Mono- and dimetallic cyano complexes with {Mo(η3-allyl)(CO)2(N-N)} fragments

Article abstract of DOI:10.1002/ejic.200390142

Treatment of [MoCl(η³-allyl)(CO)₂(phen)] with NaCN in CH₂Cl₂/MeOH afforded [Mo(CN) (η³-allyl)(CO)₂(phen)] [al-lyl = C₃H₅ (1a); 2-MeC₃H₄ (1b)] as

Full text of DOI:10.1002/ejic.200390142

FULL PAPER
Mono- and Dimetallic Cyano Complexes with {Mo(η3-allyl)(CO)2(N؊N)}
Fragments
[a]
[a]
[a]
[a]
[a]
´
´
´
´
Julio Perez,* Eva Hevia, Lucıa Riera, Vıctor Riera, Santiago Garcıa-Granda,
[b]
[c]
´
´
Esther Garcıa-Rodrıguez, and Daniel Miguel
Keywords: Allylic compounds / Cyanides / Heterometallic compounds / Molybdenum / Manganese / Rhenium
Treatment of [MoCl(η3-allyl)(CO)2(phen)] with NaCN in
CH2Cl2/MeOH afforded [Mo(CN)(η3-allyl)(CO)2(phen)] [al-
4), in which the C and N atoms of the cyano bridge are bon-
ded to Mo and M (M = Mn, Re), respectively. The linkage
lyl = C3H5 (1a); 2-MeC3H4 (1b)] as the sole products (no prod- isomer of 4 (C and N atoms of the cyano group bonded to
ucts of cyanide attack on the allyl group were detected).
Treatment of 1a,b with [Mo(OTf)(η3-C3H5)(CO)2(phen)] and
NaBArЈ4 in CH2Cl2 yielded the compounds [{Mo(η3-
allyl)(CO)2(phen)}(µ-CN){Mo(η3-C3H5)(CO)2(phen)}]BArЈ4
(2a,b). Analogous treatment of 1a with fac-[M(OTf)(CO)3(b-
Re and Mo, respectively) (6) was prepared by treatment of
[Re(CN)(CO)3(bipy)] (5) with [Mo(OTf)(η3-C3H5)(CO)2-
(phen)] and NaBArЈ4. Compounds 1a, 2b, 3, and 6 were char-
acterized by X-ray diffraction.
ipy)] (M = Mn, Re) and NaBArЈ4 resulted in the synthesis of ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
[{Mo(η3-C3H5)(CO)2(phen)}(µ-CN){M(CO)3(bipy)}]BArЈ4 (3,
Germany, 2003)
Introduction
study on the reactivity of [MoX(η3-allyl)(CO)2(NϪN)]
complexes towards cyanide, as well as the behavior of the
resulting cyano complexes as ligands.
Monometallic complexes with terminal cyano ligands
can act as metalloligands toward a second metal fragment
through the uncoordinated nitrogen atom of the cyano
group, affording dimetallic complexes with CN bridges,[1Ϫ6]
simpler models of the supramolecular and solid-state entit-
ies in which cyano groups act as links between metal atoms.
We have recently found that pseudooctahedral [MoX(η3-
allyl)(CO)2(NϪN)] (NϪN ϭ 2,2Ј- bipyridine, bipy; 1,10-
phenanthroline, phen) complexes react with organolithium
or organomagnesium reagents and with sodium alkoxides
to afford new alkyl,[7] alkynyl,[8] and alkoxo[9] complexes by
selective halide substitution. A similar reactivity pattern
would provide access to the previously unknown
[Mo(CN)(η3-allyl)(CO)2(NϪN)] complexes. Attractive fea-
tures of the known [MoX(η3-allyl)(CO)2(NϪN)] com-
pounds are their ease of preparation[10] and the robustness
of the {Mo(η3-allyl)(CO)2(NϪN)} fragment[11] that directs
the reactivity towards the remaining coordination
position.[7Ϫ9] This paper summarizes the results of our
Results and Discussion
Treatment of [MoCl(η3-C3H5)(CO)2(phen)][12] with ex-
cess sodium cyanide in CH2Cl2/MeOH resulted in the
formation of [Mo(CN)(η3-C3H5)(CO)2(phen)] (1a) as the
only product, as depicted in Scheme 1. Employment of
methanol as co-solvent was needed to provide sufficient
solubility for the sodium cyanide. The product 1a was easily
separated from the excess sodium cyanide and the sodium
chloride by-product by extraction into pure CH2Cl2, fol-
lowed by filtration and crystallization.
[a]
´
´
´
Inorganica/
Departamento de Quımica Organica
e
´
I.U.Q.O.E.M., Facultad de Quımica, Universidad de Oviedo
Ϫ C.S.I.C.,
Scheme 1
´
´
Julian Claverıa s/n, 33071 Oviedo, Spain
Fax: (internat.) ϩ 34-985/103446
E-mail: japm@sauron.quimica.uniovi.es
The IR spectrum of 1a shows, in addition to the two
strong bands corresponding to the cis-Mo(CO)2 fragment,
a weak band indicative of the presence of a cyano group.[1,2]
Its νCN value (2113 cmϪ1) is higher than that of the free
cyanide anion (2080 cmϪ1), as is typically found for C-
[b]
[c]
´
´
´
Departamento de Quımica Fısica y Analıtica, Facultad de
´
´
Quımica, Universidad de Oviedo Ϫ C.S.I.C.,
´
Julian Claverıa s/n, 33071 Oviedo, Spain
´
´
Departamento de Quımica Inorganica, Facultad de Ciencias,
Universidad de Valladolid,
47071 Valladolid, Spain
Eur. J. Inorg. Chem. 2003, 1113Ϫ1120  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0306Ϫ1113 $ 20.00ϩ.50/0 1113

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J. Perez et al.
FULL PAPER
bound cyano ligands in transition metal complexes.[13] The °] values are typical for MϪCϪN groupings,[1,2] and the
1H NMR spectrum of 1a reveals the presence of a molecu- Mo(1)ϪC(3) distance [2.188(8) A] is similar to Mo-C(alky-
˚
lar mirror plane (four signals for the phen ligand), and a nyl) distances recently found in isostructural complexes.[8,15]
symmetric, static η3-allyl group. The methallyl complex
This structure concurs with the static structure in solu-
[Mo(CN)(η3-2-MeC3H4)(CO)2(phen)] (1b) was prepared in tion as deduced from the spectroscopic data (see above). In
a similar manner. Its spectroscopic features are also indicat- fact, X-ray diffraction does not allow clear differentiation
ive of a geometry like that of 1a, and so the structures between carbonyl and cyano groups, and so the spectro-
shown in Scheme 1 are assumed. The low solubility of 1a,b scopic data constitute the stronger evidence of their relative
in organic solvents precluded the observation of significant positions (two cis-carbonyl ligands related by a mirror
13C NMR spectroscopic data, but the structure of 1a was plane). The cyano complexes 1a,b are obtained in good
determined by single-crystal X-ray diffraction. A view of yield, and no products resulting from cyanide anion attack
the molecule is displayed in Figure 1, and selected distances on the allyl group could be detected. It is worth noting that,
and angles are given in Table 1.
in general, attack on the allyl moiety is preferred for stabil-
ized, soft nucleophiles, whereas hard ones preferentially at-
tack the metal atom.[16,17] For [MoX(η3-allyl)(CO)2(LϪL)]
complexes in particular, stabilized carbanions Ϫ such as
those resulting from deprotonation of dialkyl malonates Ϫ
attack the allyl ligand.[18] In contrast, we have found here
that the soft cyanide anion attacks the metal atom.
We aimed to explore the potential of the cyano com-
plexes 1a,b as ligands. We recently found that triflate ab-
straction from [Mo(OTf)(η3-allyl)(CO)2(phen)] can be
[19]
smoothly effected by use of NaBArЈ4
[ArЈ ϭ 3,5-bis(tri-
fluoromethyl)phenyl] in CH2Cl2.[20] We thus treated equim-
olar amounts of this triflato complex, 1a,b, and NaBArЈ4,
in each case obtaining a single product, the IR νCN band
of which showed the shift to higher wavenumber values ex-
pected for a change in the coordination mode of the cyano
group from terminal to bridge (νCN: 2129 cmϪ1 for 2a and
2132 cmϪ1 for 2b) (Scheme 2).[1,2]
Figure 1. Molecular structure and numbering scheme of
[Mo(CN)(η3-C3H5)(CO)2(phen)] (1a); thermal ellipsoids are drawn
at the 30% probability level
These compounds, partly due to the presence of the
BArЈ4 anion, displayed high solubility in dichloromethane,
allowing the acquisition of their 13C NMR spectra. The
most characteristic features are the weak signals at δ ϭ
169.8 ppm (2a) and δ ϭ 169.9 ppm (2b), attributable to the
CN groups. Red crystals of 2a could be obtained from
CH2Cl2/hexane mixtures, but an attempt to determine its
structure by X-ray diffraction was complicated by the severe
disorder affecting one of the allyl groups. The analogous
dimetallic compound 2b did not suffer from this problem,
and its structure could be determined with acceptable accu-
racy (see Figure 2 for a view of the cation, Tables 2 and 5
for selected geometrical data). The cation of 2b consists of
two {Mo(η3-allyl)(CO)2(NϪN)} fragments, isostructural
with that of 1a, bridged by a CN group in linear fashion
[Mo(1)ϪC(1)ϪN(1) ϭ 176.2(8)°, C(1)ϪN(1)ϪMo(2) ϭ
179.4(8)°].
3
˚
Table 1. Selected bond lengths [A] and angles [°] for [Mo(CN)(η -
C3H5)(CO)2(phen)] (1a)
Mo(1)ϪC(1)
Mo(1)ϪC(2)
Mo(1)ϪC(4)
Mo(1)ϪC(5)
Mo(1)ϪC(6)
Mo(1)ϪC(3)
C(1)ϪMo(1)ϪC(2)
1.966(7) Mo(1)ϪN(1)
1.959(9) Mo(1)ϪN(2)
2.329(7) C(1)ϪO(1)
2.229(7) C(2)ϪO(2)
2.325(7) C(3)ϪN(3)
2.188(8)
2.243(5)
2.255(5)
1.140(7)
1.155(8)
1.103(8)
79.0(3)
C(2)ϪMo(1)ϪC(3)
89.0(2)
81.5(2)
N(1)ϪMo(1)ϪN(2) 73.65(17) C(3)ϪMo(1)ϪN(1)
C(1)ϪMo(1)ϪN(1) 169.8(2)
C(2)ϪMo(1)ϪN(2) 169.6(2)
C(3)ϪMo(1)ϪN(2)
N(3)ϪC(3)ϪMo(1) 178.3(6)
81.09(19)
C(1)ϪMo(1)ϪC(3)
88.4(2)
The bond between the cyano group and a second metal
The molecule is isostructural with previously known fragment is therefore formed without disruption of the
[MoX(η3-allyl)(CO)2(NϪN)] compounds.[14] It can thus be MoϪCN bond. In contrast, the alkynyl group (for which
described, if the η3-allyl group is regarded as occupying one similarities with CN as a ligand have been noted)[21] is
coordination position, as pseudooctahedral: the molyb- transferred from {Mo(η3-allyl)(CO)2(NϪN)} to other
denum atom is surrounded by the two carbonyl groups, the metal fragments.[15] Since the two metal fragments of 2b
cyano group, the η3-allyl group, and the two nitrogen atoms are distinguishable, and only one species is present both in
of the phenanthroline ligand. The two CO groups are mutu- solution and in the crystal, the complex is stable with re-
Ǟ
ǟ
ally cis, and each is trans to a phen nitrogen atom. The spect to CN NC isomerization of the bridge.
cyano and allyl groups are therefore mutually trans. The
C(3)ϪN(3) [1.103(8) A] and N(3)ϪC(3)ϪMo(1) [178.3(6) lic cyanomolybdenum complexes to act as ligands towards
We wanted to evaluate the ability of the new monometal-
˚
1114
Eur. J. Inorg. Chem. 2003, 1113Ϫ1120

Mono- and Dimetallic Cyano Complexes with {Mo(η3-allyl)(CO)2(NϪN)} Fragments
FULL PAPER
Scheme 2
3
˚
Table 2. Selected bond lengths [A] and angles [°] for the [{Mo(η -
C3H4-Me-2)(CO)2(phen)}(µ-CN){Mo(η3-C3H5)(CO)2(phen)}]ϩ
cation of 2b
Mo(1)ϪC(2)
Mo(1)ϪC(3)
Mo(1)ϪC(6)
Mo(1)ϪC(7)
Mo(1)ϪC(8)
Mo(1)ϪC(1)
Mo(1)ϪN(2)
Mo(1)ϪN(3)
C(2)ϪO(2)
1.930(11) Mo(2)ϪC(4)
1.935(11) Mo(2)ϪC(5)
2.330(8) Mo(2)ϪC(10)
2.250(9) Mo(2)ϪC(11)
2.317(8) Mo(2)ϪC(12)
2.135(9) Mo(2)ϪN(1)
2.229(7) Mo(2)ϪN(4)
2.219(7) Mo(2)ϪN(5)
1.172(10) C(4)ϪO(4)
1.168(10) C(5)ϪO(5)
1.142(9)
1.966(12)
1.904(13)
2.325(11)
2.226(12)
2.258(11)
2.195(8)
2.250(8)
2.249(8)
1.173(11)
1.193(12)
C(3)ϪO(3)
C(1)ϪN(1)
C(2)ϪMo(1)ϪC(3) 82.0(4)
C(2)ϪMo(1)ϪN(3) 167.1(3)
C(3)ϪMo(1)ϪN(2) 167.7(3)
N(2)ϪMo(1)ϪN(3) 74.3(3)
C(1)ϪMo(1)ϪC(2) 87.7(4)
C(1)ϪMo(1)ϪC(3) 89.7(4)
C(1)ϪMo(1)ϪN(2) 78.8(3)
C(1)ϪMo(1)ϪN(3) 79.5(3)
Mo(1)ϪC(1)ϪN(1) 176.2(8)
C(4)ϪMo(2)ϪC(5) 76.3(5)
C(4)ϪMo(2)ϪN(4) 164.3(4)
C(5)ϪMo(2)ϪN(5) 170.1(4)
N(4)ϪMo(2)ϪN(5) 73.4(3)
N(1)ϪMo(2)ϪC(4) 86.2(4)
N(1)ϪMo(2)ϪC(5) 87.9(4))
N(1)ϪMo(2)ϪN(4) 79.0(3)
N(1)ϪMo(2)ϪN(5) 82.8(3)
C(1)ϪN(1)ϪMo(2) 179.4(8)
Figure 2. Thermal ellipsoid (30% probability) plot of the [{Mo(η3-
C3H4-Me-2)(CO)2(phen)}(µ-CN){Mo(η3-C3H5)(CO)2(phen)}]ϩ
cation of 2b, with hydrogen atoms omitted for clarity
py)(NCR)]BArЈ4 (R ϭ Me, Ph),[22] indicating that the cyano
complex is a stronger donor than nitriles. On the other
different metal centers. Treatment of the triflato complex hand, the frequencies corresponding to the cis-Mo(CO)2
[Re(OTf)(CO)3(bipy)] with the salt NaBArЈ4 in the presence fragment are little shifted with respect to those of the mon-
of neutral, two-electron ligands has recently been used to ometallic precursor. Thus, coordination of the cyano nitro-
synthesize [Re(L)(CO)3(bipy)]BArЈ4 compounds.[22] Sim- gen atom to the rhenium atom modifies the electron density
ilarly, [Mo(CN)(η3-C3H5)(CO)2(phen)] (1a) reacted with at the molybdenum center only a little. The presence of the
[M(OTf)(CO)3(bipy)] (M ϭ Mn, Re)[23] and NaBArЈ4 to af- bridging cyano group is shown by the weak CϪN stretches
ford the dimetallic compounds 3 and 4, respectively, as pre- in the IR spectra (2145 cmϪ1 for 3, 2140 cmϪ1 for 4), and
sented in Scheme 3.
by the low-intensity signals in the 13C NMR spectra (δ ϭ
The new compounds 3 and 4 could be isolated as solids 166.6 and 163.8 ppm for 3 and 4, respectively). The close
by filtration, followed by crystallization (see Exp. Sect.). similarity between these 13C NMR chemical shifts and
The simultaneous presence of the molybdenum and the those of the homodimetallic compounds 2a,b is consistent
manganese or rhenium fragments was indicated by the ap- with coordination of the cyano bridge to the molybdenum
pearance of both the bipy and phen signals in a 1:1 ratio in atom through the carbon atom in compounds 3 and 4 (see
1
the H NMR spectra. Accordingly, the IR spectra of 3 and below for carbon coordination to a rhenium atom). Crys-
4, in their ν(CO) regions, show two bands of similar intens- tals of 3 suitable for structural determination by X-ray dif-
ity, attributed to the cis-Mo(CO)2 moiety, and bands similar fraction were obtained, and the results are presented in Fig-
to those of cationic fac-[M(CO)3(bipy)(L)]ϩ (M ϭ Mn, Re) ure 3, Tables 3 and 5. These results confirm the [{Mo(η3-
complexes. For the rhenium compound 4 the latter bands C3H5)(CO)2(phen)}(µ-CN){Mn(CO)3(bipy)}]BArЈ4 formu-
are some 10 cmϪ1 lower than those of [Re(CO)3(bi- lation for 3.
Eur. J. Inorg. Chem. 2003, 1113Ϫ1120
1115

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J. Perez et al.
FULL PAPER
Scheme 3
4, those isomers would feature MoϪN and MϪC (M ϭ
Mn or Re) bonds. As recently pointed out, linkage isomers
of cyano-bridged dimetallic complexes have been isolated
in only a few instances.[24] This prompted us to attempt the
synthesis of the linkage isomers of 3 and 4. The Mo/Mn
complex proved to be labile in solution, and attempts to
isolate it by crystallization afforded crystals of the dimolyb-
denum compound 2a. Therefore, only the Mo/Re complex
is discussed.
The first step, just as in the synthesis of 3 and 4, was to
prepare the mononuclear cyano complexes. [Re(CN)(CO)3(-
bipy)] had previously been synthesized by heating
[ReCl(CO)3(bipy)] at reflux with a 100-fold molar excess of
sodium cyanide in water or an ethanol/water mixture and
subsequent extraction with dichloromethane.[25,26]
We have found that [Re(CN)(CO)3(bipy)] (5) can be con-
veniently prepared by treatment of the labile triflato com-
plex [Re(OTf)(CO)3(bipy)] with tetraethylammonium cyan-
ide. The reaction takes place in dichloromethane within 2 h
at room temperature when 1.2 equiv. of [Et4N]CN is used,
and the IR spectrum of the resulting solution shows only
the bands of [Re(CN)(CO)3(bipy)] (5). The coordinated cy-
ano group appears as a weak signal at δ ϭ 156.1 ppm in
the 13C NMR spectrum. However, the isolated material (see
Exp. Sect.) was contaminated with [Et4N]CN, as indicated
by the 1H NMR spectrum. Since purification of this
mononuclear complex proved difficult, the crude material
was employed for the synthesis of the targeted dimetallic
compound. Thus, by the methodology used for the syn-
thesis of 2, [Re(CN)(CO)3(bipy)] (5) was added to the fil-
tered solution obtained from the reaction between [Mo(η3-
allyl)(OTf)(CO)2(phen)] and NaBArЈ4 in CH2Cl2.
Figure 3. Thermal ellipsoid (30% probability) plot of the [{Mo(η3-
C3H5)(CO)2(phen)}(µ-CN){Mn(CO)3(bipy)}]ϩ cation of 3, with
hydrogen atoms omitted for clarity
3
˚
Table 3. Selected bond lengths [A] and angles [°] for the [{Mo(η -
C3H5)(CO)2(phen)}(µ-CN){Mn(CO)3(bipy)}]ϩ cation of 3
Mn(1)ϪN(1)
Mo(1)ϪC(1)
C(1)ϪN(1)
Mn(1)ϪC(8)
Mn(1)ϪC(7)
Mn(1)ϪC(9)
Mn(1)ϪN(5)
Mn(1)ϪN(4)
2.008(4) Mo(1)ϪC(6)
2.161(5) Mo(1)ϪC(5)
1.148(6) Mo(1)ϪN(2)
1.812(6) Mo(1)ϪN(3)
1.809(7) Mo(1)ϪC(2)
1.797(8) Mo(1)ϪC(3)
2.051(5) Mo(1)ϪC(4)
2.051(4)
1.956(7)
1.943(7)
2.255(4)
2.246(4)
2.347(6)
2.230(5)
2.336(6)
N(1)ϪC(1)ϪMo(1) 179.9(7)
C(1)ϪN(1)ϪMn(1) 170.5(4)
C(8)ϪMn(1)ϪN(1) 174.2(2)
C(6)ϪMo(1)ϪC(1) 86.8(2)
The formation of the dimetallic compound [{Mo(η3-
allyl)(CO)2(phen)}(µ-NC){Re(CO)3(bipy)}]BArЈ4 (6), de-
picted in Scheme 4, was instantaneous, as indicated by IR
monitoring, and the product could be purified and isolated
by crystallization and characterized by spectroscopy and
single-crystal X-ray diffraction. The cyano ligand of 6 gives
rise to a signal at δ ϭ 155.1 ppm in the 13C NMR spectrum.
This value, very close to that found for the mononuclear
complex 5, strongly supports C-coordination to Re in 6 (see
C(5)ϪMo(1)ϪC(1) 86.8(2)
C(1)ϪMo(1)ϪN(3) 83.31(16)
C(1)ϪMo(1)ϪN(2) 82.72(16)
N(3)ϪMo(1)ϪN(2) 73.20(16)
C(7)ϪMn(1)ϪN(1)
C(9)ϪMn(1)ϪN(1)
N(5)ϪMn(1)ϪN(4)
93.2(2)
93.4(2)
78.65(18)
Given the asymmetric nature of the cyano bridge (i.e.,
one metal atom is bound to a carbon and the other to a
nitrogen atom), heterodimetallic cyano-bridged complexes above for the chemical shifts values found for the CϪMo
such as 3 and 4 have linkage isomers. For complexes 3 and isomer). The results of the structural determination of the
1116
Eur. J. Inorg. Chem. 2003, 1113Ϫ1120

Mono- and Dimetallic Cyano Complexes with {Mo(η3-allyl)(CO)2(NϪN)} Fragments
FULL PAPER
Scheme 4
cation are displayed in Figure 4, Tables 4 and 5. The cat-
Conclusion
ionic complex consists of a cyano bridge N-bonded to the
molybdenum of an {Mo(η3-allyl)(CO)2(phen)} fragment,
and C-bonded to the rhenium atom of a {Re(CO)3(bipy)}
fragment.
In summary, [Mo(CN)(η3-allyl)(CO)2(phen)] complexes
were easily synthesized and employed as building blocks for
the preparation of cationic homo- and heterodimetallic cy-
ano-bridged complexes by treatment with neutral triflato
complexes in the presence of the salt NaBArЈ4 as triflate
abstractor. This strategy was extended to prepare the two
linkage
isomers
of
[{Mo(η3-allyl)(CO)2(phen)}(µ-
NC){Re(CO)3(bipy)}]BArЈ4.
Experimental Section
General Remarks: All manipulations were carried out under nitro-
gen by standard Schlenk techniques. Solvents were distilled from
freshly wired Na (hexanes) or CaH2 (CH2Cl2 and MeOH) prior to
use. CD2Cl2 was degassed by three freeze-pump-thaw cycles, dried
˚
with molecular sieves (4 A), and stored in the dark in a Young
tube. Elemental analyses were obtained with a PerkinϪElmer 240-
B microanalyzer. The IR and NMR spectra were recorded with
PerkinϪElmer FT 1720-X and Bruker AC 200 or AC 300 spectro-
meters, respectively. [MoCl(η3-C3H5)(CO)2(phen)],[12] [MoCl(η3-
C3H4-2-Me)(CO)2(phen)],[27] [Mo(OTf)(η3-C3H5)(CO)2(phen)],[20]
[M(OTf)(CO)3(bipy)] (M ϭ Mn, Re),[23] and NaBArЈ4 [19] were pre-
pared according to literature procedures. All other chemicals were
used as received from commercial sources. Hs and Ha designate the
syn- and anti-H atoms, respectively, of the allyl and methallyl li-
gands; Hc is the central H atom of the allyl ligand. The atom-
labeling scheme for the allyl, 1,10- phenanthroline, and BArЈ4
groups is shown below.
Figure 4. Thermal ellipsoid (30% probability) plot of the [{Mo(η3-
C3H5)(CO)2(phen)}(µ-NC){Re(CO)3(bipy)}]ϩ cation of 6, with hy-
drogen atoms omitted for clarity
3
˚
Table 4. Selected bond lengths [A] and angles [°] for the [{Mo(η -
C3H5)(CO)2(phen)}(µ-NC){Re(CO)3(bipy)}]ϩ cation of 6
Mo(1)ϪN(1)
Re(1)ϪC(1)
C(1)ϪN(1)
Re(1)ϪC(2)
Re(1)ϪC(3)
Re(1)ϪC(4)
Re(1)ϪN(2)
Re(1)ϪN(3)
2.151(7) Mo(1)ϪC(5)
2.123(8) Mo(1)ϪC(6)
1.143(9) Mo(1)ϪN(4)
1.928(8) Mo(1)ϪN(5)
1.948(9) Mo(1)ϪC(7)
1.889(10) Mo(1)ϪC(8)
2.162(6) Mo(1)ϪC(9)
2.155(7)
1.916(13)
1.961(13)
2.257(7)
2.228(8)
2.350(11)
2.227(9)
2.329(12)
N(1)ϪC(1)ϪRe(1) 174.8(6)
C(1)ϪN(1)ϪMo(1) 176.9(6)
C(2)ϪRe(1)ϪC(1) 174.5(3)
C(5)ϪMo(1)ϪN(1) 89.4(4)
C(6)ϪMo(1)ϪN(1) 88.5(3)
N(4)ϪMo(1)ϪN(1) 82.0(2)
N(5)ϪMo(1)ϪN(1) 80.0(2)
N(4)ϪMo(1)ϪN(5) 73.9(3)
C(3)ϪRe(1)ϪC(1)
C(4)ϪRe(1)ϪC(1)
N(2)ϪRe(1)ϪN(3)
94.0(3)
91.1(3)
74.9(2)
As in the isomer 4, the IR spectrum of 6 shows sets of
bands attributable to cis-{Mo(CO)2} and fac-{Re(CO)3},
together with a weak νCN absorption at a higher frequency
(2143 cmϪ1) than that of the starting monometallic cyano
complex (2122 cmϪ1).
[Mo(CN)(η3-C3H5)(CO)2(phen)] (1a): NaCN (0.013 g, 0.294 mmol)
was added to a solution of [MoCl(η3-C3H5)(CO)2(phen)] (0.100 g,
0.245 mmol) in a mixture of CH2Cl2 (20 mL) and MeOH (3 mL),
and the mixture was stirred for 2 h at room temperature. The red
solution obtained was concentrated in vacuo, and the residue was
Eur. J. Inorg. Chem. 2003, 1113Ϫ1120
1117

´
J. Perez et al.
FULL PAPER
Table 5. Crystal data and refinement details for complexes 1a, 2b, 3, and 6
1a
2b
3
6
Empirical formula
C18H13MoN3O2·
CH2Cl2
484.18
orthorhombic
Pbca
14.5230(10)
12.5750(10)
21.0800(10)
90
3849.8(4)
8
C68H40BF24Mo2N5O4·
0.25CH2Cl2
1670.47
monoclinic
P21/c
12.6202(19)
18241(3)
31.537(5)
100.241(3)
7144.2(19)
4
C64H35BF24MnMoN5O5·
CH2Cl2
1642.56
monoclinic
P21/c
17.9066(12)
20.2195(14)
19.5450(13)
105.8300(10)
6808.1(8)
4
C64H35BCl2F24MoN5O5Re·
CH2Cl2
1773.82
monoclinic
P21/c
18.3397(18)
20.457(2)
18.6142(18)
97.957(2)
6916.4(12)
4
Molecular mass
Crystal system
Space group
˚
a [A]
˚
b [A]
˚
c [A]
β [°]
V [A ]
3
˚
Z
T [K]
293(2)
1.671
1936
1.54184
295(2)
1.553
3320
0.71073
297(2)
1.603
3264
0.71073
299(2)
1.703
3464
0.71073
Dc [g cmϪ3
F(000)
]
˚
λ(Mo-Kα) [A]
Crystal size [mm]
0.19 ϫ 0.13 ϫ 0.06
0.483
0.14 ϫ 0.20 ϫ 0.34
0.566
0.09 ϫ 0.14 ϫ 0.24
2.123
µ [mmϪ1
]
8.297
Scan range [°]
5.10 to 68.17
4259
2782
1.29 to 23.33
31565
10321
1.18 to 23.29
43929
9791
1.12 to 23.33
30961
9984
No. of reflections measured
No. of ind. reflections
No. of data/
2782/0/298
10321/0/960
9791/ 0/925
9984/ 0/298
restraints/parameters
Goodness-of-fit on F2
R1/Rw2 [I Ͼ 2σ(I)]
R1/Rw2 (all data)
1.002
0.0533/0.1258
0.0697/0.1312
1.013
0.0686/0.1571
0.1436/0.1780
1.028
0.0602/0.1646
0.0759/0.1840
1.019
0.0489/0.1184
0.0822/0.1353
redissolved in CH2Cl2 and filtered through Celite. The volatiles
were removed in vacuo, and the residue was washed with hexane (3
ϫ 10 mL). Slow diffusion of hexane into a solution of [Mo(CN)(η3-
found C 48.93, H 2.38, N 4.34. IR (CH2Cl2): ν˜ ϭ 2129 (νCϵN),
1
1958, 1878 (νCO) cmϪ1. H NMR (CD2Cl2): δ ϭ 8.75, 8.59, 8.46,
7.96, 7.95 and 7.68 (m, 16 H, 2 ϫ phen), 7.78 (m, 8 H, Co-H), 7.58
C3H5)(CO)2(phen)] (1a) in CH2Cl2 (15 mL) at room temperature (m, 4 H, Cp-H), 3.27 (d, JHs,c ϭ 6.4 Hz, 2 H, Hs), 3.19 (d, JHs,c
ϭ
produced red crystals of 1a. A single crystal obtained in this way
was used for the X-ray analysis. Yield: 0.088 g, 90%.
C18H13MoN3O2 (399.26): calcd. C 54.15, H 3.28, N 10.52; found
C 54.11, H 3.07, N 10.15. IR (CH2Cl2): ν˜ ϭ 2113 (νCϵN), 1952,
6.4 Hz, 2 H, Hs), 2.87 (m, 2 H, Hc), 1.75 (d, JHa,c ϭ 9.5 Hz, 2 H,
Ha), 1.45 (d, JHa,c ϭ 9.4 Hz, 2 H, Ha) ppm. 13C{1H} NMR
(CD2Cl2): δ ϭ 223.7 and 223.2 (CO), 169.8 (CN), 152.3, 152.1,
144.7, 138.6, 138.3 and 130.3 (phen), 162.1 (q, J ϭ 49.8 Hz, Ci),
135.2 (Co), 129.3 (q, J ϭ 31.4 Hz, Cm), 124.9 (q, J ϭ 272.4 Hz,
CF3), 117.9 (Cp), 79.0 (C-2 of η3-C3H5), 60.2 (C-1 and C-3 of η3-
1
1868 (νCO) cmϪ1. H NMR (CD2Cl2): δ ϭ 9.06 (dd, J2,3-H ϭ J9,8-
ϭ 5.0, J2,4-H ϭ J7,9-H ϭ 1.5 Hz, 2 H, 2,9-H), 8.52 (dd, JH4,3
ϭ
H
JH7,8 ϭ 8.3 Hz, 2 H, 4,7-H), 7.98 (s, 2 H, 5,6-H), 7.81 (dd, 2 H, C3H5), 57.8 (C-1 and C-3 of η3-C3H5) ppm.
3,8-H), 3.35 (d, JHs,c ϭ 6.5, 2 H, Hs), 3.01 (m, 1 H, Hc), 1.83 (d,
[{Mo(η3-C3H4-Me-2)(CO)2(phen)}(µ-CN){Mo(η3-C3H5)(CO)2-
(phen)}]BArЈ4 (2b): The procedure was similar to that described
above for the preparation of 2a, starting from [Mo(CN)(η3-2-
MeC3H4)(CO)2(phen)] (1b, 0.047 g, 0.115 mmol), [Mo(OTf)(η3-
JHa,c ϭ 9.8 Hz, 2 H, Ha) ppm.
[Mo(CN)(η3-2-MeC3H4)(CO)2(phen)] (1b): The procedure was sim-
ilar to that described above for the preparation of 1a, starting from
[MoCl(η3-2-MeC3H4)(CO)2(phen)] (0.100 g, 0.237 mmol) and C3H5)(CO)2(phen)] (0.060 g, 0.115 mmol) and NaBArЈ4 (0.102 g,
NaCN (0.014 g, 0.284 mmol). Yield: 0.090 g, 92%. C19H15MoN3O2 0.115 mmol) to give complex 2b. Yield: 0.143 g, 79%.
(413.28): calcd. C 55.22, H 3.66, N 10.17; found C 55.01, H 3.34,
N 10.38. IR (CH2Cl2): ν˜ ϭ 2112 (νCϵN), 1950, 1870 (νCO) cmϪ1
1H NMR (CD2Cl2): δ ϭ 9.02 (dd, J2,3-H ϭ J9,8-H ϭ 5.0, J2,4-H
J7,9-H ϭ 1.3, 2 H, 2,9-H), 8.53 (dd, J4,3-H ϭ J7,8-H ϭ 8.2 Hz, 2 H,
4,7-H), 8.00 (s, 2 H, 5,6-H), 7.83 (dd, 2 H, 3,8-H), 3.10 (s, 2 H,
Hs), 1.81 (s, 2 H, Ha), 0.59 [s, 3 H, η3-C3H4(CH3)] ppm.
C68H40BF24Mo2N5O4 (1649.75): calcd. C 49.51, H 2.44, N 4.24;
found C 49.17, H 2.38, N 4.01. IR (CH2Cl2): ν˜ ϭ 2132 (νCϵN), 1959,
1878 (νCO) cmϪ1. 1H NMR (CD2Cl2): δ ϭ 8.73, 8.54, 8.47, 7.98 and
7.68 (m, 16 H, 2 ϫ phen), 7.74 (m, 8 H, Co-H), 7.56 (m, 4 H, Cp-
H), 3.17 (d, JHs,c ϭ 6.5 Hz, 2 H, Hs), 3.01 (s, 2 H, Hs), 2.99 (d,
JHs,c ϭ 6.7 Hz, 2 H, Hs),1.70 (s, 2 H, Ha), 1.68 (d, JHa,c ϭ 9.2 Hz,
2 H, Ha), 1.42 (d, JHa,c ϭ 9.3 Hz, 2 H, Ha), 0.42 [s, 3 H, C3H4(CH3)]
ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 223.7 and 223.6 (CO), 169.9
(CN), 152.1, 151.9, 144.8, 138.7, 138.1, 130.5, 127.8, 127.7, 125.4,
125.3, 125.2 and 119.5 (2 ϫ phen), 162.1 (q, J ϭ 49.4 Hz, Ci), 135.1
(Co), 129.2 (q, J ϭ 34.2 Hz, Cm), 124.9 (q, J ϭ 272.4 Hz, CF3),
117.8 (Cp), 88.9, 73.6, 71.4, 58.3, 58.1 and 57.7 [C-1, C-2 and C-3 of
η3-C3H5 and η3-C3H4(CH3)], 17.6 [η3- C3H4(CH3)] ppm.
.
ϭ
[{Mo(η3-C3H5)(CO)2(phen)}2(µ-CN)]BArЈ4 (2a): NaBArЈ4 (0.093 g,
0.105 mmol) was added to
a
solution of [Mo(OTf)(η3-
C3H5)(CO)2(phen)] (0.055 g, 0.105 mmol) in CH2Cl2 (20 mL), and
the resulting slurry was stirred for 15 min. The solution was filtered
by cannula into a solution of [Mo(CN)(η3-C3H5)(CO)2(phen)] (1a,
0.038 g, 0.105 mmol) in CH2Cl2 (15 mL) and the deep red solution
obtained was stirred for 2 h. The solution was then concentrated
in vacuo to a volume of 5 mL, and slow diffusion of hexane at
room temperature gave red crystals of 2a. Yield: 0.110 g, 71%.
[{Mo(η3-C3H5)(CO)2(phen)}(µ-CN){Mn(CO)3(bipy)}]BArЈ4
NaBArЈ4 (0.099 g, 0.112 mmol) was added to a solution of
(3):
C67H38BF24Mo2N5O4 (1635.73): calcd. C 49.20, H 2.34, N 4.28; [Mn(OTf)(CO)3(bipy)] (0.050 g, 0.112 mmol) in CH2Cl2 (15 mL)
1118 Eur. J. Inorg. Chem. 2003, 1113Ϫ1120

Mono- and Dimetallic Cyano Complexes with {Mo(η3-allyl)(CO)2(NϪN)} Fragments
FULL PAPER
and the resulting solution was stirred for 15 min at room temper-
ature. The color of the solution turned from yellow to orange. The
solution was filtered by cannula into a solution of [Mo(CN)(η3-
CO, MoϪCO), 193.61 (2 CO, ReϪCO) 191.78 (1 CO, ReϪCO),
162.49 (q, J ϭ 49.9 Hz, Ci), 155.67 (CN), 155.66, 153.35, 152.35,
139.95, 138.98 (bipy and phen), 135.20 (Co), 130.48, 130.40 (bipy
C3H5)(CO)2(phen)] (1a, 0.045 g, 0.112 mmol) in CH2Cl2 (15 mL) and phen), 129.27 (q, J ϭ 31.9 Hz, Cm), 127.92, 127.86, 126.79
and the color of the solution turned bright red. The resulting solu-
tion was concentrated in vacuo to a volume of 5 mL, and slow
diffusion of hexane at Ϫ20 °C gave dark orange crystals of 3. A
single crystal obtained in this way was used for the X-ray analysis.
Yield: 0.105 g, 62%. C63H33BF24MnMoN5O5 (1557.64): calcd. C
48.58, H 2.13, N 4.50; found C 48.78, H 1.98, N 4.85. IR (CH2Cl2):
ν˜ ϭ 2145 (νCϵN), 2042, 1957, 1877 (νCO) cmϪ1. 1H NMR (CD2Cl2):
δ ϭ 8.77, 8.64, 8.45 and 7.94 (m, 2 H each bipy and phen), 7.76
(m, 10 H, Co-H and 4 H, bipy), 7.57 (m, 4 H Cp-H), 7.39 (m, 2 H,
phen), 3.33 (m, 2 H, Hs), 2.96 (m, 1 H, Hc), 1.81 (m, 2 H, Ha) ppm.
13C{1H} NMR (CD2Cl2): δ ϭ 223.9 (2 CO, MoϪCO), 219.4 (2
CO, MnϪCO) 217.1 (1 CO, MnϪCO), 166.6 (CN), 155.4, 153.3,
152.5, 144.9, 139.4, 138.94, 130.4, 127.8, 127.0, 125.3 and 122.6
(bipy and phen), 78.5 (C-1 and C-3 of η3-C3H5), 59.9 (C-2 of η3-
C3H5) ppm.
(bipy and phen), 124.38 (q, J ϭ 272.3 Hz, CF3), 119.57 (phen),
117.91 (Cp), 73.87 (C-1 and C-3 of η3-C3H5), 59.9 (C-2 of η3-
C3H5) ppm.
X؊ray Crystallographic Study:[28] The crystal of 1a was measured
with a Nonius CAD4 diffractometer. Profile analysis was per-
formed on all reflections.[29,30] Symmetry-equivalent and other re-
dundant reflections were averaged, and drift, Lorentz, and polar-
ization corrections were applied. The structure was solved by Pat-
terson methods with DIRDIF-96.[31] Isotropic least-squares refine-
ment was carried out on F2 by use of SHELXL-97.[32] An empirical
absorption correction was applied at this stage, by use of
XABS2.[33] All atoms were located by Fourier synthesis. During the
final stages of the refinement, all positional parameters and the
anisotropic temperature factors of all the non-H atoms were refined
with SHELXL-97.[31] The atoms were isotropically refined. Plots
were made with the EUCLID package.[34] Geometrical calculations
were performed with PARST.[35] Data in common for compounds
2b, 3, and 6: Bruker AXS SMART 1000 CCD diffractometer, ϕ
[{Mo(η3-C3H5)(CO)2(phen)}(µ-CN){Re(CO)3(bipy)}]BArЈ4 (4): The
procedure was similar to that described above for the preparation
of 3, starting from [Re(OTf)(CO)3(bipy)] (0.050 g, 0.087 mmol),
[Mo(CN)(η3-C3H5)(CO)2(phen)] (1a, 0.034 g, 0.087 mmol), and
NaBArЈ4 (0.077 g, 0.087 mmol), to give complex 4 as a microcrys-
talline red powder. Yield: 0.040 g, 69%. C60H28BF24MoN5O5Re
(1647.84): calcd. C 43.73, H 1.71, N 4.25; found C 43.44, H 1.89,
N 4.57. IR (CH2Cl2): ν˜ ϭ 2140 (νCϵN), 2033, 1958, 1930, 1877
˚
and ω scans, Mo-Kα radiation (λ ϭ 0.71073 A), graphite monoch-
romator, T ϭ 295 K. Raw frame data integrated by use of the
SAINT[36] program. Structures were solved by direct methods with
SHELXTL,[37] semiempirical absorption correction with SAD-
ABS.[38] All non-hydrogen atoms were refined anisotropically. Hy-
drogen atoms were set in calculated positions and refined as riding
atoms, with a common thermal parameter. All calculations were
performed with SHELXTL.
1
(νCO) cmϪ1. H NMR (CD2Cl2): δ ϭ 8.76, 8.63 and 8.50 (m, 2 H
each bipy and phen), 8.12 (m, 4 H, bipy), 7.99 (m, 2 H, phen), 7.76
(m, 8 H, Co-H, 2 H, phen and 2 H, bipy), 7.57 (m, 4 H Cp-H), 7.45
(m, 2 H, phen), 3.36 (d, JHs,c ϭ 6.5 Hz, 2 H, Hs), 2.98 (m, 1 H,
Hc), 1.83 (d, JHa,c ϭ 9.2 Hz, 2 H, Ha) ppm. 13C{1H} NMR
(CD2Cl2): δ ϭ 225.3 (2 CO, MoϪCO), 196.1 (2 CO, ReϪCO),
189.8 (1 CO, ReϪCO), 163.8 (CN), 157.7, 155.2, 154.5, 146.9,
142.3, 140.6, 132.6, 129.9, 128.7, 127.4 and 119.9 (bipy and phen),
81.0 (C-1 and C-3 of η3-C3H5), 62.5 (C-2 of η3-C3H5) ppm.
Acknowledgments
´
We thank the Ministerio de Ciencia y Tecnologıa (Projects MCT-
00-BQU-0220 and BQU2002-03414) and FICYT (PR-01-GE-7) for
support, and predoctoral scholarships (to E. H. and L. R.).
[Re(CN)(CO)3(bipy)] (5): NEt4CN (0.016 g, 0.104 mmol) was ad-
ded to a solution of [Re(OTf)(CO)3(bipy)] (0.050 g, 0.087 mmol) in
CH2Cl2 (20 mL), the mixture was stirred for 2 h at room temper-
ature, and the color of the solution turned from yellow to orange.
The volatiles were removed in vacuo and the residue was washed
with Et2O (3 ϫ 15 mL). IR (CH2Cl2): ν˜ ϭ 2122 (νCϵN), 2023, 1920
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(νCO) cmϪ1. H NMR (CD2Cl2): δ ϭ 9.02, 8.36, 8.14 and 7.56 (2
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53.86 (CH2, Et4N), 7.11 (CH3, Et4N) ppm.
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[{Mo(η3-C3H5)(CO)2(phen)}(µ-NC){Re(CO)3(bipy)}]BArЈ4 (6): Na-
[7]
´
´
´
J. Perez, L. Riera, V. Riera, S. Garcıa-Granda, E. Garcıa-Rod-
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a solution of
´
rıguez, J. Am. Chem. Soc. 2001, 123, 7469Ϫ7470.
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tion was filtered by cannula into a solution of [Re(CN)(CO)3(bipy)]
(5, 0.047 g, 0.105 mmol) in CH2Cl2 (15 mL), and the deep red solu-
tion obtained was stirred for 2 h. The solution was then concen-
trated in vacuo to a volume of 5 mL, and slow diffusion of hexane
at room temperature gave red crystals of 6. Yield: 0.151 g, 87%.
C60H28BF24MoN5O5Re (1647.84): calcd. C 43.73, H 1.71, N 4.25;
found C 43.61, H 2.03, N 4.17. IR (CH2Cl2): ν˜ ϭ 2143 (νCϵN),
[8]
[9]
´
´
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J. Perez, L. Riera, V. Riera, S. Garcıa-Granda, E. Garcıa-Rod-
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1
2030, 1947, 1926, 1875 (νCO) cmϪ1. H NMR (CD2Cl2): δ ϭ 8.89,
8.49, 8.15, 8.06 and 7.37 (m, 32 H, bipy, phen and BArЈ4), 3.26 (d,
J
Hs,c ϭ 6.0 Hz, 2 H, Hs), 2.70 (m, 1 H, Hc), 1.51 (d, JHa,c ϭ 9.3 Hz,
2 H, Ha) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 225.75 and 224.15 (2
Eur. J. Inorg. Chem. 2003, 1113Ϫ1120
1119

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J. Perez et al.
FULL PAPER
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1995, 38, 79Ϫ154.
´
E. Hevia, J. Perez, V. Riera, D. Miguel, A. Rheingold, S. Kas-
sel, Inorg. Chem. 2002, 41, 4673Ϫ4679.
Triflato complexes of this kind have been previously prepared.
See for instance: J. Guerrero, O. E. Pino, E. Wolcan, M. R.
Feliz, G. Ferraudi, S. A. Moya, Organometallics 2001, 20,
2842Ϫ2853. See also ref.[9]
A. L. Spek, ‘‘The EUCLID package’’, in: Computational Crys-
tallography (Ed.: D. Sayre), Clerendon Press, Oxford, 1982, p.
528.
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M. Nardelli, Comput. Chem. 1983, 7, 95.
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[25]
[26]
G. A. Stark, A. M. Arif, J. A. Gladysz, Organometallics 1997,
16, 2909Ϫ2918.
SAINTϩ SAX area detector integration program, version 6.02,
Bruker AXS, Inc., Madison, WI, 1999.
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R. M. Leasure, L. Sacksteder, D. Nesselrodt, G. A. Reitz, J. N.
Demas, B. A. DeGraff, Inorg. Chem. 1991, 30, 3722Ϫ3728.
The related [Mn(CN)(CO)3(dppe)] complex was prepared by
reaction of aqueous NaCN with [Mn(CO)3(dppe)(OH2)]BF4
[dppe ϭ 1,2-bis(diphenyphosphanyl)ethane]: S. K. Mandal, D.
M. Ho, M. Orchin, Inorg. Chem. 1991, 30, 2244Ϫ2248.
P. Powell, J. Organomet. Chem. 1977, 129, 175Ϫ179.
G. M. Sheldrick, SHELXTL, An integrated system for solving,
refining, and displaying crystal structures from diffraction data,
version 5.1, Bruker AXS, Inc., Madison, WI, 1998.
G. M. Sheldrick, SADABS, Empirical Absorption Correction
Program, University of Göttingen, Göttingen, Germany, 1997.
Received September 17, 2002
[27]
[I02524]
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