϫ4.73 (m, 2 H, FeCps), 4.27 (s, 5 H, FeCp) ppm. 13C{1H}
NMR ([D6]acetone, 20 °C): δ ϭ 263.4 (1C, RuϭC), 157.4 (1C, py2),
155.9 (1C, py6), 135.2 (1C, py4), 134.9 (6C, Ph32,6), 132.2 (3C, Ph3 ),
1
4
130.2 (3C, Ph3 ), 129.3 (6C, Ph33,5), 118.6 (1C, py3), 113.0 (1C,
py5), 87.6 (1C, FeCps1), 79.3 (5C, RuCp), 76.5 (1C, FeCps), 74.3
(1C, FeCps), 73.7 (1C, FeCps), 70.2 (5C, FeCp), 67.1 (1C, FeCps)
ppm.
2
(CDCl3, 20 °C): δ ϭ 171.4 (1C, NϭCHPh), 162.4 (1C, py ), 153.6
(1C, py 6), 145.1 (1C, Tp), 144.3 (1C, Tp), 141.7 (1C, Tp), 136.6
(1C, Tp), 135.4 (1C, Tp), 134.9 (1C, Tp), 134.4 (1C, py 4), 133.7
(1C, Ph1), 130.0 (1C, Ph4), 128.2 (2C, Ph2,6), 128.0 (2C, Ph3,5),
[RuTp{؍C(C6H4OMep)NH؊py)Cl] (11b): A solution of 5 (100 mg,
0.218 mmol) and N-(p-methoxyphenylmethylene)-2-pyridineamine
(pyϪNϭCHC6H4OMep) (92.5 mg, 0.436 mmol) in DMF (4 mL)
was heated under reflux for 2.5 h. After evaporation of the solvent
under reduced pressure, the brown product was washed with pen-
tane (2 ϫ 5 mL), and dried under vacuum. Yield: 94.4 mg (77%).
5
3
123.2 (1C, py ), 119.2 (1C, py ), 106.8 (1C, Tp), 106.6 (1C, Tp),
106.2 (1C, Tp), 75.2 (1C, CH2) ppm.
[RuCp(pyMe-NH2){؍C(NH؊pyMe)Et}]PF6 (14b): A solution of 1
(100 mg, 0.230 mmol) and N,NЈ-bis(2-picolyl)-1,1-propanediamine
1890
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 1883Ϫ1892

Formation of RutheniumϪAminocarbene Complexes from Aldimines and Aminals
FULL PAPER
Table 1. Details for the crystal structure determinations of complexes 6b·(CH3)2CO, 7a, 7b, 11a, 12, and 16
6b·(CH3)2CO
7a
7b
11a
12
16
Empirical formula C42H40F6FeN2OP2Ru C18H15F6N2OPRu C22H19F6FeN2OPRu C21H20BClN8Ru
Formula mass 921.62 521.36 629.28 531.78
C20H20F6N3PRu
548.43
C31H30F6N2P2Ru
707.58
Crystal size, mm 0.45 ϫ 0.35 ϫ 0.10
0.75 ϫ 0.07 ϫ 0.05 0.40 ϫ 0.06 ϫ 0.06 0.32 ϫ 0.22 ϫ 0.18 0.64 ϫ 0.20 ϫ 0.12 0.70 ϫ 0.04 ϫ 0.02
¯
space group
P1 (No. 2)
P21/n (No. 14)
10.485(1)
P21/n (No. 14)
10.820(7)
C2/c (No. 15)
27.131(7)
P21/n (No. 14)
10.167(2)
P21/n (No. 14)
13.469(2)
˚
a, A
11.035(1)
14.187(2)
14.450(2)
74.574(3)
70.554(3)
67.939(3)
1951.2(4)
2
˚
b, A
13.966(2)
13.369(9)
11.152(3)
11.840(2)
15.052(3)
˚
c, A
12.698(2)
30.38(2)
15.546(4)
18.149(3)
14.808(3)
α, deg
β, deg
γ, deg
90.338(3)
93.17(2)
106.24(1)
96.803(3)
100.60(1)
3
˚
V, A
1859.2(4)
4
4387(5)
8
4516(2)
8
2169.3(6)
4
2950.7(9)
4
Z
ρcalcd., g cmϪ3
T, K
1.569
173(2)
1.863
123(2)
1.000
1032
multi scan
30
1.905
123(2)
1.493
2496
none
25
1.564
297(2)
0.839
2144
multi scan
25
1.679
183(2)
0.859
1096
multi scan
30
1.593
297(2)
0.703
1432
multi scan
30
µ, mmϪ1 (Mo-Kα) 0.906
F(000)
Absorption corr. multi scan
θmax, deg. 30
936
No. of reflections 24939
measd.
12429
23139
22327
30388
40569
No. of unique
reflections
no. of reflections 9168
10853
5172
3956
7627
4022
3937
3140
6244
5260
8421
6841
I Ͼ 2σ(I)
No. of params
R1 [I Ͼ 2σ(I)][a]
R1 (all data)
515
262
0.028
0.047
0.062
367
0.080
0.162
0.219
289
0.033
0.048
0.092
295
0.032
0.041
0.091
379
0.045
0.058
0.134
0.031
0.041
0.082
wR2 (all data)
Diff. Four. peaks, Ϫ0.63/0.83
min./max., e·A
Ϫ0.42/0.56
Ϫ1.09 /1.86
Ϫ0.55/0.92
Ϫ0.86/0.85
Ϫ0.74/1.51
Ϫ3
˚
R1 ϭΣFo Ϫ Fc /ΣFo, wR2 ϭ [Σ[w(Fo2 Ϫ Fc ) ]/Σ[w(Fo ) ]]1/2
.
[a]
2 2
2 2
[pyMeϪNHCH(Et)NHϪpyMe] (59 mg, 0.20 mmol) in CH2Cl2
(8 mL) was stirred at room temperature for 3 h. The volume of the
solution was then reduced to about 1 mL. Upon addition of diethyl
ether, a brick-red solid was obtained that was collected on a glass
frit, washed with diethyl ether, and dried under vacuum. Yield:
3.47Ϫ3.15 (m, 2 H, CH2), 2.07 (s, 3 H, pyϪMe), 0.77 (t, JH,H ϭ
7.7 Hz, 3 H, CH3) ppm. 13C{1H} NMR ([D6]DMSO, 20 °C): δ ϭ
290.3 (1C, RuϭC), 160.0 (1C, py2), 150.7 (1C, py6), 148.5 (1C, py4),
145.1 (1C, Tp), 142.7 (1C, Tp), 141.6 (1C, Tp), 136.6 (1C, Tp),
135.7 (1C, Tp), 135.6 (1C, Tp), 120.7(1C, py5), 111.9 (1C, py3),
106.6 (1C, Tp), 106.5 (1C,Tp), 106.3 (1C, Tp), 39.6 (1C, CH2), 21.5
98 mg (75%). C20H25F6N4PRu (567.48): calcd. C 42.33, H 4.44;
1
found C 43.27, H 4.40. H NMR ([D6]acetone, 20 °C): δ ϭ 12.70 (1C, CH3ϪCH2), 10.9 (1C, pyϪMe) ppm.
(br. s, 1 H, NH), 9.15 (d, JH,H ϭ 6.00 Hz, 1 H, py), 8.16 (d, JH,H ϭ
6.16 Hz, 1 H, py), 7.39 (m, 1 H, py), 7.15 (d, JH,H ϭ 5.53 Hz, 1 H,
py), 6.49 (m, 1 H, py), 6.30 (br. s, 2 H, NH2), 6.19 (d, JH,H
Crystallographic
Structure
Determinations:
Crystals
of
ϭ
6b·(CH3)2CO, 7a, 7b, 11a, 12, and 16 were obtained by vapor dif-
fusion of Et2O into either CH2Cl2 or acetone solutions. Crystal
data and experimental details are given in Table 1. All X-ray data
were collected on a Bruker Smart CCD area detector dif-
5.05 Hz, 1 H, py), 4.98 (s, 5 H, Cp), 4.07 (m, JH,H ϭ 7.27 Hz, 1 H,
CH2), 3.87 (m, JH,H ϭ 7.31 Hz, 1 H, CH2), 2.43 (s, 3 H, pyϪMe),
2.08 (s, 3 H, pyϪMe), 1.43 (t, JH,H ϭ 7.50 Hz, 3 H, CH3) ppm.
13C{1H} NMR ([D6]acetone, 20 °C): δ ϭ 276.6 (1C, RuϭC), 162.6
(1C, pyq), 158.6 (1C, pyq), 154.7 (1C, py), 151.5 (1C, py), 150.5
(1C, pyq), 150.0 (1C, pyq), 121.5 (1C, py), 115.1 (1C, py), 112.4
(1C, py), 109.9 (1C, py), 82.1 (5C, Cp), 45.5 (1C, CH2CH3), 20.5
(1C, pyϪMe), 20.0 (1C, pyϪMe), 12.2 (1C, CH2CH3) ppm.
fractometer (graphite-monochromated Mo-Kα radiation,
λ ϭ
˚
0.71073 A, 0.3° ω-scan frames covering either hemispheres (7a, 7b)
or complete spheres of the reciprocal space, Bruker Kryoflex cool-
ing unit). Corrections for Lorentz and polarization effects, for crys-
tal decay, and for absorption were applied (multi-scan method with
the program SADABS[18]). All structures were solved by direct
methods using the program SHELXS-97.[19] Structure refinements
on F2 were carried out with program SHELXL-97.[20] All non-hy-
drogen atoms were refined anisotropically. Hydrogen atoms were
inserted in idealized positions and were refined riding on the atoms
to which they were bonded. Critical hydrogen atoms were refined
in positional parameters without such restraints.
[RuTp{؍C(NH؊pyMe)Et}Cl] (17): This compound was prepared
analogously to 11b by using 5 (100 mg, 0.218 mmol) and pyMe-
NHCH(Et)NH-pyMe (72.5 mg, 0.283 mmol) as the starting mate-
rials. Yield: 65.6 mg (61%). C18H22BN8ClRu (497.76): calcd. C
43.43, H 4.46; found C 43.39, H 4.49. 1H NMR ([D6]DMSO, 20
°C): δ ϭ 13.06 (s, 1 H, NH), 8.15 (d, JH,H ϭ 5.8 Hz, 1 H, py6),
8.06 (d, JH,H ϭ 1.7 Hz, 1 H, Tp), 7.98 (d, JH,H ϭ 2.2 Hz, 1 H, Tp),
7.87 (d, JH,H ϭ 2.2 Hz, 1 H, Tp), 7.82Ϫ7.70 (m, 2 H, 2Tp), 7.44
CCDC-200230 to -200235 contain the supplementary crystallo-
(s, 1 H, py3), 6.98 (dd, J1 ϭ 6.0, J2 ϭ 1.3 Hz 1 H, py5), 6.45 (vt, graphic data for this paper. These data can be obtained free of
JH,H ϭ 2.0 Hz, 1 H, Tp), 6.28 (vt, JH,H ϭ 2.0 Hz, 1 H, Tp), 5.88
charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
(vt, JH,H ϭ 2.1 Hz, 1 H, Tp), 5.79 (d, JH,H ϭ 1.9 Hz, 1 H, Tp), Cambridge Crystallographic Data Centre, 12, Union Road, Cam-
Eur. J. Inorg. Chem. 2003, 1883Ϫ1892
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1891

C. M. Standfest-Hauser, K. Mereiter, R. Schmid, K. Kirchner
FULL PAPER
bridge CB2 1EZ, UK; Fax: (internat.)
E-mail: deposit@ccdc.cam.ac.uk].
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Computational Details: All calculations were performed using the
Gaussian98 software package on the Silicon Graphics Origin 2000
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ergy of the model complexes and the transition states were optim-
ized at the B3LYP level[22] with the Stuttgart/Dresden ECP (SDD)
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[14]
[15]
the C, N, and H atoms the 6-31g** basis set was employed.[24]
A
vibrational analysis was performed to confirm that the structures
of the model compounds have no imaginary frequencies. The tran-
sition-state structure was relaxed after applying a small pertur-
bation to ensure that it is connected to the corresponding reactant
and product. A vibrational analysis was also performed to confirm
that it has only one imaginary frequency. The geometries were opti-
mized without constraints (C1 symmetry).
[16]
[17]
[18]
[19]
[20]
[21]
Acknowledgments
Financial support by the ‘‘Fonds zur Förderung der wissen-
schaftlichen Forschung’’ (Project No. P14681-CHE) is gratefully
acknowledged. Support from the EC through the COST D17 Ac-
tion is also acknowledged.
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Received December 20, 2002
1892
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 1883Ϫ1892