1,3,5-Tris(thiocyanatomethyl)mesitylene as a Ligand. Pseudooctahedral molybdenum, manganese, and rhenium carbonyl complexes and copper and silver dimers. Copper-catalyzed carbene- and nitrene-transfer reactions

Article abstract of DOI:10.1021/ic1006082

New molybdenum(0), molybdenum(II), manganese(I), rhenium(I), silver(I), and copper(I) complexes with the 1,3,5-tris(thiocyanatomethyl)mesitylene [Ms(CH₂SCN)₃] ligand have been synthesized and characterized by IR, NMR, and by X-ray diffraction (except for the rhenium complex). The Ms(CH₂SCN)₃ ligand coordinated with the molybdenum, manganese, and rhenium carbonyl fragments as a tripodal chelate. With copper and silver, dimeric dicationic species were obtained instead, with the Ms(CH₂SCN)₃ ligand acting simultaneously as a bidentate chelate and bridge. The [{Cu(Ms(CH₂SCN)₃)} ₂][BAr′₄]₂ (BAr′₄ = tetra(3,5-bis(trifluoromethyl)phenyl)borate) product is an excellent catalyst for cyclopropanation and aziridination of alkenes and cyclopropenation of alkynes by means of carbene- and nitrene-transfer reactions.

Full text of DOI:10.1021/ic1006082

6974 Inorg. Chem. 2010, 49, 6974–6985
DOI: 10.1021/ic1006082
1,3,5-Tris(thiocyanatomethyl)mesitylene as a Ligand. Pseudooctahedral
Molybdenum, Manganese, and Rhenium Carbonyl Complexes and Copper
and Silver Dimers. Copper-Catalyzed Carbene- and Nitrene-Transfer Reactions
†
,†
,†
†
‡
ꢀ
ꢀ
´
´
Hector Martınez-Garcıa, Dolores Morales,* Julio Perez,* Marcos Puerto, and Daniel Miguel
†
´
ꢀ
ꢀ
´
Departamento de Quımica Organica e Inorganica-IUQOEM, Facultad de Quımica, Universidad de
‡
ꢀ
´
´
ꢀ
Oviedo-CSIC, C/Julian Claverıa No. 8, 33006 Oviedo, Spain, and IU CINQUIMA/Quımica Inorganica,
Facultad de Ciencias, Universidad de Valladolid, Campus Miguel Delibes, 47005 Valladolid, Spain
Received March 31, 2010
New molybdenum(0), molybdenum(II), manganese(I), rhenium(I), silver(I), and copper(I) complexes with the 1,3,5-
tris(thiocyanatomethyl)mesitylene [Ms(CH2SCN)3] ligand have been synthesized and characterized by IR, NMR, and
by X-ray diffraction (except for the rhenium complex). The Ms(CH2SCN)3 ligand coordinated with the molybdenum,
manganese, and rhenium carbonyl fragments as a tripodal chelate. With copper and silver, dimeric dicationic species
were obtained instead, with the Ms(CH2SCN)3 ligand acting simultaneously as a bidentate chelate and bridge. The
[{Cu(Ms(CH2SCN)3)}2][BAr04]2 (BAr04 = tetra(3,5-bis(trifluoromethyl)phenyl)borate) product is an excellent catalyst
for cyclopropanation and aziridination of alkenes and cyclopropenation of alkynes by means of carbene- and nitrene-
transfer reactions.
Introduction
that one of these ligands can adopt different coordination
modes depending on the nature of the metal center to which it
is coordinated increases when the donor groups are linked to
the bridgehead group through flexible spacers such as
methylene groups. Molecules containing 1,3,5-trimethylben-
zene bridgehead groups have been used as ligands and as
supramolecular hosts (podands).2 Using these compounds as
ligands often produces bi- or tridimensional networks in which
the ligand bridges several metal centers.3 For the Ms(CH2SCN)3
ligand, conformational flexibility (see Scheme 1) is expected. The
preparation of 1,3,5-tris(thiocyanatomethyl)mesitylene [Ms-
(CH2SCN)3] was reported by Suzuki et al. in 1979.4 No
further chemistry of this compound has been reported since
then. We have investigated its properties as a ligand toward
midtransition, carbonyl metal centers with a strong prefer-
ence for a pseudooctahedral geometry and toward coordina-
tively more flexible copper(I) and silver(I) centers. For the
copper(I) derivative, the catalytic activity in carbene- and
nitrene-transfer reactions was also investigated. Our findings
are discussed in this paper.
Tripodal nitrogen-donor ligands such as the anionic tris-
(pyrazolyl)borates or the neutral tris(pyrazolyl)alkanes have
been extensively employed in coordination chemistry and
catalysis.1 When these and related ligands act as ligands, the
formation of six-membered rings strongly favors coordina-
tion to a single metal center as tripodal tridentates. When the
donor groups of polydentate ligands are held together by a
polyatomic fragment, instead of by a single bridgehead atom,
other coordination modes can become favorable. The possibility
*To whom correspondence should be addressed. E-mail: japm@uniovi.es
(J.P.), moralesdolores.uo@uniovi.es (D.M.).
(1) (a) Chaudhuri, P.; Kataev, V.; Buchner, B.; Klauss, H.-H.; Kersting,
€
B.; Meyer, F. Coord. Chem. Rev. 2009, 253, 2261. (b) Pettinari, C. Scorpionates
II: Chelating Borate Ligands; World Scientific Publishing: New York, 2008.
(c) Dias, H. V. R.; Lovely, C. J. Chem. Rev. 2008, 108, 3223. (d) Edelmann, F. T.
Angew. Chem., Int. Ed. 2001, 40, 1656. (e) Trofimenko, S. Scorpionates, The
Coordination Chemistry of Polypyrazolylborate Ligands; Imperial College
Press: London, 1999. (f) Reger, D. L. Comments Inorg. Chem. 1999, 21, 1.
(g) Kitajima, N.; Tolman, W. B. Prog. Inorg. Chem. 1995, 43, 419. (h) Trofimenko,
S. Chem. Rev. 1993, 93, 943. (i) Reger, D. L. Synlett 1992, 469.
(2) (a) Wiskur, S. L.; Ait-Haddou, H.; Lavigne, J. J.; Anslyn, E. V. Acc.
Chem. Res. 2001, 34, 963. (b) Cabell, L. A.; Best, M. D.; Lavigne, J. J.;
Schneider, S. E.; Perreault, D. M.; Monahan, M.-K.; Anslyn, E. V. J. Chem. Soc.,
Perkin Trans. 2001, 2, 315. (c) Yun, S.; Ihm, H.; Kim, H. G.; Lee, C.-W; Indrajit,
B.; Oh, K. S.; Gong, Y. L.; Lee, J. W.; Yoon, J.; Lee, H. C.; Kim, K. S. J. Org.
Chem. 2003, 68, 2467. (d) Amendola, V.; Boiocchi, M.; Fabbrizzi, L.; Palchetti,
A. Chem.;Eur. J. 2005, 11, 5648. (e) Kim, J.; Kim, S.-G; Seong, H. R.; Ahn,
K. H. J. Org. Chem. 2005, 70, 7227. (f) Amendola, V.; Boiocchi, M.; Colasson,
B.; Fabbrizzi, L.; Rodriguez Douton, M.-J.; Ugozzoli, F. Angew. Chem., Int. Ed.
2006, 45, 6920. (g) Turner, D. R.; Paterson, M. J.; Steed, J. W. J. Org. Chem.
2006, 71, 1598. (h) Mazik, M. Chem. Soc. Rev. 2009, 38, 935.
Results and Discussion
We have synthesized the Ms(CH2SCN)3 compound by a
slight modification of the method reported by Suzuki et al.,4
(3) Fan, J.; Sun, W. Y.; Okamura, T.; Tang, W. X.; Ueyama, N. Inorg.
Chem. 2003, 42, 3168.
(4) Suzuki, H.; Usuki, M.; Hanafusa, T. Bull. Chem. Soc. Jpn. 1979,
52, 836.
r
pubs.acs.org/IC
Published on Web 07/06/2010
2010 American Chemical Society

Article
Inorganic Chemistry, Vol. 49, No. 15, 2010 6975
Scheme 1. “Three-Up” and “Two-Up, One-Down” Conformers of
Ms(CH2SCN)3
donor than theset of three acetonitriles. This suggests that the
higher electronegativity of the SR vis-a-vis the CH3 group
predominates over the electron delocalization of the sulfur
lone pairs shown in Figure 2; i.e., the inductive effect pre-
dominates over the mesomeric effect. A single, weak νCN band
is observed for each complex. In 2-4, this band occurs at
higher frequencies than that in free Ms(CH2SCN)3 (2154 and
2164 cm-1 in 2, 2196 cm-1 in 3, and 2188 cm-1 in 4), whereas
in 1, it appears at the same frequency as that in Ms(CH2SCN)3.
The shift to higher frequencies of the νCN band of an NCSR
ligand upon coordination, previously observed, has been
attributed to some degree of coupling of the C-N and
N-M stretching modes.6
Scheme 2. Synthesis of Ms(CH2SCN)3
The NMR spectra of complexes 1-4 showed single sets of
signals for the CH2 and CH3 groups, indicating C3 symmetry.
This is the actual symmetry of the instantaneous structure of
the tricarbonyl complexes but not of 2. Several pseudoocta-
hedral [Mo(η3-allyl)(CO)2L3] complexes showed this appar-
ent symmetry insolution because of the operation of dynamic
processes that are fast on the NMR time scale at room
temperature.9 To investigate if this is the case for 2, the
1H NMR spectrum of 2 in CD2Cl2 was recorded at different
temperatures (Figure 3). At room temperature, the Ms-
(CH2SCN)3 ligand featured two broad singlets at 4.49 and
2.49 ppm, corresponding to the CH2 and CH3 groups,
respectively. Below 10 °C, these signals started to split, and
at -20 °C, two distinct singlets for the CH3 groups are
observed at 2.49 and 2.33 ppm, integrating as six and three
hydrogen atoms, respectively. At this temperature, the CH2
groups give rise to a two-hydrogen singlet at 4.42 ppm and
two doublets at 3.39 and 4.21 ppm, integrating as two
hydrogen atoms each. This pattern indicates the presence
of a molecular mirror plane and diastereotopic character of
the hydrogen atoms on two of the CH2 groups. Therefore, an
instantaneous Cs-symmetric solution structure similar to the
one found in the solid state can be assumed for the cationic
complex in 2. The signals corresponding to the allyl group did
not undergo significant changes upon temperature lowering.
From the coalescence temperature (282 K), the free energy
of activation for the dynamic process can be estimated as
employing refluxing isopropyl alcohol (iPrOH; instead of N,
N-dimethylformamide) as the solvent, as shown in Scheme 2.
A high yield was obtained using a reaction time of 3 h and a
stoichiometric amount of potassium thiocyanate (KSCN);
therefore, unlike in the original procedure, we did not find it
necessary to use an excess of KSCN.
In the IR spectrum of Ms(CH2SCN)3 in KBr, three νCN
bands were observed at 2159, 2153, and 2140 cm-1,5 while a
single band at 2154 cm-1 was observed in a CH2Cl2 solution.
In the 1H NMR spectrum, single signals for both theCH2 and
CH3 groups were observed. The results of single-crystal
X-ray diffraction showed that in the solid state the ligand
adopts a “two-up, one-down” conformation (Figure 1).
The N-C-S angles fall between 176.2(4) and 179.0(4)°,
indicating sp hybridization of the central carbon, for which
two resonance forms can be envisaged (Figure 2).
Organometallic Compounds of Molybdenum, Manganese,
and Rhenium
ΔGq = 57 kJ mol-1 10
.
Ms(CH2SCN)3 was allowed to react with stoichiometric
amounts of the labile compounds fac-[Mo(CO)3(NCMe)3],
fac-[Mo(η3-methallyl)(CO)2(NCMe)3][BAr04], fac-[Mn(CO)3-
(NCMe)3][BAr04], and fac-[Re(CO)3(NCMe)3][BAr04].
(6) (a) Quick, M. H.; Angelici, R. J. Inorg. Chem. 1976, 15, 160–164.
(b) Drago, R. S.; Purcell, K. F. J. Am. Chem. Soc. 1966, 88, 919.
ꢀ
(7) Perez, J.; Morales, D.; Nieto, S.; Riera, L.; Riera, V.; Miguel, D.
In each case, a single product was obtained in high yield,
with spectroscopic and analytical data consistent with [Mo-
(CO)3(Ms(CH2SCN)3)] (1), [Mo(η3-methallyl)(CO)2(Ms-
(CH2SCN)3)][BAr04] (2), [Mn(CO)3(Ms(CH2SCN)3)][BAr04]
(3), and [Re(CO)3(Ms(CH2SCN)3)][BAr04] (4) formulation.
For the cationic complexes, the same result was obtained
either from the preformed tris(nitrile) compound or from the
in situ generated compound resulting from the mixing of
equimolar amounts of [MoCl(η3-methallyl)(CO)2(NCMe)2]
or fac-[M(OTf)(CO)3(NCMe)2] (M = Mn, Re) and NaBAr04,
as indicated in Scheme 3 (see also the Experimental Section).
In CH2Cl2 solutions, the average of the νCO bands in the IR
spectra is slightly higher than that of the corresponding
tris(nitrile) precursors (see Table 1 and the Experimental
Section), indicating that the tripodal ligand is slightly less
Dalton Trans. 2005, 884.
(8) For IR(νCO) data of [M(CO)3(NCMe)3]þ (M = Mn, Re) with
different counteranions (OTf, BPh4, and PF6), see:(a) Reimann, R. H.;
Singleton, E. J. Organomet. Chem. 1973, 59, C24. (b) Walker, P. J. C.; Mawby,
R. J. Inorg. Chim. Acta 1973, 7, 621. (c) Kane-Maguire, L. A. P.; Sweigart, D. A.
Inorg. Chem. 1979, 18, 700. (d) Minutolo, F.; Katzenellenbogen, J. A. J. Am.
Chem. Soc. 1998, 120, 4514.
(9) (a) Santa Marıa, M. D.; Claramunt, R. M.; Alkorta, I.; Elguero, J.
´
Dalton Trans. 2007, 3995. (b) Van Staveren, D. R.; Bill, E.; Bothe, E.; Buhl, M.;
Weyhermuller, T.; Metzler-Nolte, N. Chem.;Eur. J. 2002, 8, 1649. (c) Espinet,
P.; Hernando, R.; Iturbe, G.; Villafane, F.; Orpen, A. G.; Pascual, I. Eur. J. Inorg.
Chem. 2000, 1031. (d) Faller, J. W.; Haitko, D. A.; Adams, R. D.; Chodosh, D. F.
J. Am. Chem. Soc. 1979, 101, 865.
(10) Usinga coalescence temperatureof 282K (9 °C) for the δ 2.49 1H NMR
signal [CH3 of the Ms(CH2SCN)3 ligand] and a chemical shift difference
between the CH3a/CH3b of Δν = 66 Hz and ΔGq = 57 kJ mol-1, based on
ΔGq = RTc[22.96 þ ln(Tc/Δν)] (R = 8.31 J K-1). Considering the data of the
couplet diastereotopic CH2 hydrogen atoms of the Ms(CH2SCN)3 ligand, δA
4.38, δB 4.21, and JA-B = 11.1 Hz and applying kc = π[(νA - νB)2 þ 6JAB
2 1/2
] /
2
1/2 and ΔGq = RTc[23.76 - ln(kcoal/Tc)] (R = 8.31 J K-1), the free energy of
(5) Nakamoto, N. Infrared and Raman Spectra of Inorganic and Coordi-
nation Compounds, 5th ed.; John Wiley & Sons, Inc.: New York, 1997;
Part B, p 116.
activation at the coalescence temperature (ΔGq) is 55 kJ mol-1. See: NMR
Spectroscopy, 2nd ed.; G€unther, H., Ed. John Wiley & Sons: West Sussex, England,
1995; pp 343 and 355.

6976 Inorganic Chemistry, Vol. 49, No. 15, 2010
Martınez-Garcıa et al.
Figure 1. Thermal ellipsoid (30%) plot of Ms(CH2SCN)3. The view on the right shows the “two-up, one-down” disposition of the CH2SCN groups.
Selected bond distances (A) and angles (deg): S(1)-C(1) 1.680(5), S(1)-C(11) 1.842(4), S(2)-C(2) 1.676(5), S(2)-C(12) 1.841(4), S(3)-C(3) 1.682(4),
S(3)-C(13) 1.828(4), N(1)-C(1) 1.150(5), N(2)-C(2) 1.139(6), N(3)-C(3) 1.141(5); C(1)-S(1)-C(11) 100.26(19), C(2)-S(2)-C(12) 99.5(2), C(3)-
S(3)-C(13) 99.70(18), N(1)-C(1)-S(1) 176.2(4), N(2)-C(2)-S(2) 178.6(4), N(3)-C(3)-S(3) 179.0(4), C(21)-C(11)-S(1) 114.4(3), C(23)-C(12)-S(2)
114.9(3), C(25)-C(13)-S(3) 109.0(2).
Figure 2. Resonance forms for the RSCN group.
Scheme 3. Synthesis of Carbonyl Compounds of Molybdenum,
Manganese, and Rhenium with the Ms(CH2SCN)3 Ligand
Figure 3. VT 1H NMR of 2 in CD2Cl2.
metal complexes have a pseudooctahedral geometry, with the
ligand Ms(CH2SCN)3 coordinated as fac tridentate through
the nitrogen atoms. The M-N-C angles are close to linear
(average of 177°), indicating the major contribution of the
resonance form a (Figure 2). In 2, the open mouth of the
methallyl group points toward the two cis-carbonyls, the
Table 1. IR νCO (cm-1) in a CH2Cl2 Solution
most energetically favorable arrangement.11 Neither the
[Mo(CO)3(MeCN)3]
1922, 1800
1
2
3
4
1920, 1840
1975, 1904
2066, 1985
2057,1963
angle around the sulfur atom (very close to 100°) nor the
H2C-S, S-C, or C-N distances of the Ms(CH2SCN)3
ligand undergo a significant distortion by coordination to
the metal centers (see Table 2).
[Mo(η3-methallyl)(CO)2(NCMe)3][BAr04]7 1974, 1894
2068, 1978
2055, 1952
[Mn(CO)3(NCMe)3][BAr04]8
[Re(CO)3(NCMe)3][BAr04]8
The solid-state structures of compounds 1-3 were deter-
mined by X-ray crystallography (Figures 4 and 5). The three
(11) Curtis, M. D.; Eisenstein, O. Organometallics 1984, 3, 887.

Article
Inorganic Chemistry, Vol. 49, No. 15, 2010 6977
Figure 4. Thermal ellipsoid plot (30% probability) of 1 (left) and the cation in 2. Selected bond distances (A) and angles (deg) in 1: Mo-N(1) 2.219(4),
Mo-N(2) 2.194(4), Mo-N(3) 2.211(4), Mo-C(1) 1.951(5), Mo-C(2) 1.954(5), Mo-C(3) 1.949(5), N(1)-C(4) 1.155(6), N(2)-C(5) 1.142(6), N(3)-C(6)
1.150(6), S(1)-C(4) 1.662(5), S(2)-C(5) 1.680(5), S(3)-C(6) 1.677(5); C(4)-N(1)-Mo 172.6(4), C(5)-N(2)-Mo 177.6(4), C(6)-N(3)-Mo 172.4(4),
N(2)-Mo-N(3) 82.69(14), N(2)-Mo-N(1) 82.79(14), N(3)-Mo-N(1) 81.17(14), N(1)-C(4)-S(1) 175.2(4), N(2)-C(5)-S(2) 175.8(4), N(3)-C(6)-
S(3) 174.8(4), C(4)-S(1)-C(11) 101.9(2), C(5)-S(2)-C(12) 100.7(2), C(6)-S(3)-C(13) 101.1(2). Those in the cation in 2: Mo-N(1) 2.212(5), Mo-N(2)
2.158(6), Mo-N(3) 2.192(5), Mo-C(6) 2.323(7), Mo-C(7) 2.236(8), Mo-C(8) 2.302(8), Mo-C(1) 1.960(8), Mo-C(2) 1.964(7), N(1)-C(3) 1.129(7),
N(2)-C(4) 1.138(8), N(3)-C(5) 1.131(7), S(1)-C(5) 1.668(6), S(2)-C(3) 1.665(7), S(3)-C(4) 1.656(8); N(2)-Mo-N(1) 80.47(19), N(3)-Mo-N(1)
85.09(19), N(2)-Mo-N(3) 80.73(19), C(2)-Mo-N(2) 90.0(3), C(1)-Mo-C(2) 81.7(3), C(3)-N(1)-Mo 177.2(5), C(4)-N(2)-Mo 178.8(5), C(5)-
N(3)-Mo 173.3(5), N(1)-C(3)-S(2) 178.1(6), N(2)-C(4)-S(3) 176.3(6), N(3)-C(5)-S(1) 177.0(5), C(5)-S(1)-C(11) 100.3(3), C(3)-S(2)-C(12)
101.1(3), C(4)-S(3)-C(13) 102.3(3).
Table 2. Average Bond Distances (A) and C-S-C Angles (deg) of Free and
Complexed Ms(CH2SCN)3
compound
d H C-S (A)
d S-CN (A)
d C-N (A)
.
2
Ms(CH2SCN)3
1.835(4)
1.872(5)
1.839(6)
1.856(8)
1.679(5)
1.671(5)
1.662(8)
1.689(7)
1.140(6)
1.148(6)
1.133(7)
1.145(9)
99.5(2)
100.7(2)
101.1(3)
101.2(3)
1
2
3
(Me3tach = 1,3,5-trimethyl-1,3,5-triazacyclohexane),12 indi-
cating that Ms(CH2SCN)3 is less labile than Me3tach. Never-
theless, 1 reacted with KTp* to instantaneously afford
K[MoTp*(CO)3] [Tp* = hydrotris(3,5-dimethylpyrazolyl)-
borate]13 at room temperature. The neutral ligand 2,20:6,200-
terpyridine (terpy) also displaces Ms(CH2SCN)3 from 1 at
room temperature in CH2Cl2; in this case, IR monitoring of
the reaction indicated the formation of [Mo(CO)4(terpy)]14
as the only CO-containing species in solution. The product of
this reaction, a decomposition as a tetracarbonyl is produced
from a tricarbonyl, is not surprising because [Mo(CO)4-
(terpy)] is also the product of the reaction of terpy with
[Mo(CO)6].14
When the equimolar amount of iodine was added to a
dichloromethane solution of 1, a large shift to higher wave-
number values of the νCO bands in the IR spectrum occurred,
indicating the oxidation of molybdenum. The νCO bands
(2034vs, 1966s, and 1943sh cm-1) of the product are very
close to those of the previously known complex [MoI2-
(NCMe)2(CO)3] (2038, 1968, and 1940 cm-1), the product
of the reaction of [Mo(NCMe)3(CO)3] with iodine.15 The 1H
NMR spectrum of the product (the reaction crude when the
Figure 5. Representative ORTEP (50% probability) of 6. Selected bond
distances (A) and angles (deg): Mo-I(1) 2.8280(7), Mo-I(2) 2.8786(7),
N(1)-Mo 2.187(3), N(2)-Mo 2.183(6), C(1)-Mo 1.998(7), C(2)-Mo
1.983(9), C(3)-Mo 2.005(8), C(4)-N(1) 1.146(11), C(4)-S(1) 1.658(8),
C(5)-N(2) 1.162(11), C(5)-S(2) 1.674(8), C(13)-I(3) 2.181(8); N(1)-
C(4)-S(1) 174.5(7), N(2)-Mo-N(1) 83.2(2), I(1)-Mo-I(2) 160.94(3),
C(4)-N(1)-Mo 169.3(7), C(5)-N(2)-Mo 174.6(6), N(2)-C(5)-S(2)
175.1(7), C(21)-C(11)-S(1) 115.7(5), C(4)-S(1)-C(11) 103.2(4),
C(5)-S(2)-C(12) 101.9(4).
(12) Baker, M. V.; North, M. R. J. Organomet. Chem. 1998, 565, 225.
(13) Trofimenko, S. J. Am. Chem. Soc. 1969, 91, 588.
(14) Ganokar, M. C.; Stiddard, M. H. B. J. Chem. Soc. 1965, 5346–5348.
[Mo(terpy)(CO)4] was first described by: Behrens, H.; Anders, U. Z. Naturforsch.
1964, 19b, 767.
(15) Baker, P. K.; Frases, S. G.; Keys, E. M. J. Organomet. Chem. 1986,
309, 319.
As mentioned above, 1 was synthesized by the reaction of
[Mo(CO)3(NCMe)3] with Ms(CH2SCN)3 in CH2Cl2. Upon
standing in an acetonitrile solution for several hours, 1 did
not regenerate [Mo(CO)3(NCMe)3]. This stands in con-
trast with the behavior reported for [Mo(Me3tach)(CO)3]

6978 Inorganic Chemistry, Vol. 49, No. 15, 2010
Scheme 4. Proposed Oxidative Addition of I2 to 1
Martınez-Garcıa et al.
Scheme 5. Proposed Reaction of 5 with NaBAr04
(2062vs, 2006vs, and 1984 m cm-1), reflecting the formation
of a cationic complex 7. We propose that the third thio-
cyanate group, free in 5, coordinated the metal, substituting
one of the iodide atoms (see Scheme 5) so that Ms(CH2SCN)3
is coordinated in a tripodal fashion in the product 7.
Compound 7 is also fluxional because only single signals
appear for the CH2 (4.48 ppm) and CH3 (2.54 ppm) groups.
The solubility of 7 in organic solvents of moderate polarity (e.g.,
CH2Cl2) is larger than those of 5 and 6, as expected for a BAr04
salt. Its 13C NMR spectrum shows a single CO signal at 225.6
ppm. Lowering the temperature down to -60 °C (below this,
precipitation occurred) only caused a slight broadening of the
signals, a fact that suggests that the dynamic process is still
operative at this temperature. Whereas a CH2Cl2 solution of 7 is
quite stable under a dinitrogen atmosphere, solutions of tetra-
hydrofuran (THF), diethyl ether, or acetone decompose quickly
by a decarbonylation process because the product did not show
reaction was carried out in CD2Cl2 in an NMR tube) showed
itto be a mixture of two compounds, 5 and 6, in a 2:3approxi-
mate ratio. The solubility of both compounds in dichloro-
methane and in most common organic solvents was found to
be low, as is typical of [MoI2(CO)3L2] complexes.16 However,
the higher solubility of 6 in CH2Cl2 made the separation of 5
and 6 possible (see the Experimental Section). The IR νCO
bands of 5 and 6 are identical, reflecting the close similarity
between the sets of ligands in both compounds. The nature of
compound 6 was unambiguously established by a single-
crystal X-ray determination of its structure, the results of
which are shown in Figure 5. The molecule of 6 consists of a
MoI2(CO)3 fragment, similar to the ones encountered in
previously reported [MoI2(CO)3L2] complexes, coordinated
to the nitrogen atoms of the two CH2SCN groups of an iodo-
methylbis(thiocyanatomethyl)mesitylene ligand, formally
resulting from the substitution by iodide of one of the three
1
νCO bands in the IR spectrum.
SCN groups present in the tridentate ligand of 1. The H
NMR spectrum of 6 in CD2Cl2 indicates the presence of a
molecular mirror plane, in accordance with the solid-state
structure. Thus, there are two singlets at 2.53 and 2.46 ppm,
with integrals in a 1:2 ratio, that correspond to the methyl
groups. A two-hydrogen singlet at 4.53 ppm and two doub-
lets (two hydrogen atoms each) at 4.69 and 4.21 ppm are
assigned to the methylene groups. In the molecule repre-
sented in Figure 5, the mirror plane [passing through C(23),
C(26), I(2), Mo, I(1), C(2), and O(2)] would make the two
CH2I hydrogen atoms equivalent, while the two hydrogen
atoms of each CH2SCN group are diastereotopic, in accor-
Copper and Silver Compounds
Copper(8) and silver (9) complexes of Ms(CH2SCN)3 were
prepared by a stoichiometric reaction of the ligand with
CuOTf or AgOTf and NaBAr04, as described in the Experi-
mental Section and shown in Scheme 6.
In each case, a single product is obtained in almost
quantitative yield. The IR spectrum in a CH2Cl2 solution
showed a νCN band at 2174 cm-1 for 8 and at 2168 cm-1 for 9,
which split into two bands in KBr at 2189 and 2144 cm-1 for
8 and at 2191 and 2150 cm-1 for 9.
1
1
dance with the H NMR spectrum described above. In the
The H NMR spectra of 8 and 9 showed a 1:1 ratio of
13C NMR spectrum (CD2Cl2), two different methyl groups
and four different signals for the carbon atoms of the
aromatic ring are observed, in agreement with the solid-state
structure. However, only one signal is observed for the three
carbonyl ligands, and only one signal is seen for the methyl-
ene groups probably because of the operation of a fast dynamic
process, as is commonly encountered in heptacoordinated halo-
carbonyl complexes of molybdenum(II).17
Ms(CH2SCN)3/BAr04. For the Ms(CH2SCN)3 ligand, single
sets of signals for the CH2 and CH3 groups were observed.
The variable-temperature (VT) 1H NMR spectra of 8 showed
that the CH2 and CH3 signals broadened and slightly shifted
upfield when the temperature was raised to 203 K (see the
Supporting Information), but no splitting was observed.
The solid-state structures of 8 and 9 were determined by
single-crystal X-ray diffraction. Each compound is a salt
consisting of a dicationic complex and two BAr04 anions. The
copper and silver dicationic complexes are isostructural, centro-
symmetric [M2{Ms(CH2SCN)3}]2þ dimers (see Figure 6). A
neutral [HBpz3Cu]2 species with a structure similar to that
found in 8 had been previously described by Marks and co-
workers.18 Each dicationic complex consists of two Mþ metal
centers bridged by two Ms(CH2SCN)3 ligands. One NCSR
group of each Ms(CH2SCN)3 ligand acts as a nitrogen bridge
between both metal centers, whereas the other two NCSR
groups act as terminal ligands, one to each metal. As a result,
each metal atom is tetracoordinated. The four atoms of the
On the basis of the similarity between the IR spectra (νCO
region) of 5 and 6 and the 1H NMR spectra discussed below,
the structure depicted in Scheme 4 can be proposed for 5. At
room temperature, the 1H NMR spectrum of 5 in (CD3)2CO
features single, broad signals for the CH2 (4.62 ppm) and
CH3 (2.32 ppm) groups. At 0 °C, the CH2 signal becomes a
multiplet and that of CH3 remains a singlet.
0
The reaction of 5 with an equimolar amount of NaBAr4
led to a large shift to higher frequencies in the νCO bands
(16) (a) Baker, P. K.; Coles, S. J.; Durrant, M. C.; Harris, S. D.; Hughes,
D. L.; Hursthouse, M. B.; Richards, R. L. J. Chem. Soc., Dalton Trans. 1996,
4003. (b) Curtis, M. D.; Shiu, K.-B. Inorg. Chem. 1985, 24, 1213.
(17) (a) Baker, P. K. Chem. Soc. Rev. 1998, 27, 125–131. (b) Baker, P. K.
Adv. Organomet. Chem. 1996, 40, 45–115.
(18) Mealli, C.; Arcus, C. S.; Wilkinson, J. L.; Marks, T. J.; Ibers, J. A.
J. Am. Chem. Soc. 1676, 98, 711.

Article
Inorganic Chemistry, Vol. 49, No. 15, 2010 6979
Figure 6. Thermal ellipsoid (30%) plots of the cations in 8 (a) and 9 (b). Selected bond distances (A) and angles (deg) for the cation in 8: Cu(1)-N(1)
1.896(4), Cu(1)-N(2) 1.911(4), Cu(1)-N(3) 2.158(4), Cu(1)-N(3) 12.275(4), S(1)-C(1) 1.669(5), S(1)-C(101a) 1.854(5), C(1)-N(1) 1.151(6), S(2)-C(2)
1.675(5), C(2)-N(2) 1.139(6), S(3)-C(3) 1.647(4) C(3)-N(3) 1.139(5), N(3)-Cu(1a) 2.275(4); N(1)-Cu(1)-N(2) 136.47(19), N(1)-Cu(1)-N(3)
108.52(17), N(2)-Cu(1)-N(3) 102.23(15), N(1)-Cu(1)-N(3a) 100.83(15), N(2)-Cu(1)-N(3a) 105.17(16), N(3)-Cu(1)-N(3a) 97.11(13), N(1)-
Cu(1)-Cu(1a) 112.28(14), N(2)-Cu(1)-Cu(1a) 111.01(13), N(3)-Cu(1)-Cu(1a) 50.27(11), N(3a)-Cu(1)-Cu(1a) 46.84(10), C(1)-S(1)-C(101a)
100.3(2), N(1)-C(1)-S(1) 177.9(5), C(1)-N(1)-Cu(1) 176.3(5), C(2)-S(2)-C(102) 100.8(2), N(2)-C(2)-S(2) 177.3(4), C(2)-N(2)-Cu(1) 175.7(4).
Selected bond distances (A) and angles (deg) for the cation in 9: Ag(1)-N(1) 2.490(5), Ag(1)-N(1a) 2.525(5), Ag(1)-N(2) 2.155(5), Ag(1)-N(3a) 2.153(5),
C(3)-N(3) 1.135(8), C(2)-N(2) 1.130(7), C(1)-N(1) 1.132(7), C(2)-S(2) 1.682(6), C(3)-S(3) 1.675(6), C(1)-S(1) 1.659(5); N(3A)-Ag(1)-N(2) 145.8(2),
N(3A)-Ag(1)-N(1) 110.8(2), N(2)-Ag(1)-N(1) 93.50(17), N(3A)-Ag(1)-N(1A) 95.64(18), N(2)-Ag(1)-N(1A) 108.13(18), N(1)-Ag(1)-N(1A)
90.78(15), C(1)-N(1)-Ag(1) 141.3(5), C(1)-N(1)-Ag(1A) 129.4(5), Ag(1)-N(1)-Ag(1A) 89.22(15), C(2)-N(2)-Ag(1) 176.6(5), C(3)-N(3)-Ag(1A)
174.8(6), N(1)-C(1)-S(1) 175.9(5), N(2)-C(2)-S(2) 176.6(5), N(3)-C(3)-S(3) 178.9(6), C(1)-S(1)-C(10) 103.1(2), C(2)-S(2)-C(20) 100.4(2),
C(3)-S(3)-C(30) 100.2(3).
Scheme 6. Synthesis of 8 and 9
M2N2bridge unit are in a plane, with an almost ideal square
geometry in 9 [Ag-N-Ag 89.2(1) and N-Ag-N 90.8(1)°],
while 8 shows a significant rhombic distortion [Cu-N-Cu
82.9(1) and N-Cu-N 97.5(1)°]. For the terminal NCSR
groups, the N-M-N angles are wider than those of the
bridging groups [136.5(5)° in 8 and 145.8(2)° in 9]. The
distances M-Nterminal [1.894(4) and 1.911(4) A in 8 and
2.155(5) and 2.153(5) A in 9] are shorter than M-Nbridge
[2.158(4) and 2.275(4) A in 6 and 2.490(5) and 2.525(5) A in 9].
The Ag-Nbridge bond lengths are slightly longer than those in
the only known silver complex with a nitrile bridge (2.383(4)
and 2.467(4) A),19 as expected because in that case each silver
atom is tricoordinated, whereas in 9, it is tetracoordinated.
The Cu-Nterminal distances in 8 [1.894(4) and 1.911(4) A]
are only slightly longer than those found in tetracoordinated
copper(I) complexes with the anionic N-thiocyanate ligand
(1.841-1.985 A)20 and shorter than typical CuI-N(nitrile)
distances.21 As discussed above, 8 has two NCSR groups
acting as bridges between the copper atoms; to the best of our
knowledge, there are no examples of a nitrile nitrogen bridge
between two copper atoms and only a few examples with
other metals.20,22 The bridging coordination of one of the
NCS groups in 8 and 9 suggests a significant contribution of
the resonance form depicted in Figure 2b in the copper and
silver complexes. The N-C [average of 1.135(7) A in 9 and
1.143(6) A in 8] and C-S [average of 1.663(5) A in 9 and
1.663(6) A in 8] bond lengths are similar to the distances
(21) The Cambridge Structural Database (2007) gives a copper-nitrile
distance average of 2.040 A. In the compound [Cu(NCMe)4][B(C6F5)4], the
copper-nitrile distances are between 2.000(2) and 2.029(2) A. See: Zhang,
€
Y.; Sun, W.; Freund, C.; Santos, A. M.; Herdtweck, E.; Mink, J.; Kuhn, F. E.
Inorg. Chim. Acta 2006, 359, 4723.
(22) (a) Lin, P.; Clegg, W.; Harrington, R. W.; Henderson, R. A. Dalton
Trans. 2005, 2349. (b) Franceschi, F.; Solari, E.; Scopelliti, R.; Floriani, C.
Angew. Chem., Int. Ed. 2000, 39, 1685. (c) Evans, W. J.; Greci, M. A.; Ziller,
J. W. Chem. Commun. 1998, 2367. For a nitrogen-bridging thiocyanate ligand
between two metal atoms, see: Kapoor, R.; Kataria, A.; Pathak, A.; Venugopalan,
P.; Hundal, G.; Kapoor, P. Polyhedron 2005, 224, 1221 and references therein.
(19) Al-Mandhary, M. R. A.; Fitchett, C. M.; Steel, P. J. Aust. J. Chem.
2006, 59, 307.
(20) Kabesova, M.; Boca, R.; Melnik, M.; Valigura, D.; Dunaj-Jurco, M.
Coord. Chem. Rev. 1995, 140, 115.

6980 Inorganic Chemistry, Vol. 49, No. 15, 2010
Martınez-Garcıa et al.
found in complexes of the anionic thiocyanate ligand.23
In each complex, the N-C and C-S distances are similar
for terminal and bridge groups. As described above
for compounds 1-3, the angle around the sulfur atom
(100°) does not undergo distortion upon Ms(CH2SCN)3
coordination.
In 9, the Ag-Ag distance [3.522(1) A] is too large to be
considered as indicative of argentophilic interactions.24 The
Cu-Cu distance in 8 is 2.936(2) A. In some copper(I)
complexes, Cu-Cu interactions (cuprophilic interactions)
have been proposed,25 but they are weaker than the well-
established aurophilic interactions.26 Schwerdtfeger et al.
mentioned that the shortest Cu-Cu distances found
were 235 pm in tris[1,5-ditolylpentaazadienidocopper(I)],27
which is shorter than that in the metal (256 pm). A longer
Cu-Cu distance, considered as cuprophilic, was found in
[Cu2(ophen)2] (Hophen = 2-hydroxy-1,10-phenanthroline),
3.596 A.28 All compounds for which cuprophilic interactions
have been proposed have an anionic ligand, such as alkyl or
halide. In contrast, 8 has only neutral ligands, so that Cu-Cu
repulsions due to the noncompensated positive charge on
each metal atom should exist. Therefore, the relatively short
Cu-Cu distance of 2.936(2) A could be indicative of some
Cu-Cu stabilizing interaction. Such an interaction could be
partly responsible for the formation of the dimeric struc-
ture of 8 instead of a monomeric complex, with the Ms-
(CH2SCN)3 ligand acting as a tripodal tridentate. The latter
is the geometry most often encountered in tetracoordinated
copper(I) complexes with N-tridentate ligands, such as tris-
(pyrazolyl)borates and tris(pyrazolyl)alkanes,29 and the
structures of compounds 1-4 demonstrate that Ms(CH2-
SCN)3 is able to coordinate a metal center in a tripodal mode.
Tridentate coordination is also found in the [(TriMIm)-
Cu]BF4 complex (Figure 7), where the copper(I) atom is in
a trigonal-planar geometry and the ligand has a mesitylene
core as the bridgehead group.30
Figure 7. Structure of the [(TriMIm)Cu]þ complex in its tetrafluorobo-
rate salt.
Catalytic Carbene- and Nitrene-Transfer Reactions
We have found that [Cu(TpN)(THF)]2[BAr04]2 [TpN =
tris(2-pyridyl)amine] is an efficient catalyst for carbene- and
nitrene-transfer reactions.31 These results prompted us to test
the catalytic activity of 8 in carbene- and nitrene-transfer
reactions to olefins (Scheme 7) and carbene transfer to
alkynes (Scheme 8). No catalytic activity could be found
for the silver complex. Ethyldiazoacetate (EDA) and PhId
NTs were employed as sourcesof carbene and nitrene groups,
respectively.
The reactions were carried out at room temperature in
dichloromethane. In cyclopropanation, when EDA was
added in one portion to a solution of styrene (5:1 styrene/
EDA) in CH2Cl2 in the presence of 8 as the catalyst (1 mol
1
Cu %), a H NMR spectrum taken 2 h latter showed a
quantitative EDA conversion into a mixture of the two
diasteromers of [(2-phenylethoxy)carbonyl]cyclopropane
(87%; Table 3) and the olefins resulting from formal carbene
dimerization, namely, diethylfumarate and diethylmaleate.
When EDA was slowly added over 5 h, formation of the
carbene dimers was avoided and cyclopropanation was
found to be quantitative. With the other olefins employed,
the yields of cyclopropanes obtained reflect their relative
reactivity.32 The results are collected in Table 3.
The color of the final solution was yellow, and no green or
blue color, indicative of copper(II) species, was observed.
Complexes with nitrile ligands have been largely used in
carbene and nitrene catalytic reactions, mainly because of
the lability of nitriles, which provide a vacant coordination
site necessary for the formation of the carbene or nitrene
intermediate.29b,31,33 However, nitrilecopper complexes
could be unstable, limiting the life of the catalyst. Because
the Ms(CH2SCN)3 ligand can be regarded, as a first ap-
proach, as a tris(nitrile) ligand, we tested the stability of 8
under the reaction conditions. Thus, we carried out a cyclo-
propanation experiment with a 5:1 styrene/EDA ratio, 1 mol
% of 8 (relative to EDA), and EDA addition over 2 h using a
syringe pump. After complete EDA addition, an aliquot was
Many copper complexes with the thiocyanate (SCN)
ligand are known;20 however, to the best of our knowledge,
8 is the first example of a copper complex with an alkylthio-
cyanate ligand.
(23) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J. Chem. Soc., Dalton Trans. 1989, S1.
(24) (a) Zheng, X.-D.; Jiang, L.; Feng, X.-L.; Lu, T.-B. Inorg. Chem. 2008,
47, 10858. (b) Rim, C.; Zhang, H.; Son, D. Y. Inorg. Chem. 2008, 47, 11993.
(c) Goodwin, A. L.; Keen, D. A.; Tucker, M. G.; Dove, M. T.; Peters, L.; Evans,
J. S. O. J. Am. Chem. Soc. 2008, 130, 9660.
(25) (a) Kuganathan, N.; Green, J. C. Chem. Commun. 2008, 2432.
(b) Zhang, J.-X.; He, J.; Yin, Y.-G.; Hu, M.-H.; Li, D.; Huang, X.-C. Inorg.
Chem. 2008, 47, 3471. (c) Tronic, T. A.; De Krafft, K. E.; Lim, M. J.; Ley, A. N.;
Pike, R. D. Inorg. Chem. 2007, 46, 8897. (d) Sevryugina, Y.; Rogachev, A. Y.;
Petrukhina, M. A. Inorg. Chem. 2007, 46, 7870.
1
taken and analyzed by H NMR spectroscopy, showing
quantitative cyclopropanation (100 turnovers). To the reaction
(26) Bardajı, M.; Calhorda, M. J.; Costa, P. J.; Jones, P. G.; Laguna, A.;
´
ꢀ
Perez, M. R.; Villacampa, M. D. Inorg. Chem. 2006, 59, 307.
€
(27) Strahle, J.; Beck, J. Angew. Chem., Int. Ed. Engl. 1985, 24, 409.
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K.-F.; Tong, Y.-X.; Chen, X.-M. Chem.;Eur. J. 2002, 8, 3187.
(29) (a) Despagnet-Ayoub, E.; Jacob, K.; Vendier, L.; Etienne, M.;
(31) Perez, J.; Morales, D.; Garcı
Miguel, D.; Bernad, P. Dalton Trans. 2009, 375.
(32) Dıaz-Requejo, M. M.; Mairena, M. A.; Belderraı
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a-Escudero, L. A.; Martı
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a, H.;
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n, T. R.; Nicasio,
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Alvarez, E.; Caballero, A.; Dı
´
az-Requejo, M. M.; Perez, P. J. Organo-
M. C.; Trofimenko, S.; Perez, P. J. Chem. Commun. 2001, 1804.
€
(33) (a) Li, Y.; Diebl, B.; Raith, A.; Kuhn, F. E. Tetrahedron Lett. 2008,
49, 5954. (b) Rodríguez, P.; Caballero, A.; Díaz-Requejo, M. M.; Nicasio, M. C.;
Perez, P. J. Org. Lett. 2006, 8, 557. (c) Conry, R. R.; Tipton, A. A.; Striejewske,
W. S.; Erkizia, E.; Malwitz, M. A.; Caffaratti, A.; Natkin, J. A. Organometallics
2004, 23, 5210. (d) Caballero, A.; Díaz-Requejo, M. M.; Belderraín, T. R.;
metallics 2008, 27, 4779. (b) Yap, G. P. A.; Jove, F.; Urbano, J.; Alvarez, E.;
Trofimenko, S.; Díaz-Requejo, M. M.; Perez, P. J. Inorg. Chem. 2007, 46, 780.
(c) Fujisawa, K.; Ono, T.; Ishikawa, Y.; Amir, N.; Miyashita, Y.; Okamoto, K.-I.;
Lehnert, N. Inorg. Chem. 2006, 45, 1698. (c) Dias, H. V. R.; Lu, H.-L.; Kim, H.-J.;
Polach, S. A.; Goh, T. K. H. H.; Browning, R. G.; Lovely, C. J. Organometallics
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Nicasio, M. C.; Trofimenko, S.; Perez, P. J. J. Am. Chem. Soc. 2003, 125, 1446.
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2000, 39, 4913.

Article
Inorganic Chemistry, Vol. 49, No. 15, 2010 6981
Scheme 7. Cyclopropanation and Aziridination of Olefins
Scheme 8. Catalytic Synthesis of Cyclopropenes
Table 3. Yields of Cyclopropanes and Aziridines in the Copper-Catalyzed
Reactions of EDA with Olefins
olefin
% cyclopropanesa
% aziridinese
styrene
styrene
1-hexene
cyclooctene
cis-stilbene
87 (70:17)b
99 (78:21)c
35d
Figure 8. Study of the stability of 8 in the reaction conditions. Each
point is the average of two experiments.
90
28
90
27
13
40
92d
82 (57:25)d
47d
Table 4. Cyclopropenation of Alkenes Catalyzed by 8a
trans-stilbene
1,1-diphenylethylene
90d
substrate
% cyclopropene
a Standard conditions: 5 mmol of substrate, 1 mmol of EDA, 1 mol %
8, and CH2Cl2 (20 mL). In parentheses, ratio of the trans/cis products.
Yield based on EDA and determined by 1H NMR spectroscopy, average
of two runs. Mass balance accounted for by diethylmaleate and diethyl-
fumarate formation. b EDA added over 0 h. c EDA added over 5 h.
d EDA added over 10 h. e Reactions run for 5 h with 5 mmol of substrate,
1 mmol of PhIdNTs, 2 mol % 8, CH2Cl2 (15 mL). Yield based on
PhIdNTs and determined by 1H NMR spectroscopy, average of two
runs.
phenylacetylene
diphenylacetylene
1-hexyne
3-hexyne
1-phenyl-1-propyne
ethyl propiolate
46
53
32
53
51
42
a Standard conditions: 5 mmol of substrate, 1 mmol of EDA (added
over 11 h), 1 mol % 8, CH2Cl2. Yield based on EDA and determined by
1H NMR spectroscopy, average of two runs. Mass balance accounted
for by diethylmaleate and diethylfumarate formation.
crude, 100 more equiv of EDA was added over 2 h, and the
solution was analyzed by 1H NMR. The EDA addition and the
immediate 1H NMR analysis were repeated a total of six times.
Figure 8 represents the total cyclopropane yield obtained after
each EDA addition.
As can be seen, there is a small yield decrease after each
EDA addition. Note that no additional styrene was added for
each new addition of EDA. Therefore, in the points shown in
Figure 8, the styrene/EDA ratios are 5:1 (as in the cyclopro-
panation reactions described above), 4:1, 3:1, 2:1, 1:1, and,
finally, 0:1. In the final point, the 1H NMR spectrum showed
the presence of diethylfumarate and diethylmaleate as major
products, reflecting the catalytic activity of 8, even in the
absence of styrene.
We studied the activity of 8 as a catalyst in aziridination
reactions (Table 3) using the same olefins as those in cyclo-
propanation (see above) and PhIdNTs as the nitrene source.
The aziridination reactions took place in 5 h, at which time
the solution became clear; i.e., PhIdNTs was completely
dissolved. The solution immediately changed to a green color
after PhIdNTs addition, suggesting the formation of copper-
(II) species, which could be the resting state of the catalyst.
Compound 8 was employed as a catalyst in cyclopropena-
tion reactions (Scheme 8), and the results are shown in Table 4.
The yields obtained are clearly inferior to those obtained in
the cyclopropanation and aziridination reactions, a fact
generally encountered when the three reactions employing
the same catalyst are compared. The results obtained using 8
as catalysts for cyclopropanation, aziridination, and cyclo-
propenation showed this new copper compound to be a
highly active catalyst.31,34
The generation of a catalytic active species could require a
Cu-N bond scission to generate a coordination site neces-
sary for the formation of the carbene or nitrene intermediate.
The Cu-Nbridge bond is longer and, presumably, weaker
than the Cu-Nterminal [d(Cu-Nbridge) = 2.158(4) and
2.275(4) A; d(Cu-Nterminal) = 1.894(4) and 1.911(4) A].35
Therefore, the cleavage of the bridge could create the open
position required for catalytic activity. On the other hand, we
do not rule out the possibility that in solution the active
catalyst was a mononuclear species, such as that found in the
[Cu(TpN)(THF)]2[BAr04]2 complex.31
The tris(thiocyanato) Ms(CH2SCN)3 ligand is special because,
being neutral (and, therefore, each copper center is cationic; note
that high electrophilicity is considered to be a desirable feature for
copper-catalyzed carbene- and nitrene-transfer reactions),33d it is
able to form a nitrogen bridge between two copper atoms, with
long Cu-N distances, presumably indicative of weak Cu-N
bonds that would facilitate the creation of empty sites at metal as
discussed above. This combination of features could be respon-
sible for the high activity of 8 as the catalyst.
Conclusions
Ms(CH2SCN)3 is a versatile ligand that can act as a fac
tripodal tridentate in molybdenum(0), molybdenum(II),
ꢀ
(34) (a) Dıaz-Requejo, M. M.; Perez, P. J. J. Organomet. Chem. 2001,
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617-618, 110. (b) Perez, P. J.; Brookhart, M.; Templeton, J. L. Organometallics
(35) Harding, C.; McDowell, D.; Nelson, J.; Raghunathan, S.; Stevenson,
C.; Drew, M. G. B.; Yates, P. C. J. Chem. Soc., Dalton Trans. 1990, 2521.
1993, 12, 261.

6982 Inorganic Chemistry, Vol. 49, No. 15, 2010
Martınez-Garcıa et al.
manganese(I), and rhenium(I) complexes or as a bidentate
chelate and a bridge in copper(I) and silver(I) compounds.
This ligand did not need distortion for both types of co-
ordination, with the angle about sulfur remaining 100° upon
coordination. For pseudooctahedral complexes, the close to
linear M-N-C angles indicate the predominance of the
resonance form a (see Figure 2), whereas in the bridging
groups of the copper and silver complexes, the lower angles
reflect the major contribution of form b. The dimeric copper
complex 8 is an efficient catalyst for carbene- and nitrene-
transfer reactions to afford cyclopropanes, cyclopropenes,
and aziridines.
63%. Anal. Calcd. for C18H15MoN3O3S3: C, 42.11; H, 2.94; N,
8.18. Found: C, 42.35; H, 3.21; N, 7.91. IR (CH2Cl2, cm-1): νCN
2155 w, νCO 1920 vs, 1813 s. 1H NMR (CD3CN): δ 4.48 [s, 6H,
CH2SCN], 2.50 [s, 9H, CH3].
[Mo(η3-methallyl)(CO)2(Ms(CH2SCN)3)][BAr04] (2). To a
solution of [MoCl(η3-methallyl)(CO)2(NCMe)2] (0.030 g, 0.090
mmol) in CH2Cl2 (10 mL) were added NaBAr04 (0.079 g, 0.090
mmol) and Ms(CH2SCN)3 (0.031 g, 0.090 mmol), and the mixture
was stirred for 15 min. After filtration through diatomaceous earth
and in vacuo concentration, the yellow solution was layered with
hexane (10 mL) and placed at -20 °C, affording yellow crystals,
one of which was used for the structure determination by X-ray
diffraction. Yield: 0.112 g, 94%. Anal. Calcd for C53H34BF24Mo-
N3O3S3 CH2Cl2: C, 35.79; H, 2.93; N, 5.56. Found: C, 36.11; H,
3
3.09; N, 5.65. IR (CH2Cl2, cm-1): νCN 2164 w, νCO 1975 vs, 1904 s.
IR (KBr, cm-1): νCN 2179, 2164, νCO 1965, 1899. 1H NMR
(CD2Cl2): δ 7.77 [s, 8Ho of BAr04], 7.60 [s, 4Hp of BAr04], 4.39
[s, 6H, CH2SCN], 3.28 [s, 2H, Hsyn], 2.49 [s, 9H, CH3 of Ms], 2.06
[s, 3H, CH3 of methallyl], 1.39 [s, 2H, Hanti]. 13C{1H} NMR
(CD2Cl2): δ 220.3 [s, CO], 163.3 [c (J(C,B) = 49.8 Hz), Ci of
BAr04], 141.7 [s, CMsCH2], 136.4 [s, Co of BAr04], 131.5 [s,
CMsCH3], 130.5 [q (J(C,F) = 31.1 Hz), Cm of BAr04], 126.2
[c (J(C,F) = 272.5 Hz), CF3 of BAr04], 119.1 [s, Cp of BAr04], 90.1
[s, Cc of methallyl], 61.8 [s, Ct of methallyl], 35.2 [s, CH2SCN], 21.4
[CH3 of Ms], 18.1 [s, CH3 of methallyl].
Experimental Section
All manipulations were carried out at room temperature
under a dinitrogen atmosphere employing Schlenk techni-
ques. iPrOH (technical grade) was used as received (the same
i
results were obtained by employing pure PrOH distilled
under a dinitrogen atmosphere), and CH2Cl2 was dried over
CaH2, THF over sodium benzophenone, and hexane over
sodium. IR and NMR spectra were recorded on Perkin-
Elmer FT1720-X and Bruker AV-400 spectrometers, respec-
tively. Deuterated solvents were degassed by three freeze-
pump-thaw cycles, dried over 4 A molecular sieves, and
stored in the dark. EDA was added using a Cole Parmer
(74900 series) syringe pump and a Hamilton gastight 20 mL
syringe. [Mo(CO)3(NCMe)3],36 [MoCl(η3-methallyl)(CO)2-
(NCMe)2],37 [MnBr(CO)5],38 [ReBr(CO)3(NCMe)2],39
NaBAr04,40 and PhIdNTs (stored at -20 °C under a dinitro-
gen atmosphere)41 were prepared according to literature
procedures. All other chemicals were purchased and used
without further purification.
[Mn(CO)3(Ms(CH2SCN)3)][BAr04] (3). [MnBr(CO)5] (0.053 g,
0.182 mmol) was refluxed in MeCN (10 mL) until the disappear-
ance of the νCO bands of the starting material and the appearance
of the νCO bands of [MnBr(CO)3(NCMe)2] (2042 vs, 1955s, and
1934s; ca. 30 min). After in vacuo evaporation to dryness, AgOTf
(0.050 g, 0.194 mmol), MeCN (1 mL), and CH2Cl2 (10 mL) were
added, and the mixture was stirred for 1 h in the dark and filtered
through diatomaceous earth. To this solution were added Ms-
(CH2SCN)3 (0.045 g, 0.182 mmol) and NaBAr04 (0.170 g, 0.182
mmol), and after stirring for 1 h, the mixture was filtered through
diatomaceous earth. In vacuo concentration and the addition of
hexane (10 mL) causes the precipitation of a yellow microcrystal-
line solid. Crystals of good quality for X-ray analysis were obtained
by the slow diffusion of hexane (10 mL) into a concentrated
solution of 3 in CH2Cl2 at -20 °C. Yield: 0.223 g, 91%. Anal.
Calcd for C50H27BF24MnN3O3S3: C, 44.96; H, 2.04; N, 3.15.
Found: C, 45.03; H, 2.13; N, 3.21. IR (CH2Cl2, cm-1): νCN 2196
w, νCO 2066 s, 1985 s. 1H NMR (CD2Cl2): δ 7.72 [s, 8Ho of BAr04],
7.57 [s, 4Hp of BAr04], 4.40 [s, 6H, CH2SCN], 2.49 [s, 9H, CH3 of
Ms]. 13C{1H} NMR(CD2Cl2): δ 215.1 [s, CO], 161.7 [c (J(C,B) =
50.2 Hz), Ci of BAr04], 140.34 [s, CMsCH2], 137.7 [s, Co of BAr04],
129.9 [s, CMsCH3], 128.7 [q (J(C,F) = 27.2 Hz), Cm of BAr04],
124.6 [c (J(C,F) = 272.7 Hz), CF3 of BAr04], 120.3 [s, Cp of BAr04],
117.6 [s, SCN], 33.5 [s, CH2SCN], 16.8 [CH3 of Ms].
[Re(CO)3(Ms(CH2SCN)3)][BAr04] (4). AgOTf (0.035 g, 0.130
mmol) was added to a solution of [ReBr(CO)3(NCMe)2] (0.053
g, 0.123 mmol) in a mixture of CH2Cl2/MeCN (10 mL/0.5 mL).
After stirring for 1 h and filtration through diatomaceous earth,
Ms(CH2SCN)3 (0.043 g, 0.130 mmol) and NaBAr04 (0.115 g,
0.130 mmol) were added and stirred for 1 h. The mixture was
filtered through diatomaceous earth, and in vacuo concentra-
tion and the addition of hexane (10 mL) caused the precipitation
of a white microcrystalline solid, which was washed with hexane
(3 ꢀ 10 mL) and dried under vacuum. Yield: 0.166 g, 92%. Anal.
Calcd for C50H27BF24N3O3ReS3: C, 40.94; H, 1.86; N, 2.86.
Found: C, 41.07; H, 1.94; N, 2.95. IR (CH2Cl2, cm-1): νCN 2193
w, νCO 2055 s, 1965 s. IR (KBr, cm-1): νCN 2196, νCO 2058, 1971,
1953. 1H NMR (CD2Cl2): δ 7.73 [s, 8Ho of BAr04], 7.58 [s, 4Hp of
BAr04], 4.56 [s, 6H, CH2SCN], 2.49 [s, 9H, CH3 of Ms]. 13C{1H}
NMR(CD2Cl2): δ 197.2 [s, CO], 161.7 [c (J(C,B) = 50.2 Hz ), Ci
of BAr04], 140.34 [s, CMsCH2], 137.7 [s, Co of BAr04], 129.9 [s,
CMsCH3], 128.7 [q (J(C,F) = 27.2 Hz), Cm of BAr04], 124.6
[c (J(C,F) = 272.7 Hz), CF3 of BAr04], 120.3 [s, Cp of BAr04],
117.6 [s, SCN], 33.5 [s, CH2SCN], 16.8 [CH3 of Ms].
1,3,5-Tris(thiocyanatomethyl)mesitylene [Ms(CH2SCN)3]. A
mixture of 1,3,5-tris(bromomethyl)mesitylene (0.500 g, 1.253
mmol) and KSCN (0.393 g, 4.010 mmol) in iPrOH (20 mL) was
refluxed for 3 h. After reaching room temperature, the solution
was allowed to settle, and the white solid was redissolved in
CH2Cl2 and filtered through diatomaceous earth. In vacuo
concentration to 10 mL and the addition of hexane (20 mL)
caused the precipitation of a microcrystalline white solid, which
was washed with hexane and dried under vacuum. Colorless
crystals of X-ray quality were obtained by the slow diffusion of
hexane into a concentrated solution of Ms(CH2SCN)3 in
CH2Cl2 at -20 °C. Yield: 0.387 g, 92%. IR (CH2Cl2, cm-1):
1
νCN 2154. IR (KBr, cm-1): νCN 2158, 2153, 2140. H NMR
(CDCl3): δ 4.43 [s, 6H, CH2SCN], 2.53 [s, 9H, CH3].
[Mo(CO)3(Ms(CH2SCN)3)] (1). To a solution of freshly
prepared [Mo(CO)3(NCMe)3] (0.230 mmol) in CH2Cl2 (10 mL)
was slowly added a solution of Ms(CH2SCN)3 (0.076 g, 0.230
mmol) in CH2Cl2 (20 mL). Immediately, yellow crystals of 1 were
formed, one of which was used for X-ray analysis. Yield: 0.075 g,
(36) Tate, D. P.; Knipple, W. R.; Augl, J. M. Inorg. Chem. 1962, 1, 433.
(37) Tom Dieck, H.; Friedel, H. J. Organomet. Chem. 1968, 14, 375.
(38) Schmidt, S. P.; Trogler, W. C.; Basolo, F. Inorg. Synth. 1990, 28, 160.
(39) Farona, M. F.; Graus, K. F. Inorg. Chem. 1970, 9, 1700.
(40) Brookhart, M.; Grant, B.; Volpe, A. F., Jr. Organometallics 1992, 11,
3920.
(41) White, R. E.; McCarthy, M. B. J. Am. Chem. Soc. 1984, 106, 4922.

Article
Reaction of 1 with I2. A solution of I2 (0.113 g, 0.440 mmol) in
Inorganic Chemistry, Vol. 49, No. 15, 2010 6983
NMR (CD2Cl2): δ 7.76 [s, 8Ho of BAr04], 7.60 [s, 4Hp of BAr04],
4.34 [s, 6H, CH2SCN], 2.52 [s, 9H, CH3 of Ms]. 13C{1H} NMR
(CD2Cl2): δ 161.8 [c (J(C,B) = 49.8 Hz), Ci of BAr04], 139.4
[s, CMsCH2], 134.9 [s, Co of BAr04], 130.3 [s, CMsCH3], 129.1 [q
(J(C,F) = 31.6 Hz), Cm of BAr04], 124.7 [c (J(C,F) = 272.3 Hz),
CF3 of BAr04], 117.6 [s, Cp of BAr04], 114.3 [s, SCN], 32.5 [s,
CH2SCN], 16.8 [CH3 of Ms].
CH2Cl2 (10 mL) was added, via canula, to a solution of 1 (0.230 g,
0.440 mmol) in CH2Cl2 (10 mL) at 0 °C, and the mixture was
allowed to reach room temperature and stirred for 15 min. After
filtration through diatomaceous earth and in vacuo concentra-
tion, the addition of hexane (10 mL) caused the precipitation of
a light-brown microcrystalline solid, a mixture of [MoI2(CO)3-
(Ms(CH2SCN)3)] (5) and [MoI2(CO)3{Ms(CH2SCN)2(CH2I)}]
(6). Compound 6 was extracted with CH2Cl2 (5 ꢀ 5 mL), and by
the slow diffusion of hexane into that solution at room temp-
erature, orange crystals of good quality for X-ray analysis were
obtained (yield: 0.100 g, 27%). The brown solid sparingly
soluble in CH2Cl2 corresponded to 5 (yield: 0.070 g, 20%). IR
(CH2Cl2, cm-1): νCN 2181w, 2155 w, νCO 2033vs, 1965s, 1943 sh.
Cyclopropanation. A solution of EDA (1 mmol, 0.105 mL) in
CH2Cl2 (10 mL) was added, over the time indicated, using a
syringe pump and a Hamilton gastight 20 mL syringe to a
solution of 8 (0.005 mmol, 12.6 mg) and the olefin (5 mmol)
dissolved in CH2Cl2 (15 mL). The solution was stirred for 2 h
after the complete addition of EDA. An internal standard,
C6Me6 (0.055 mmol, 9 mg), was added. An aliquot (1 mL) was
then filtered through a plug of silica gel, and the solution was
concentrated to ∼0.5 mL. CDCl3 (0.5 mL) was added, and the
sample was transferred to an NMR tube. Yields were estimated
1
Spectroscopic data of 5. H NMR (acetone-d6): δ 4.62 (s, 6H,
CH2), 2.32 (s, 9H, CH3). Insufficient solubility of 5 in all common
organic solvents precluded the 13C NMR acquisition. Spectroscopic
data of 6. 1H NMR (CD2Cl2): δ 4.69 (d(12), 2H, CH2), 4.53 (s, 2H,
CH2), 4.21 (d(12), 2H, CH2), 2.53 (s, 3H, CH3), 2.46 (s, 6H, CH3).
13C{1H} NMR (CD2Cl2):225.7[s, CO], 138.9, 137.5, 129.0, 124.0 [s,
CMs], 34.1 [s, CH2SCN], 16.2, 15.4 [CH3 of Ms].
1
using H NMR spectroscopy by integration of product reso-
nances relative to the internal hexamethylbenzene standard.
Only for cyclopropane from styrene did the signals due to the
different diasteromers appear at sufficiently different chemical
shifts so that their integration could be used to obtain an
estimation of the trans/cis ratio.
[MoI(CO)3(Ms(CH2SCN)3)][BAr04] (7). NaBAr04 (0.195 g,
0.220 mmol) was added to a suspension of 5 (0.170 g, 0.220
mmol) in CH2Cl2 (15 mL), and the mixture was stirred for 1 h.
After filtration through diatomaceous earth and in vacuo con-
centration, the addition of hexane caused the precipitation of 7
as a light-brown microcrystalline solid. Yield: 0.285 g, 86%. IR
Aziridination. To a mixture of 8 (0.01 mmol, 24 mg), the olefin
(5 mmol), and 4 A molecular sieves (ca. 1 g) in 15 mL of CH2Cl2
was added PhIdNTs (1 mmol, 348 mg), and the mixture was
stirred until PhIdNTs was completely dissolved (5 h). An
internal standard, C6Me6 (0.055 mmol, 9 mg), was added. An
aliquot (1 mL) was filtered through silica gel and concentrated
to ∼0.5 mL. CDCl3 (0.5 mL) was added, and the sample was
1
(CH2Cl2, cm-1): νCN 2183 m, νCO 2062 s, 2006 s, 1984 s. H
NMR (CD2Cl2): δ 7.87 [s, 8Ho of BAr04], 7.69 [s, 4Hp of BAr04],
4.48 [s, 6H, CH2SCN], 2.54 [s, 9H, CH3 of Ms]. 13C{1H} NMR
(CD2Cl2): δ 225.6 [s, CO], 161.9 [c (J(C,B) = 50.2 Hz), Ci of
BAr04], 140.6 [s, CMsCH2], 134.9 [s, Co of BAr04], 129.9 [s,
CMsCH3], 128.7 [q (J(C,F) = 27.2 Hz), Cm of BAr04], 127.0
[s, SCN], 124.6 [c (J(C,F) = 272.7 Hz), CF3 of BAr04], 117.6 [s,
Cp of BAr04], 33.9 [s, CH2SCN], 16.5 [CH3 of Ms].
1
transferred to an NMR tube. Yields were estimated using H
NMR spectroscopy by integration of product resonances rela-
tive to the internal standard.
Cyclopropenation. A solution of EDA (1 mmol, 0.105 mL) in
CH2Cl2 (10 mL) was added over 11 h using a syringe pump to a
solution containing 8 (0.005 mmol, 12.6 mg) and the alkyne
(5 mmol) in CH2Cl2 (15 mL). The solution was stirred for 2 h
after the complete addition of EDA. Analysis of the results was
as described for cyclopropanation.
[Cu(Ms(CH2SCN)3)]2[BAr04]2 (8). [Cu(OTf)]2 C6H6 (0.050 g,
3
0.099 mmol) and Ms(CH2SCN)3 (0.066 g, 0.198 mmol) were
stirred in a mixture of THF/MeCN (10 mL/1 mL) until forma-
tion of a white precipitate (in a few minutes). After decantation
of the solution, the microcrystalline solid was washed with
hexane (2 ꢀ 10 mL) and redissolved in CH2Cl2 (20 mL).
NaBAr04 (0.175 g, 0.198 mmol) was added, and the mixture
was stirred for 30 min and filtered through diatomaceous earth.
After in vacuo concentration (to ca. 10 mL), the solution was
layered with hexane (20 mL) and placed at -20 °C, affording
white crystals, one of which was used for determination of the
structure of 8 by X-ray diffraction. Yield: 0.427 g, 85%. Anal.
Calcd for C47H27BCuF24N3S3: C, 44.79; H, 2.16; N, 3.33.
Found: C, 44.83; H, 2.23; N, 3.38. IR (CH2Cl2, cm-1): νCN
X-ray Crystallography. Crystallographic data for Ms-
(CH2SCN)3, 1, 2, 8, and 9 were collected with a Bruker AXS
SMART 1000 diffractometer with graphite-monochromatized
Mo KR radiation (λ = 0.710 73 A) for 1, 2, and 9 and Cu KR
radiation (λ = 1.5418 A) for 8 and a CCD area detector. Raw
frame data were integrated with the program SAINT.42
A
semiempirical absorption correction was applied with the pro-
gram SADABS.43 Trifluoromethyl groups are disordered in 8.
For compound 6, data collection was performed on an Oxford
Diffraction Xcalibur Nova single-crystal diffractometer, using
Cu KR (λ = 1.5418 A). The intensities were measured using the
oscillation method. The crystal structure was solved by direct
methods. The refinement was performed using full-matrix least
squares on F2. Crystal structures were solved by direct methods,
using the program SIR-9244 under WINGX45 and refined
against F2 with SHELXTL-97.46 All non-hydrogen atoms were
refined anisotropically. Hydrogen atoms were geometrically
placed riding on their parent atoms with isotropic displace-
ment parameters set to 1.2Ueq of the atoms to which they are
attached (1.5 for methyl groups). Flack parameter:47 0.08(1).
1
2174. IR (KBr, cm-1): νCN 2189, 2144. H NMR (CD2Cl2): δ
7.75 [s, 8Ho of BAr04], 7.50 [s, 4Hp of BAr04], 4.37 [s, 6H,
CH2SCN], 2.48 [s, 9H, CH3 of Ms]. 13C{1H} NMR (CD2Cl2):
δ 161.7 [c (J(C,B) = 50.1 Hz), Ci of BAr04], 139.3 [s, CMsCH2],
134.8 [s, Co of BAr04], 131.6 [s, CMsCH3], 129.3 [q (J(C,F) =
33.6 Hz), Cm of BAr04], 124.8 [c (J(C,F) = 271.3 Hz), CF3 of
BAr04], 118.5 [s, Cp of BAr04], 113.2 [s, SCN], 33.9 [s, CH2SCN],
17.4 [CH3 of Ms].
[Ag(Ms(CH2SCN)3)]2[BAr04]2 (9). A mixture of AgOTf
(0.050 g, 0.195 mmol), Ms(CH2SCN)3 (0.065 g, 0.195 mmol),
and NaBAr04 (0.172 g, 0.195 mmol) in CH2Cl2 (10 mL) was
stirred in the dark for 1 h. After filtration through diatomaceous
earth and in vacuo concentration, the addition of hexane (10 mL)
caused the precipitation of a white microcrystalline solid, which
was washed and dried under vacuum. By the slow diffusion of
hexane (10 mL) into a concentrated solution of 9 in CH2Cl2 at
-20 °C, white crystals were obtained, one of which was used for
the X-ray structure determination. Yield: 0.478 g, 93%. Anal.
Calcd for C47H27AgBF24N3S3: C, 43.27; H, 2.09; N, 3.22. Found:
(42) SAINTþ. SAX area detector integration program, version 6.02; Bruker
AXS, Inc.: Madison, WI, 1999.
(43) Sheldrick, G. M. SADABS, Empirical Absorption Correction Pro-
€
€
gram; University of Gottingen: Gottingen, Germany, 1997.
(44) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Burla,
M. C.; Polidori, G.; Camalli, M. J. Appl. Crystallogr. 1994, 27, 435.
(45) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837.
(46) Sheldrick, G. M. SHELXL-97. A computer program for refinement of
€
crystal structures; University of Gottingen: Gottingen, Germany, 1997.
1
C, 43.33; H, 2.14; N, 3.27. IR (CH2Cl2, cm-1): νCN 2168. H
(47) Flack, H. D. Acta Crystallogr. 1983, A39, 876.

6984 Inorganic Chemistry, Vol. 49, No. 15, 2010
Martınez-Garcıa et al.
Table 5
Ms(CH2SCN)3
1
2
empirical formula
fw
cryst syst
space group
a (A)
C15H15N3S3
333.48
triclinic
C19H17Cl2MoN3O3S3
598.35
monoclinic
P2(1)/n
10.317(2)
15.328(3)
15.115(3)
90
102.84(3)
90
2330.6(8)
4
293(2)
1.665
1168
C54H36BCl2F24MoN3O3S3
1488.69
triclinic
P1
P1
8.808(9)
10.401(11)
10.617(11)
63.225(19)
73.88(2)
76.59(2)
827.8(15)
2
10.496(11)
17.091(18)
18.91(2)
b (A)
c (A)
R (deg)
β (deg)
γ (deg)
V (A3)
Z
72.58(2)
74.470(19)
72.62(2)
3029(5)
2
293(2)
T (K)
Dcalc (g cm-3
F(000)
293(2)
1.338
348
)
1.632
1484
λ(KR) (A)
cryst size (mm)
0.710 73
0.27 ꢀ 0.14 ꢀ 0.06
0.444
1.5418
0.25 ꢀ 0.12 ꢀ 0.10
0.710 73
0.48 ꢀ 0.47 ꢀ 0.21
μ(KR) (mm-1
)
9.448
0.526
collection range (deg)
max/min transm factors
reflns collected
2.19-23.78
1.000/0.576
3784
4.16-68.75
1.201/0.841
17 758
1.15-23.36
1.000/0.703
13 480
indep reflns [R(int)]
GOF on F2
2405 [0.0281]
0.978
4192 [0.0426]
1.117
8526 [0.0191]
1.028
R1, wR2 (all data)
R1, wR2 [I > 2σ(I)]
largest diff peak
0.0754, 0.1389
0.0513, 0.1271
0.329, -0.289
0.0469, 0.1203
0.0415, 0.1021
0.843, -0.688
0.0815, 0.1888
0.0687, 0.1744
1.207, -0.702
3
6
8
9
empirical formula
fw
cryst syst
space group
a (A)
C168H96B3F72Mn4N12O12S3
C17H15I3MoN2O3S2
836.09
orthorhombic
Pbca
17.6096(4)
9.7609(2)
27.6001(5)
90
90
90
4744.06(17)
8
293(2)
2.341
3104
C47H27BCuF24N3S3
1260.25
triclinic
C94H54Ag2B2F48N6S6
2609.15
triclinic
1335.67
cubic
P43n
21.6980(1)
21.6980(1)
21.6980(1)
90
P1
P1
13.1045(2)
13.1857(2)
16.1827(2)
80.3460(9)
84.7997(10)
64.6597(11)
2490.85(7)
2
150(2)
1.680
1256
1.5418
13.154(3)
13.204(3)
16.343(3)
83.39(3)
78.76(3)
64.24(3)
2506.0(9)
2
150(2)
1.729
1292
b (A)
c (A)
R (deg)
β (deg)
γ (deg)
V (A3)
Z
90
90
10215.49(8)
2
150(2)
1.456
4478
T (K)
Dcalc(g cm-3
F(000)
)
λ(KR) (A)
cryst size (mm)
1.5418
0.37 ꢀ 0.25 ꢀ 0.25
1.5418
0.043 ꢀ 0.086 ꢀ 0.203
1.5418
0.22 ꢀ 0.20 ꢀ 0.05
0.22 ꢀ 0.20 ꢀ 0.01
μ(KR) (mm-1
)
4.208
37.004
2.982
0.656
collection range (deg)
max/min transm factors
reflns collected
2.88-68.21
1.47/0.82
5881
3.20-74.00
1.00/0.18
19 275
2.77-68.31
0.97/0.86
39 612
1.27-68.90
0.84/1.15
38 201
indep reflns [R(int)]
GOF on F2
3129 [0.0253]
1.041
4787 [0.0743]
1.059
9011 [0.0360]
1.090
9115 [0.0411]
1.031
R1, wR2 (all data)
R1, wR2 [I > 2σ(I)]
largest diff peak
0.0837, 0.2272
0.0777, 0.2187
0.616, -1.295
0.0648, 0.1699
0.0609, 0.1651
2.010, -2.247
0.0754, 0.1861
0.0684, 0.1781
1.205, -1.088
0.0788, 0.1940
0.0718, 0.1856
1.659, -1.077
For compound 3, data collection was performed at 150(2) K on
a Nonius Kappa CCD single-crystal diffractometer, using Cu
KR radiation (λ = 1.5418 A). Images were collected at a 29 mm
fixed crystal-detector distance, using the oscillation method,
with 2° oscillation and 30 s exposure time per image. The data
collection strategy was calculated with the program Collect.48
Data reduction and cell refinement were performed with the
programs HKL Denzo and Scalepack.49 Unit cell dimensions
were determined from 18 112 reflections between θ = 2.2° and
68.2°. Multiple observations were averaged, Rmerge= 0.0253,
resulting in 3129 unique reflections, of which 2759 were ob-
served with I > 2σ(I). A semiempirical absorption correction
was applied using the program SORTAV.50 Trifluoromethyl
groups are disordered. The crystal structure exhibits some voids
that may be filled with crystallization solvents (hexane and
dichoromethane). However, these solvents could not be appro-
piately modeled, and the residual density in these spaces was
removed using the SQUEEZE procedure,51 as implemented in
the program PLATON.52 The final cycle of full-matrix least-
squares refinement based on 3129 reflections and 251 para-
meters converged to a final value of R1[F2 > 2σ(F2)] = 0.0777,
wR2[F2 > 2σ(F2)] = 0.2187, R1(F2) = 0.0837, wR2(F2) =
0.2272. Final difference Fourier maps showed no peaks higher
than 0.616 e A-3 or deeper than -1.295 e A-3
.
(51) Sluis, P. v. d.; Spek, A. L. Acta Crystallogr. 1990, A46, 194.
(52) Spek, A. L. PLATON, a multipurpose crystallographic tool; Utrecht
University: Utrecht, The Netherlands, 2005.
(48) Collect; Enraf-Nonius BV: Rotterdam, The Netherlands1997-2004.
(49) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307.
(50) Blessing, R. H. Acta Crystallogr. 1995. A51, 33.

Article
For compounds 2, 3, 8, and 9, containing the anion BAr04, the
Inorganic Chemistry, Vol. 49, No. 15, 2010 6985
sterio de Ciencia y Tecnologıa (Grants CTQ2006-07036/BQU
´
ꢀ
trifluoromethyl groups are affected by some degree of disorder.
Only in some cases for structures 3 and 8 was it possible to find a
correct model for alternate (staggered) positions. In the remain-
ing cases, the incipient disorder affects the shape and size of the
ellipsoids of the fluorine atoms, which are abnormally bigger
when compared to those of the pivotal carbon atoms in which
they ride (Table 5).
and CTQ-2006-08924), and Junta de Castilla y Leon (Grants
VA017B08 and VA070A08) for support. D.M. thanks the Mini-
ꢀ
sterio de Educacion y Ciencia for a Ramon y Cajal contract.
ꢀ
Supporting Information Available: X-ray crystallographic
data in CIF format, molecular representation of the crystal
structures of 3 and 8, VT 1H NMR of 5 in CD2Cl2, 13C NMR of
7 at room temperature and -60 °C, and references giving the
spectroscopic data of the catalysis products. This material is
available free of charge via the Internet at http://pubs.acs.org.
Acknowledgment. We thank Principado de Asturias
(Grants IB05-069 and IB08-104 administered by FICYT), Mini-