Experimental and computational studies on the formation of cyanate from early metal terminal nitrido ligands and carbon monoxide

Article abstract of DOI:10.1039/c3dt52738g

An important challenge in the artificial fixation of N₂ is to find atom efficient transformations that yield value-added products. Here we explore the coordination complex mediated conversion of ubiquitous species, CO and N₂, into isocyanate. We have conceptually split the process into three steps: (1) the six-electron splitting of dinitrogen into terminal metal nitrido ligands, (2) the reduction of the complex by two electrons with CO to form an isocyanate linkage, and (3) the one electron reduction of the metal isocyanate complex to regenerate the starting metal complex and release the product. These steps are explored separately in an attempt to understand the limitations of each step and what is required of a coordination complex in order to facilitate a catalytic cycle. The possibility of this cyanate cycle was explored with both Mo and V complexes which have previously been shown to perform select steps in the sequence. Experimental results demonstrate the feasibility of some of the steps and DFT calculations suggest that, although the reduction of the terminal metal nitride complex by carbon monoxide should be thermodynamically favorable, there is a large kinetic barrier associated with the change in spin state which can be avoided in the case of the V complexes by an initial binding of the CO to the metal center followed by rearrangement. This mandates certain minimal design principles for the metal complex: the metal center should be sterically accessible for CO binding and the ligands should not readily succumb to CO insertion reactions.

Full text of DOI:10.1039/c3dt52738g

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Experimental and computational studies on the
formation of cyanate from early metal terminal
nitrido ligands and carbon monoxide†
Cite this: DOI: 10.1039/c3dt52738g
Anthony F. Cozzolino, Jared S. Silvia, Nazario Lopez and Christopher C. Cummins*
An important challenge in the artificial fixation of N2 is to find atom efficient transformations that yield
value-added products. Here we explore the coordination complex mediated conversion of ubiquitous
species, CO and N2, into isocyanate. We have conceptually split the process into three steps: (1) the six-
electron splitting of dinitrogen into terminal metal nitrido ligands, (2) the reduction of the complex by two
electrons with CO to form an isocyanate linkage, and (3) the one electron reduction of the metal iso-
cyanate complex to regenerate the starting metal complex and release the product. These steps are
explored separately in an attempt to understand the limitations of each step and what is required of a
coordination complex in order to facilitate a catalytic cycle. The possibility of this cyanate cycle was
explored with both Mo and V complexes which have previously been shown to perform select steps in
the sequence. Experimental results demonstrate the feasibility of some of the steps and DFT calculations
suggest that, although the reduction of the terminal metal nitride complex by carbon monoxide should
be thermodynamically favorable, there is a large kinetic barrier associated with the change in spin state
which can be avoided in the case of the V complexes by an initial binding of the CO to the metal center
followed by rearrangement. This mandates certain minimal design principles for the metal complex: the
metal center should be sterically accessible for CO binding and the ligands should not readily succumb to
CO insertion reactions.
Received 1st October 2013,
Accepted 16th January 2014
DOI: 10.1039/c3dt52738g
www.rsc.org/dalton
center with input of one electron (Fig. 1, Step 3) to give the
overall reaction presented in eqn (1). Ideally, this transform-
Introduction
The fixation of N2 directly into value added chemicals is an ation can be driven either electrochemically or chemically as
exciting, yet challenging problem. Recently, we reported the illustrated in eqn (1) or (2). Here it can be seen that the for-
transfer of an N2-derived terminal nitrido ligand, NuMo- mation of the salt is much more enthalpically favorable than
(N[tBu]Ar)3 (1, Ar = 3,5-Me2C6H3), into organic nitriles with con- the formation of isocyanic acid, however the formation of the
comitant regeneration of the starting material, Mo(N[tBu]Ar)3
(2).1 In a related approach, the terminal nitride ligand in 1 was
converted to cyanide, where the carbon atom source was the
methylene carbon of methoxymethyl chloride.2 While both of
these studies demonstrated the functionalization of N2 derived
N, neither represents a particularly atom-efficient set of trans-
formations. A more appealing transformation is depicted in
Fig. 1: the reduction of an N2-derived metal nitride (Fig. 1,
Step 1, a six electron process) by carbon monoxide, which acts
as a two electron reductant, to produce an isocyanate linkage
(Fig. 1, Step 2) that, in turn, can be reduced off the metal
Department of Chemistry, Massachusetts Institute of Technology, Cambridge,
MA 02139-4307, USA. E-mail: ccummins@mit.edu
†Electronic supplementary information (ESI) available: For spectra, tables of
crystallographic data and tables of DFT optimized coordinates. CCDC
961016–961023. For ESI and crystallographic data in CIF or other electronic
Fig. 1 Proposed reaction cycle for coordination complex [M] mediated
format see DOI: 10.1039/c3dt52738g
isocyanate formation from CO, N2 and an electron source.
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isocyanic acid is thermodynamically spontaneous in the gas complex is cleanly formed, but Step 3, the reduction of the
phase at 298.15 K.
complex to liberate the isocyanate, was not demonstrated
(Fig. 2b). A third example of Step 2, which remains a relatively
rare transformation, involves the reduction of a ruthenium
bound nitrido ligand to an isocyanate accompanied by
addition of a carbonyl ligand (Fig. 2c).8 An additional example
has a molybdenum(II) dicarbonyl form an isocyanate concomi-
tant with N2O cleavage.9 In all these examples, however, the
nitrogen source is an azide or N2O. Two examples of (µ2,η1,η2-
N2)Hf2 complexes show N2 cleavage that is facilitated by
reduction with CO to form an equivalent of isocyanate for each
mole of N2 (Fig. 2d).10,11 We were, therefore, curious if a
similar transformation could be realized with dinitrogen-
derived metal nitride ligands. This would entail either starting
from a system that is already known to cleave dinitrogen, or
preparing a new system capable of all three steps.
CO þ 1=2N2 þ eꢀ ! OCNꢀ
ð1Þ
ð2Þ
KðsÞ þ COðgÞ þ 1=2N2ðgÞ ! KOCN
ðsÞ
ΔH 0 ¼ ꢀ73:4 kcal molꢀ1 3;4
1=2H2ðgÞ þ COðgÞ þ 1=2 N2ðgÞ ! HNCO
ðgÞ
ΔH0 ¼ 2:1 kcal molꢀ1 3
ð3Þ
ΔG0 ¼ ꢀ 0:8 kcal molꢀ1 3
Isocyanate salts, specifically the sodium and potassium
salts are of commercial importance. Collectively, the world-
wide demand for cyanate salts is 8000–10 000 tonnes per
annum.5 The salts are prepared industrially through the treat-
ment of sodium carbonate with urea, effectively requiring two
moles of NH3 for each mole of cyanate that is produced, and
takes place at temperatures in excess of 400 °C.5 The cyanate
salts find application from steel hardening to fine chemical
and pharmaceutical synthesis, and are still used in the agro-
chemical industry in developing nations where there is an
increase in new production.5
Evidence for Step 2 from the cycle in Fig. 1 has been
observed with two different terminal vanadium nitrides,
[NuV(N[tBu]Ar)3]− (3)6 and NuV(nacnac)(N[p-tol]2) (4, nacnac =
Ar′NC(CH3)CHC(CH3)NAr′), Ar′ = 2,6-iPr2C6H3).7 In the case
of 3, the isocyanate is spontaneously lost as the cyanate salt
liberating V(N[tBu]Ar)3 (Fig. 2a). In the case of 4, the isocyanate
The present work outlines our efforts towards the formation
of an isocyanate moiety from the direct reduction of early tran-
sition metal (Mo or V) nitrido complexes with carbon monox-
ide. Initially, the reduction of
a
dinitrogen-derived
molybdenum(VI) nitride containing complex (1) by CO is
explored under a variety of experimental conditions. DFT cal-
culations are used to find molybdenum(VI) nitride complexes
(9 and 11) with more favorable enthalpies for reduction by CO.
Driven by a further lack of observed reactivity, a related
vanadium(II) complex (13) is prepared for the purpose of six
electron reduction of dinitrogen, with the expectation of a
more reactive nitrido ligand. Characterization data are pres-
ented for
a bimetallic dinitrogen complex of the new
vanadium system (14). DFT calculations are presented with the
aim of elucidating the differences in CO reactivity between 1
and an isoelectronic vanadium complex (4) by way of acquiring
design principles for future studies of this nature. Finally, the
characterization of the independently synthesized thermochro-
mic OCN–Mo(N[tBu]Ar)3 (5) is presented and the origin of the
phenomenon elucidated.
Results and discussion
Treatment of N2-derived 1 with CO
We first probed the possibility of the direct conversion of a
terminal nitride ligand to an isocyanate ligand by carbon mon-
oxide treatment with 1 (Scheme 1a); the latter is obtained
directly from the facile cleavage of dinitrogen by 2.12 The
Fig. 2 Examples of isocyanate formation from the reduction of N2-
derived complexes by CO.6–8,11
Scheme 1 Treatment of (a) 1 with CO in an attempt to generate 5 and
(b) 2 with AgOCN to generate 5.
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treatment of 1 with carbon monoxide was screened under a
variety of conditions including: 1 and 14 atm CO over 1 dis-
solved in pentane or THF, under reducing (Na{Hg}) conditions,
and under UV (254 and 300 nm) irradiation. Isocyanate for-
mation was monitored by IR absorbance; an OCN stretching
frequency of 2225 cm−1 was monitored as determined by inde-
pendent synthesis of the desired product (see below). None of
the above reaction conditions led to the appearance of a band
that could be assigned to isocyanate formation and no
changes were observed by 1H NMR spectroscopy. In light of
the recent results demonstrating CO assisted N2 cleavage with
Me2Si(η5-C5Me4)(η5-C5H3-3-tBu)Hf,11,13 the bridging dinitrogen
complex (µ-N2)[Mo(N[tBu]Ar)3]2 (6)14 was also treated with CO,
however only the previously reported carbonyl complex OC–
Mo(N[tBu]Ar)3 was observed in the reaction mixture.15
Table 1 Comparison of calculated and experimental chemical shifts
(δ, ppm) [and linewidths (Hz)] for 5
Position
Experimental
DFT calculated
tBu
MeAr
o-Ar
p-Ar
27.16 [80]
−2.20 [11]
−2.90 [155]
−7.84 [13]
36.2 [238]
−2.5 [46]
−4.7 [421]
−13.0 [50]
linewidths in this case are a function of the hydrogen atom
distances from the metal center.23 The infrared spectrum of
complex 5 displayed an intense absorbance at 2225 cm−1 that
can be attributed to the isocyanate and is consistent with the
calculated vibrational frequency (2266 cm−1).
DFT calculations were performed on a model system,
NuMo(NMe2)3 (1-mod),16 in order to estimate the thermodyn-
Stability and reactivity of 5
amic driving force for eqn (4) starting from nitride 1. The cal- To determine the thermal stability of isocyanate 5, a sample
culated entropy for eqn (4), corrected for the basis set was sealed in a glass NMR tube and monitored by 1H NMR
superposition error (BSSE, ∼1 kcal mol−1), is 0.5 kcal mol−1 spectroscopy as a function of time. No change was observed
and the Gibbs free energy at 298.15 K is 11.5 kcal mol−1 with a after 144 h at 21 °C, however above 60 °C isobutylene for-
GGA only functional (PW91)17 and ΔH298.15 = −8.8 kcal mol−1 mation could be observed after 8 h which is indicative of tert-
and ΔG298.15 = 5.3 kcal mol−1 when exchange is included using butyl radical ejection, or cation ejection together with proton
a
hybrid functional (B3PW: exchange B88,18 correlation transfer, from one of the anilide ligands.21,24 At 90 °C the
PW91,17 30% HF19). The electronic energy calculated for eqn process was accelerated and complete depletion of 5 was
(4) using the full model of 1 is −8.6 kcal mol−1 (PW91) which observed within 5 h concomitant with the appearance of new
is more favorable than for the model 1-mod (0.1 kcal mol−1
,
products that were not characterized.
PW91). Accordingly, low temperatures and high CO pressures
should favor the formation of isocyanate complex 5.
The photolytic stability of isocyanate 5 was probed since the
photolysis of metal azide complexes is an established route to
prepare the metal nitride complexes.25,26 Furthermore, the
reductive decarbonylation of a niobium isocyanate complex
was shown to yield an anionic niobium nitride complex that is
isoelectronic with 1.27 In benzene and borosilicate glass, a
Nu½Mꢁ þ CO ! OCN–½Mꢁ
ð4Þ
Preparation and characterization of OCNMo(N[tBu]Ar)3, 5
In order to determine if 5 is stable towards CO loss and esta- sample of 5 was irradiated for 12 h with broadband visible
blish the precise spectral signatures of 5, a sample of 5 was light with a maximum at 419 nm. Under these conditions only
independently prepared by the treatment of 2 with a stoichio- residual 5 and the products associated with thermal decompo-
metric amount of AgOCN in THF (Scheme 1b). Following fil- sition were observed as a result of the heating of the sample
tration and solvent removal, the product was isolated in 77% induced by the lamps. A sample in pentane and quartz, irra-
yield as analytically pure crystals grown from diethyl ether– diated at 254 nm for 6 h, was found to slowly decarbonylate to
pentane solutions at −35 °C. 1H NMR spectroscopy in C6D6 produce 1 and CO in addition to the products of thermal degra-
revealed four broad resonances ranging from 28 to −10 ppm. dation. While the formation of small amounts of 1 could be
1
Evans method solution magnetic susceptibility measurements confirmed by H NMR spectroscopy, the formation of CO was
gave a μeff of 2.33μB, which is lower than the spin-only value confirmed by trapping the CO with Cp*RuCl(PCy3) to form
for an S = 1 system implying a degree of spin–orbit coupling. Cp*RuCl(PCy3)(CO) and measuring the conversion by analyzing
This value is lower than the magnetic susceptibility deter- the 31P NMR spectrum as was previously reported.28 A conver-
mined by variable-temperature SQUID magnetometry measure- sion of only 3% was determined from this NMR experiment.
ments (μeff of 2.66μB, see below), however differences between
When treated with KC8 in THF under an Ar atmosphere, iso-
solution and the solid state such as this have been previously cyanate 5 does not decarbonylate,6 but rather generates complex
observed with Mo complexes in similar ligand fields.20,21 DFT 2 and releases the cyanate anion. The potassium cyanate was
calculations of the paramagnetic NMR shifts22,23 for triplet 5 quantified by recovering the pentane insoluble portion of the
are in good agreement (slope = 0.74, correlation (r2) = 0.997) reaction mixture, dissolving it in water and precipitating the
with the observed resonances (Table 1). The assignments are cyanate as AgOCN in 60% yield. The clean reduction of 5 rep-
further confirmed by linewidth calculations which correlated resents an important step (Step 3) if the overall transformation
well (r2 = 0.999, slope = 0.57) with the experimental linewidths envisioned in eqn (1) or (2) is to be realized.
(Table 1) and indicate that the observed linewidths are domi-
During the manipulation of 5 it was noted that, upon
nated by the dipolar contribution—in other words the cooling, solid samples of
5
underwent
a
reversible
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thermochromic transformation and the origin of this effect is with two equivalents of CO.11,13 Additionally, one of the
described in detail in a later section.
anilide ligands has been transformed to an imide ligand, pre-
sumably as a result of effective tert-butyl cation dissociation.
The tert-butyl cation can serve as a proton source with con-
Attempted preparation of 5 from 1 and oxalyl chloride
In an effort to realize the formation of isocyanate 5 from comitant formation of isobutene.21,24 In this case, the proton
nitride 1 via an alternative route, 1 was treated with 0.5 equiva- was located in the electron density difference map on the
lents of oxalyl chloride in the presence of triisopropylsilyl tri- nitrogen of the oxamidide ligand, thereby completing the
flate (TIPSOTf) (Scheme 2). The reaction proceeded upon mass and charge balance.
warming in a dichloromethane solution. 1H NMR spectroscopy
of the recovered product revealed the loss of a tert-butyl group
Treatment of MouN containing complexes with CO
and 19F NMR spectroscopy showed the presence of a triflate In an effort to make the reduction potential of the MoVI center
group. IR data were consistent with incorporation of the oxalyl more accessible, we employed an analogue with a more elec-
group (vCvO, 1613 cm−1) and also contained a new NH stretch tronegative ligand set. The monofluorinated variant, Mo(N[R]-
at 3361 cm−1. Reduction of the material with KC8 in THF led ArF)3 (8, R = C(CD3)2CH3, ArF = 4-C6H4F), had been previously
to a dark blue, thermally sensitive solution. When the THF prepared and was known to cleave N2 to give the terminal
solution was stored at −35 °C no decomposition was observed nitride, NuMo(N[R]ArF)3 (9).16 DFT calculations predicted that
and after 36 h a mixture of dark blue and colorless crystals the reduction of 9 by CO to give the isocyanate linkage (eqn
had formed. The structure of the blue crystals was elucidated (4)) should be more favorable than for nitride 1 by 22 kcal
by X-ray diffraction and is shown in Fig. 3. The structure is mol−1, enough to overcome the predicted entropy that was cal-
consistent with the spectroscopic data for [7][OTf]2 with the culated with model complex 1-mod, 11.0 kcal mol−1 at
exception of the triflate signal, which is absent as a result of 298.15 K. Cyclic voltammetry (Fig. S8†) showed an anodic shift
loss of triflate as the coproduct KOTf upon reduction. The in the reduction potential by 0.2 V. The treatment of nitride 9
structure in Fig. 3 illustrates that the oxalyl moiety becomes with CO under the same set of conditions that were screened
incorporated into an oxamidide ligand which bridges the two with 1, however, resulted in no discernable reaction.
Mo centers and is the twice-protonated variant of the ligand
We had in hand a MoIV species, Cl2Mo(N[R]ArMeL)2 (10, R =
that is formed when either [Me2Si(η5-C5Me4)(η5-C5H3-3-tBu)- C(CD3)2CH3, ArMeL = 2-NMe2-5-MeC6H3), that could potentially
Hf]2(µ2,η2,η2-N2) or [(η5-C5Me4H)2Hf]2(µ2,η2,η2-N2) is treated be treated with an azide source to yield a new terminal nitride.
We postulated that the energetic cost of breaking the strong
MouN triple bond in the conversion of the terminal nitride to
the isocyanate could be offset by the formation of a Mo–Naniline
dative bond. DFT calculations were performed on the reaction
of N(N3)Mo(N[R]ArMeL)2 (see below) with CO to give OCN(N3)-
Mo(N[R]ArMeL)2 according to eqn (4) which accordingly was esti-
mated to be thermodynamically favorable by 21.2 kcal mol−1
according to the electronic energies. This is significantly more
favorable than the conversion of nitride 1 to isocyanate 5 is pre-
dicted to be. In fact, this energy is more comparable to that cal-
Scheme 2 Treatment of 1 with oxalyl chloride to give [7][OTf]2 and
culated, using the same method, for Mindiola’s recently
subsequent reduction to give 7.
reported reaction of the terminal VuN triple bond in 4 with CO
to form an isocyanate linkage (−41.9 kcal mol−1).7 With this
motivation, we set about preparing such a terminal nitride.
Compound 10 was prepared by treatment of MoCl3(THF)3
29
with LiN[R]ArMeL
in Et2O with a 2 : 3 stoichiometry. The
initial MoIII center is oxidized over the course of reaction to
30
MoIV. The source of the chlorine is presumably MoCl3(THF)3
which is present in excess under the optimized conditions.
Recrystallization from Et2O gave an analytically pure material
which had an Evans method magnetic susceptibility of μeff
=
2.31 μB which is lower than the S = 1 spin-only value 2.83 μB.
As in the case of 5, this value is anomalously low and is likely
not representative of the actual g value. In the absence of vari-
able temperature solid-state data, this value is taken as being
indicative of a paramagnetic system as opposed to a thermally
populated S = 0 system. Diffraction quality crystals were also
obtained from Et2O and the asymmetric unit is shown in
Fig. 4. The Mo center is six-coordinate with a pseudo-
Fig. 3 Thermal ellipsoid plot (50% probability) of 7 (where the two
halves of the molecule are related by an inversion center) with modelled
hydrogen atoms and all THF molecules omitted for clarity.
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following section, we turn to DFT in order to contrast the
possible mechanistic differences between the terminal nitrides
probed in this study and the neutral VV system, 4, that was pre-
viously shown to be successfully reduced by CO (Fig. 2b)7 in
order to account for the lack of reaction in the above systems.
Design of a new VII system for N2 activation
In the previous section, the reaction of CO with a MoVI nitride
(Fig. 1, Step 2) was focused on due to the precedent for N2 clea-
vage by MoIII centers, specifically with 2 and 8.12 An alternative
approach is to use systems in which the nitride-to-isocyanate
transformation has more precedent. Since two of the examples
of Step 2 involve a vanadium supported nitride,6,7 we sought
to prepare a low-valent V complex with the requisite number of
electrons such that two equivalents can reduce N2 by 6
electrons.32–35 There is precedent for N2 activation by low
valent VII complexes included in the work from the groups of
Gambarotta,32–34 Cloke,36 and Mindiola.35 A VII complex had
been previously prepared in the Cummins group with a
similar ligand set to [N[R]ArMeL],37 the N2 chemistry of which
was not explored. We sought to prepare the related low valent
vanadium complex supported by the monoanionic bidentate
ligand [N[R]ArMeL]−.
Fig. 4 Thermal ellipsoid plot (50% probability) of 10 with hydrogen
atoms omitted for clarity.
octahedral environment. The coordination sphere contains
two Mo–Nanilide (2.009(2) and 2.033(2) Å), two Mo–Naniline
(2.364(2) and 2.393(2) Å) and two Mo–Cl (2.3950(8) and 2.4216(8)
Å) bonds arranged such that one Nanilide is trans to one
N
aniline and the other is trans to a Cl as represented in Fig. 4.
Treatment of 10 with excess NaN3 resulted in the formation
of
(2061 cm−1) in the IR spectrum, formulated as N(N3)Mo(N[R]-
ArMeL 2 (11). Suitable crystals were grown from pentane and
a diamagnetic product with a single azide stretch
To prepare a pure material, a VIII species was first prepared
which was subsequently reduced to the desired VII species. A
)
the crystal structure (Fig. 5) revealed the hemilabile nature of
the amino-anilide ligand. Upon formation of the azide–nitride
product, one of the XL-type ligands31 remains bidentate, while
the other dissociates at the aniline-N leaving a pentacoordinate
Mo center with a pseudo square-pyramidal geometry com-
posed of one nitrido nitrogen (1.654(2) Å) two anilide nitro-
gens (2.011(2) and 2.036(2) Å), one azide nitrogen (2.119(2) Å)
and one aniline nitrogen (2.362(2) Å). It is noteworthy that if
reduction from MoVI to MoIV by CO can take place, then the
cost of breaking the MouN triple bond can be offset, not only
by the formation of the stable isocyanate linkage, but also by
the formation of the additional Mo–Naniline dative bond as
observed in 10. Treatment of this new terminal nitride
complex with CO did not, however, result in any reaction. In a
sample of ClV(N[R]ArMeL 2 (12) was prepared by treating
)
VCl3(THF)3 with two equivalents of the ligand in a frozen Et2O
slurry. The purified material had a room temperature magnetic
susceptibility, μeff, of 2.89 μB which compares well with the
spin-only value of 2.83 μB for an S = 1 system.
The desired product had paramagnetically broadened 1H
and 2H NMR spectra which could be fully assigned with the
aid of DFT calculations.22,23 Table 2 shows the assignment of
the 1H and 2H NMR spectra of 12. The strong correlation
between the calculated and experimental values indicates that
the relative distribution of unpaired electron density is cor-
rectly calculated by DFT in this case, although the non-unity
slope would indicate that the absolute value of the unpaired
electron density at each hydrogen is systematically in error. An
X-ray diffraction quality crystal of 12 was grown from Et2O and
the asymmetric unit is displayed in Fig. 6. Here it can be seen
that the vanadium(III) ion is pentacoordinate with one Cl
(2.338(1) Å), two Naniline (2.259(3) and 2.269(3) Å) and two
Table 2 Assignment of paramagnetic resonances (δ, ppm) in 1H NMR
spectra of 12 and 13 by correlating with DFT calculations
Position
12 (Exp.)
12 (DFT)
13 (Exp.)
13 (DFT)
tBu
NMe2
MeAr
9.15
−5.16
4.71
10.32
−7.26
3.99
38
68/105
1.62
61
100/193
0.59
H(3-Ar)
H(5-Ar)
−10.83
−17.32
0.98
0.96
0.60
−25.67
−31.49
−6.20
−11.1
−14.8
13.1
0.98
0.57
−12.6
−18.3
8.2
H(6-Ar)
Correlation (r2)
Slope
Fig. 5 Thermal ellipsoid plot (50% probability) of 11 with hydrogen
atoms omitted for clarity.
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material (Fig. 7). The crystal structure of 13 (from 13·1/
2 VCl2(TMEDA)2, Fig. 7) reveals a pseudotetrahedral coordi-
nation environment with inequivalent V–N distances (2.028(2)/
2.032(2) or 2.218(2)/2.200(2) Å for Nanilide or Naniline, respect-
ively). These values are slightly shorter and longer, respectively,
than the distances determined for 12. The angle between the
N2V planes is 68.68(5)° which is much more acute than in an
idealized tetrahedral geometry (90°) and reflects the restraint
imposed by the acute bite angle (∼78°) of the ortho-amino-
anilide ligand.
Although the reactions to produce 13 were initially per-
formed under Ar, no reaction with N2 was observed, even
under elevated pressures (up to 14 atm) or in the presence of a
reducing agent such as KC8. There is precedent for hetero-
bimetallic N2 activation and in some cases N2 cleavage when 2 is
employed as a co-reagent.39–41 An immediate color change was
observed when a solution of 13 was treated with a solution of 2
Fig. 6 Thermal ellipsoid plot (50% probability) of 12 with hydrogen under an atmosphere of N2. It has been proposed that the for-
mation of a reduced 2 (“2−”) leads to the facile reaction of 2
atoms omitted for clarity.
with N2 as evidenced by the reaction of 2 with N2 in the pres-
ence of Na.39 It is conceivable that a similar phenomenon is
Nanilide (1.944(3) 1.949(3) Å) atoms completing the coordi-
1
2
occurring here. H and H NMR studies revealed a new series
of paramagnetically broadened resonances and an Evans
method magnetic susceptibility measurement revealed a room
temperature susceptibility of 2.81 μB for the structural formula
(Ar[tBu]N)3Mo(μ-N2)V(N[R]ArMeL)2 (14) (cf. 2.83 μB for spin-only
S = 1). Prolonged drying under vacuum at room temperature
resulted in loss of N2. Crystallization from tetramethylsilane
(TMS) yielded a solid sample of the desired material. The
difficulties in manipulating this material, related to easy loss
of N2 and general sensitivity, resulted in only a reasonable
elemental analysis of 14 (0.95% error in hydrogen). The infra-
red absorption spectrum of 14 features a band at 1646 cm−1
that is not present in the infrared absorption spectra of either
2 or 13, and which we tentatively assign to the vNvN stretching
mode. This frequency lies between that of [(N2)Mo(N[tBu]Ar)3]−
nation sphere.
Ultimately, the desired product, 13, could be obtained in
pure form upon sodium amalgam reduction of 12. It should
be noted that the product can also be obtained using Na and
catalytic amounts of naphthalene in THF. Evans method room
temperature magnetic susceptibility measurements of 13
revealed a susceptibility that was lower than the spin-only
value (3.55 vs. 3.87 μB for S = 3/2). Again, the proton NMR res-
onances could be confidently assigned by correlating their
chemical shifts with the DFT predicted resonances. Here the
two aniline methyl groups are inequivalent, unlike in 12, an
observation which suggests a tighter binding of the bidentate
ligand.
Initial attempts to prepare 13 involved the treatment of the
38
VII salt VCl2(TMEDA)2 with two equivalents of LiN[R]ArMeL
(1761 cm−1 39
[tBu]N)3Mo(μ-N2)Nb(N[Np]Ar)3 (1564 cm−1, Np = neopentyl),40
(Ar[tBu]N)3Mo(μ-N2)Ti(N[tBu]Ar)3 (1575 cm−1 39
and (Ar[1-Ad]-
N)3Mo(μ-N2)U(N[tBu]Ar)3 (1568 cm−1, 1-Ad = 1-adamantyl),41
)
and those of the heterobimetallic systems (Ar-
in Et2O. 2H NMR spectroscopy revealed the presence of a
single paramagnetic species in the mixture that could be crys-
tallized out as diffraction quality crystals. Single crystal analy-
)
sis revealed that the desired product, V(N[R]ArMeL)2 (13) had
cocrystallized with half of an equivalent of the starting
and it is on par with (Ar[tBu]N)3Mo(μ-N2)SiMe3 (1650 cm−1 39
)
and (μ-N2)[Mo(N[tBu]Ar)3]2 (1630 cm−1).20
The single crystal structure of 14 was obtained from crystals
grown in tetramethylsilane. The structure, which is shown in
Fig. 8, confirms the bimetallic bridging-N2 nature of the
complex. The Mo–N bond is 1.802(3) Å and is shorter than the
Mo–N interatomic distance in both [(N2)Mo(N[tBu]Ar)3]− and
(μ-N2)[Mo(N[tBu]Ar)3]2 (1.84(1) and 1.868(1) Å, respectively),39
but longer than those in (Ar[tBu]N)3Mo(μ-N2)SiMe3 (1.753(2) Å)
and (Ar[tBu]N)3Mo(μ-N2)Ti(N[tBu]Ar)3 (1.787(3) Å).39 The N–N
bond is longer than in [(N2)Mo(N[tBu]Ar)3]− (1.210(5) vs.
1.17(1) Å) which is consistent with the lower energy vibrational
mode in 14 that is indicative of a weaker bond. Despite the
apparent degree of N2 activation, and the presence of the
requisite number of electrons for N2 cleavage, neither thermal
nor photochemical cleavage14,42 could be realized. Heating a
Fig. 7 Thermal ellipsoid plot (50% probability) of 13 with hydrogen
atoms, solvent of crystallization and disordered VCl2(TMEDA)2 omitted
for clarity.
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Table 3 DFT calculated electronic energy (ΔE, kcal mol−1), enthalpy
(ΔH, kcal mol−1), entropy (ΔS, kcal mol−1) and BSSE corrected Gibbs free
energy (ΔG, kcal mol−1) of terminal metal nitride reduction by carbon
monoxide (eqn (4))
Nitrido complex
ΔE
ΔH298.15
ΔS298.15
ΔG298.15
1 [Mo]
9 [Mo]
1-mod [Mo]
11 [Mo]
4 [V]
−8.6
−30.7
0.1
−0.5
−11.0
−11.0
11.5
−24.3
−41.9
−39.2
4-mod [V]
−38.8
−26.8
Fig. 8 Thermal ellipsoid plot (50% probability) of 14 with hydrogen
atoms and minor disordered component omitted for clarity.
toluene solution of 14 to 90 °C or irradiating a pentane solution
with an emission maximum of 254 nm or with an emission
maximum of 419 nm both resulted in the loss of N2 and liber-
ation of the starting complexes 2 and 13. Furthermore, treat-
ment of 14 with the strong reductant KC8 resulted in the
liberation of 13 and the generation of K[(N2)Mo(N[tBu]-Ar)3]. In
an effort to access the desired isocyanate directly, 14 was treated
with excess CO, resulting in the displacement of N2; here the
product of the reaction of tricoordinate molybdenum complex 2
with CO can be observed by 1H NMR spectroscopy.15
Fig. 10 DFT derived triplet (solid line) and singlet (hashed line) PES for
varying the NC distance in CO + nitride 4-mod. Only the parameter
(dNC) was fixed.
DFT investigations of step 2
In order to probe the mechanism of CO reduction of 1 to give
5, a potential energy surface (PES) was constructed where the
NC distance (dNC) was varied in both the triplet and the singlet
state (Fig. 9). In order to accomplish this in a computationally
crossing point calculation was attempted in order to determine
the crossing point of the two surfaces, but no solution was
obtained. Instead, the barrier to the reaction was estimated to
be 19 kcal mol−1 from the crossing point on the PESs. In an
attempt to obtain the same set of surfaces for a truncated
model of 4, NuV(nacnac′)(NMe2) (4-mod, nacnac′ = MeN-
(CH)3NMe), it was found that while the triplet surface followed
the same general trend, the singlet surface appeared to be
negative at all points up to and including the singlet/triplet
surface crossing (Fig. 10).
t
efficient manner, the aryl and Bu groups of 1 were replaced
with methyl groups (NuMo(NMe2)3, 1-mod). The overall reac-
tion electronic energy difference was slightly less favorable
with this substitution than with the full ligand set (see
Table 3). The singlet and triplet surfaces crossed in the vicinity
of 1.4 Å, the triplet being more stable at shorter distances and
the singlet at longer distances (Fig. 9). A minimum energy
Inspection of the geometries at various points reveals that
the CO molecule favorably binds to the V center as a first step
in the reaction.7 An isomerization to the isocyanate ensues
with an activation energy of 10.9 kcal mol−1, estimated from
the singlet PES, before crossing onto the triplet surface of the
final product. Interestingly, a similar pathway was proposed
for the extrusion of N2 from the azido precursor to 4, analo-
gous to the reverse of this reaction.7 This analysis suggests that
a thermodynamic driving force is insufficient for the forward
reaction to take place and that an accessible metal site might
be key to reducing the activation barrier for the formation of
the isocyanate in these cases. From a practical point of view,
caution must be used when choosing a ligand to support
this type of unsaturated metal site because CO insertion
into the metal–ligand bonds can easily become a competitive
reaction.43
Fig. 9 DFT derived triplet (solid line) and singlet (hashed line) PES for
varying the NC distance in CO + nitride 1-mod. Only the parameter
(dNC) was fixed.
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Thermochromism of solid-state 5
In order better to understand the origin of the solid-state
thermochromism, variable temperature visible absorption
spectra of 5 were obtained from 22 to −170 °C as a KBr diluted
solid mixture that was pressed into an optically transparent
pellet. These spectra are displayed in Fig. 13 and are compared
with the room temperature solution absorption spectrum
where it can be noted that the profile of the solid-state absorp-
tion spectrum at 22 °C is consistent with that of the solution
spectrum. The only changes that are observed upon lowering
the temperature are a narrowing of the absorption envelopes
for the peaks centered at 480 and 680 nm. As the changes are
quite subtle, a difference absorption spectrum, where the spec-
trum at 22 °C is used as the zero, is provided in Fig. 14. Here
During the manipulation of 5 it was noted that upon cooling,
solid samples underwent a reversible thermochromic trans-
formation as shown in Fig. 11. In order to determine the
origin of this property a variety of variable temperature studies
were performed. SQUID magnetometry was performed to
determine if the thermochromism was the result of a change
in spin state (triplet to singlet). The data, shown in Fig. 12,
were collected at two different field strengths. Although no
change in magnetic behavior was observed in the temperature
regime where the thermochromism was observed, a decay in
magnetic moment was observed below 50 K attributable to
either antiferromagnetic coupling between two metal centers
or to a zero-field splitting (ZFS). The data were fit to an S = 1
spin Hamiltonian for a single metal center (see Fig. 12) from
which the following parameters were extracted: g = 1.88 cm−1
and D = 37 cm−1. A ZFS value of this magnitude is suggestive
of a large anisotropy as indeed would be expected for the geo-
metry of 5, in fact similar ZFS values (g = 1.69 cm−1 and D =
42 cm−1) were found for μ-N2 complex 6 which has a geometry
between tetrahedral and trigonal-monopyramidal at each of
the molybdenum centers.14
Fig. 13 Visible absorption spectra of 5. Solution spectrum (hashed line)
in diethyl ether at 22 °C. Solid state spectra in KBr window at 22, −40,
−100, −140 and −170 °C.
Fig. 11 Representative photographs of β-5 and α-5.
Fig. 12 SQUID magnetometry of 5 as a function of temperature at
applied fields of 0.5 (open circles) and 1 T (closed circles). Red and blue
2
lines represent fits at 0.5 and 1 T from a spin Hamiltonian (H = D[Sz
−
Fig. 14 Solid state difference absorption spectra of 5 relative to spec-
trum at 22 °C. Solid state spectra in KBr window at 0, −40, −60, −80,
−100, −110, −120, −130, −140, −160 and −170 °C.
1/3S(S + 1) + E/D(Sx − Sy2)] + gβ S¯·B¯)44,45 for an S = 1 state with g =
2
1.88 and D = 36.6 cm−1 (solid blue).
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(Fig. 15) of 5 reveals a reversible solid–solid phase transition at
−128 °C (onset) with an enthalpy of transition of −4.3 kJ mol−1
when cooling from the β-modification (β-5) to the α modifi-
cation (α-5). There is a 20° hysteresis in the phase change
temperature; the phase transition in the reverse direction
occurs at −108 °C (onset) with an enthalpy of transition of
4.0 kJ mol−1. No shattering of the single crystals occurred at
−100 °C allowing a data set to be acquired of the high-temp-
erature phase, β-5. The asymmetric unit for β-5 is shown in
Fig. 16a. The geometry around Mo is typical for a MoIV species
with similar ligand sets.2,46,47 It should be noted that the
t
thermal ellipsoids on the Bu and isocyanate groups are quite
large; attempts to model these groups as disordered over two
positions did not lead to an improved model suggesting that
these groups may be somewhat dynamic at this temperature.
The lower temperature phase, α-5, was structurally investi-
gated by slowly cooling a crystal of β-5, that was heavily coated
in oil, through the phase change. Although some fracturing of
the crystal occurred upon phase change, a sufficiently large
portion of the crystal remained intact to allow for the collec-
tion of a data set. Both α-5 and β-5 crystallize in the same
space group (P21/c). Overall, there is a 2.9% decrease in the
volume of the unit cell that results from the a and c axes short-
ening by 5.3% and 3.2% respectively, the b axis lengthening by
6.2% and the β angle becoming more obtuse by 1.8%. Inspec-
tion of the single molecule in the asymmetric unit of α-5
(Fig. 16b) reveals that the thermal motion of the isocyanate
and tBu groups have decreased as a result of the conformation
becoming locked as compared to β-5. Beyond this, the major
Fig. 15 Differential scanning calorimetric curve of 5. Increasing temp-
erature denoted with red and decreasing temperature denoted with blue.
the effect of the narrowing of the bands is much more appar-
ent with the two isosbestic points (630 and 715 nm) separating
regions of increasing (670 nm) and decreasing (550 and
790 nm) absorption intensity. The narrowing of the bands and
resulting changes in absorption can be attributed to a loss of
thermally induced vibrational motion. TD-DFT calculations
were performed on 5 and the calculated spectrum, upon appli-
cation of a Lorentzian function (Fig. S21†), had features con-
sistent with both the solution and solid-state spectra of 5. The
absorption bands at 480 nm and 680 nm can be attributed to
transitions from the HOMO or HOMO−1 to the LUMO or a
combination of the LUMO+1 and LUMO+2. While these are
predominantly d–d transitions, the near-degenerate set of
HOMO and HOMO−1 both have significant overlap with the π
orbitals of the isocyanate group.
structural differences are the
Nanilide–Mo–NvC dihedral
angles and the Mo–NvC angle which are the result of a
change in the isocyanate position. Further subtle changes are
observed in the Mo coordination sphere but the majority of
the structural parameters are identical between the two phases
within 3σ. Considering the progressive change in the absorp-
X-ray diffraction quality crystals of 5 were grown from
pentane–THF solutions at −30 °C. Attempts to obtain a data
set at −177 °C resulted in the crystal fracturing. A DSC scan
tion spectrum as
a function of temperature, it seems
Fig. 16 Thermal ellipsoid plot (50% probability) of (a) β-5 (collected at 177 K) and (b) α-5 (collected at 100 K) with hydrogen atoms and minor dis-
ordered component omitted for clarity.
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reasonable that the thermal motion decreased as the tempera- or a Varian Mercury 300 spectrometer equipped with an
ture was lowered and then, upon reaching the phase change Oxford Instruments Ltd. superconducting magnet. Proton
temperature, the thermal motion was reduced to the point NMR spectra were referenced to residual C6D5H (7.16 ppm) or
where a void was created; the potential solvent accessible void residual CHCl3 (7.26 ppm). 19F NMR spectra were referenced
in β-5 is 102.7 Å3. The phase change occurs in response to this. externally to Et2O·BF3 (153.35 ppm) that had been previously
In fact, the percent filled space increases from 63.1% to 65.5% referenced to CFCl3. 2H NMR spectra were referenced to the
2
from β-5 to α-5 and the potential solvent accessible void naturally abundant H signals in the solvent. IR spectra were
becomes zero. The hysteresis in the phase change temperature collected on a Bruker Tensor 37 FT-IR spectrophotometer or a
is consistent with the packing having to change in order to Bruker Alpha FTIR spectrometer fitted with a diamond ATR
accommodate the density decrease associated with the increas- and stored in an N2 purged glovebox. Elemental analysis was
ing thermal motion. This type of phase change is consistent performed by Midwest Microlab, Indianapolis, IN.
with that of D-amphetamine sulfate which proceeds through a
Synthesis
similar order–disorder mechanism.48
The optimized geometry of 5 using single molecules from
OCNMo(N[tBu]Ar)3 (5). Solid 2 (1.15 g, 1.84 mmol) was
α-5 or β-5 as a starting point led to the same minimum energy added to a stirring suspension of AgOCN (0.28 g, 1.9 mmol) in
structure in both cases. The bond distances and angles around THF (40 mL). The mixture was allowed to stir for 2 h during
Mo are well reproduced with the exception of the Mo–NvC which time the solution darkened from the initial orange
angle which is calculated to be linear. The difference in elec- color. The solution was filtered through a bed of Celite. The
tronic energies for the two single point calculations, where the solvent was removed under vacuum and the solids were taken
Mo–NvC angle is fixed in at the crystallographically refined up in a minimal amount of ether. Hexane (10 mL) was added
angle or at the linear angle, is only 0.4 kcal mol−1 suggesting to the solution before reducing the volume by a third. The
that the observed angle in the crystal structure is simply the resulting solution was stored at −35 °C for 24 h. Dark crystals
result of crystal packing.
formed and were collected by vacuum filtration and washed
Based on the above data, the origin of the thermochromism with 6 mL of cold pentane. Further crops of crystals can be
in isocyanate complex 5 is the result of restricted vibrational obtained by reducing the volume and repeating the above pro-
motion in a denser low-temperature phase leading to a narrow- cedure. Yield: 0.95 g (77%, 1.4 mmol). mp. 154–156 °C (dec).
t
ing of the absorption envelopes.
1H NMR (C6D6, δ ppm) 27.14 (9H, Bu), −2.21 (6H, Me), −2.95
(2H, o-Ar), −7.84 (p-Ar). μeff = 2.33μB (2H NMR, C6D6 in THF,
298 K, Evans method). UV/vis λ = 457 nm (ε = 1900 L mol−1
cm−1) λ = 676 nm (ε = 550 L mol−1 cm−1), IR 2225 cm−1 vs
(OCN). Anal. Calcd for C37H54MoN4O: C, 66.65; H, 8.16; N,
8.40. Found: C, 66.44; H, 8.13; N, 8.28.
Experimental
General considerations
Unless otherwise stated, all manipulations were carried out
either in a Vacuum Atmospheres model MO-40M glovebox
Photolysis of OCNMo(N[tBu]Ar)3 (5)
under an atmosphere of N2 or using standard Schlenk tech- A 0.1211 g (0.1818 mmol) sample of 5 was dissolved in 50 mL
niques. All solvents were degassed and dried using a solvent- of pentane and placed in a quartz reaction flask. The quartz
purification system provided by Glass Contour. After purifi- reaction flask was attached through a bridge to a flask contain-
cation, all solvents were stored under an atmosphere of N2 ing 0.0741 g (0.0140 mmol) of Cp*RuCl(PCy3). The apparatus
over 4 Å molecular sieves. Deuterated benzene, deuterated was degassed with three freeze–pump–thaw cycles and left
toluene and deuterated chloroform (Cambridge Isotope Labs) under static vacuum. The portion of the apparatus containing
were dried by stirring over CaH2 for 24 h and was subsequently 5 was irradiated (16 bulbs at 254 nm) for 20 hours while the
vacuum-transferred onto 4 Å molecular sieves. MoCl3(THF)3,30 portion of the apparatus containing the Cp*RuCl(PCy3) was
(Et2O)Li[N(CCH3(CD3)2)ArMeL],29 Cp*RuCl(PCy3)49 and com- kept outside of the irradiation chamber. After 20 h, the
pounds 1,1 2,14 816 and 916 were prepared according to litera- portion of the apparatus containing the Cp*RuCl(PCy3) was
ture methods. All other reagents were used as supplied by the cooled with a liquid nitrogen bath causing all the volatiles
vendor without further purification. Celite 435 (EMD Chemi- from the reaction flask to be transferred. The flask was isolated
cals), alumina (Aldrich) and 4 Å molecular sieves were dried and allowed to warm to 20 °C with stirring. After achieving this
prior to use by heating at 200 °C for 48 h under dynamic temperature, the solvent was removed under dynamic vacuum.
vacuum. All glassware was oven dried at 220 °C prior to use.
Reduction of OCNMo(N[tBu]Ar)3 (5). An Ar sparged THF
All photochemical reactions were performed in a Rayonet solution (10 mL) of 5 (0.222 g, 0.333 mmol) was treated with
Photochemical Reactor (RPR-200, Southern New England Ultra KC8 (0.052 g, 0.382 mmol) and allowed to stir for 120 min
Violet Company) using either 16 RPR-2540 or 16 RPR-4190 under Ar. The THF mixture was filtered through Celite to
lamps. NMR spectra were obtained on either a Varian 500 remove any isocyanate salts and the isocyanate containing
Inova spectrometer equipped with an Oxford Instruments Ltd. Celite was set aside. The orange solution was recovered and
superconducting magnet, a Bruker 400-AVANCE spectrometer the solvent was removed. The residue was triturated with
equipped with a Magnex Scientific superconducting magnet, pentane and 0.167 g (0.267 mmol, 80.2%) of an orange powder
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was obtained. IR analysis revealed that no cyanate stretch was s, 2869 s, 2217 m (CD), 2155 w (CD), 2063 w (CD), 1589 s, 1489
present and 1H NMR spectroscopic analysis was consistent s, 1458 s, 1397 m, 1281 m, 1254 m, 1237 m, 1126 s, 1051 w,
with production of 2. The isocyanate containing Celite was 1002 s, 896 m, 807 m, 693 w, 633 w, 574 m, 459 m cm−1. Anal.
washed with water and treated with AgNO3. A pale pink solid, Calcd for C26H30D12MoN4Cl2: C, 52.98; H, 7.33; N, 9.51.
identified as AgOCN by IR (vOCN 2175 cm−1 (neat Di ATR) cf. Found: C, 53.05; H, 7.42; N, 9.52.
lit. 2170 cm−1 (KBr)50), precipitated out and was recovered
(0.0302 g, 0.202 mmol, 60.1%).
(N3)NMo(N[R]ArMeL)2 (11). Complex 10 (0.10 g, 0.17 mmol)
was dissolved in THF (5 mL) to which solid NaN3 (0.11 g,
[(OCNH)2(Mo(NAr)(N[tBu]Ar)2)2]OTf2 ([7][OTf]2). Solutions 1.7 mmol) was added. The mixture was allowed to stir for 16 h
of oxalyl chloride (0.0348 g, 0.274 mmol) and triisopropylsilyl during which time the solution turned from the initial dark
triflate (0.1684 g, 0.5496 mmol) were frozen, each in 2 mL of red/purple to red. The solution was filtered through a bed of
dichloromethane. The thawing solutions were mixed and Celite. The solvent was removed under vacuum and triturated
allowed to stir for 30 seconds before the resulting mixture was three times with pentane. The material was recrystallized from
frozen. This mixture was added to a thawing solution of 1 pentane to yield diffraction quality crystals. Yield: 0.06 g (60%,
1
(0.3506 g, 0.5495 mmol) in 3 mL of dichloromethane and 0.1 mmol). H NMR (C6D6, δ ppm) 6.94 (1H, d, HAr), 6.87 (1H,
allowed to stir while warming to 21 °C. After 30 minutes, the s, HAr), 6.58 (1H, d, HAr), 6.41 (1H, br, HAr), 6.30 (1H, br, HAr),
solvent was removed and the product was triturated twice with 5.14 (1H, br, HAr), 2.45 (6H, s, NMe2), 2.27 (3H, s, MeAr), 2.20
t
diethyl ether and twice with n-hexane. n-Hexane was added (6H, br, NMe2), 2.01 (3H, br, MeAr), 1.68 (3H, br, Bu), 1.3 (3H,
and the orange precipitate was collected on a frit, washed with s, tBu). 2H NMR (THF, δ ppm) 1.53 (12H, tBu). 13C NMR
additional n-hexane and dried under vacuum. Yield 0.3768 g (CDCl3, δ ppm) 148.4, 143.4, 142.0, 138.8, 122.6, 122.0, 119.4,
1
(90.26%, 0.2480 mmol). H NMR (C6D6, δ ppm) 7.93 (1H, br, 117.3, 116.3, 113.6, 62.0, 48.8 (br), 44.4, 32.8, 32 (br), 29.8,
NH), 6.96 (1H, p-Ar′), 6.90 (2H, o-Ar′), 6.74 (2H, br, Ar), 6.67 25.6, 21.7, 21.0, 15.3. IR 2965 m, 2925 s, 2865 m, 2826 m, 2778
(2H, br, Ar), 6.46 (2H, br, Ar), 2.27 (12H, CH3Ar), 2.23 (6H, w, 2221 w, 2057 vs (NNN), 1591 m, 1517 w, 1489 s, 1457 m,
CH3Ar′), 1.31 (18H, CH3Ar). 19F NMR (C6D6, δ ppm) −79 (1F 1332 m, 1280 m, 1167 m, 1129 m, 1032 m, 911 m, 878 m,
O3SCF3). IR 3360 w (NH), 2977 s, 2921 m, 2863 w, 1613 vs 806 m, 391 w cm−1. Anal. Calcd for C26H30D12MoN8: C, 54.36;
(CO), 1467 m, 1294 m, 1232 s, 1218 s, 1161 s, 1025 s, 932 w, H, 7.52; N, 19.50. Found: C, 53.98; H, 7.35; N, 19.42.
634 m, 467 w cm−1. Anal. Calcd for C34H46MoN4O4F3S: C,
ClV(N[R]ArMeL)2 (12). An Et2O (15 mL) suspension of
53.75; H, 6.10; N, 7.37. Found: C, 53.49; H, 6.15; N, 7.22. A VCl3(THF)3 (1.0 g, 2.7 mmol) was frozen. Solid (Et2O)Li[N(R)-
diffraction quality crystal of the product could not be obtained, ArMeL] (1.55 g, 5.31 mmol) was added to the frozen mixture
however reduction of this material led to a highly crystalline and the sample was allowed to warm to room temperature with
mixture. A solution of [7][OTf]2 (0.05 g, 0.0335 mmol) in THF stirring. Stirring was continued for 2 h after reaching room
was treated with 0.0091 g (0.0669 mmol) of KC8. The initially temperature. The bright green solution was filtered through
red solution turned dark blue within two minutes. The solu- Celite and the Celite was rinsed with Et2O. The total volume of
tion was filtered through Celite to remove the graphite. the liquid was reduced to 10 mL and transferred to a −35 °C
Attempts to remove the solvent or further purify the product freezer. A bright green solid was recovered by filtration and
led to decomposition. Storage of the filtered blue solution at was rinsed with pentane and dried under vacuum. The mother
−35 °C led to the formation of large, diffraction quality, blue liquor was returned to the freezer for additional fractions.
crystals mixed with small transparent crystals (presumably Yield 0.94 g (69%, 1.8 mmol). 1H NMR (C6D6, δ ppm) 9.15 (br),
K[O3SCF3]) within 12 h.
Cl2Mo(N[R]ArMeL 2
4.71 (br), 0.98 (br), −5 (br), −10.8 (br), −17.4 (br). 2H NMR
t
)
(10). MoCl3(THF)3 (4.05 g, 9.67 mmol) (C6H6, δ ppm) 9.25 (12H, Bu). μeff = 2.89μB (1H NMR, HMDSO
was frozen in Ar sparged Et2O (60 mL). To this was added in C6D6, 298 K, Evans method). IR 2958 m, 2919 s, 2866 m,
3.98 g of (Et2O)Li[N(R)ArMeL] (13.6 mmol). The mixture was 2217 m, 2151 w, 2063 w, 1586 m, 1482 s, 1401 m, 1280 m,
allowed to warm with stirring for 6 h during which time the 1246 m, 1173 m, 1173 s, 1141 s, 1050 w, 1013 w, 908 m, 797 m,
solution turned from the initial orange to deep red. The solu- 734 w, 632 w, 575 m, 525 w, 450 m cm−1. Anal. Calcd for
tion was filtered through a bed of Celite which was sub- C26H30D12VN4Cl: C, 61.36; H, 8.51; N, 11.01. Found: C, 61.33;
sequently rinsed with Et2O. The solvent was removed under H, 8.84; N, 11.09.
vacuum and the solids (crude: 3.44 g) were taken up in a
V(N[R]ArMeL)2 (13). A THF (5 mL) solution of 12 (0.3 g,
minimal amount of THF and Et2O (50/50). The resulting solu- 0.6 mmol) was added to Na{Hg} (0.025 g in 5 g) and was
tion was stored at −35 °C for 24 h. Dark crystals formed and stirred vigorously under N2 for 8 h. The amalgam was allowed
were collected by vacuum filtration and washed with 6 mL of to settle, and the solution was decanted and filtered through
cold pentane. Further crops of crystals were obtained by redu- Celite. The solvent was removed and the material was taken up
cing the volume and repeating the above procedure. Yield: in benzene and the solution was filtered through Celite.
1
2.86 g (71.3% based on ligand, 4.85 mmol). H NMR (C6D6, δ Removal of the solvent afforded 0.26 g (92% yield, 0.55 mmol)
1
ppm) 19.2, 15.0, −1.0, −4.1, −8.5, −25.7, −38.7, −56.1. 2H of an olive green powder. H NMR (C6D6, δ ppm) 105 (br), 68
t
t
2
NMR (THF, δ ppm) 18.3 (3H, Bu), 17.8 (3H, Bu), 14.2 (3H, (br), 38 (br), 13.1 (br), 0.6 (br), −11.1 (br), −14.8 (br). H NMR
tBu), 14.0 (3H, Bu). μeff = 2.31μB (1H NMR, hexamethyldisilox- (C6H6, δ ppm) 37.8 (12H, Bu). μeff = 3.55μB (1H NMR, HMDSO
t
t
ane (HMDSO) in C6D6, 298 K, Evans method). IR 2921 s, 2902 in C6D6, 298 K, Evans method). IR 2952 s, 2919 s, 2862 m,
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2208 m, 2144 w, 2055 w, 1586 s, 1481 s, 1449 m, 1402 s, 1314 those of Perdew and Wang (PW-LDA, PW91).17 In all cases
s, 1290 s, 1174 m, 1152 m, 1097 w, 1051 w, 1009 m, 907 m, 838 where a crystal structure was determined, the coordination
w, 783 m, 631 w, 578 m, 449 w cm−1. Anal. Calcd for geometry was reproduced by this method within 0.1 Å for
C26H30D12VN4: C, 65.95; H, 9.17; N, 11.83. Found: C, 65.92; H, bond distances, 1° for bond angles and 2° for dihedral angles.
9.26; N, 11.87.
The one exception was in the calculated geometry of 5 where
(14). A green solution of the Mo–NvC bond angle deviates from the crystal structure
(Ar[tBu]N)3Mo(μ-N2)V(N[R]ArMeL 2
)
complex 13 (0.88 g, 1.9 mmol) in THF (20 mL) was added to an and was determined to be the result of packing effects in the
orange THF (20 mL) solution of 2 (1.28 g, 2.05 mmol). The crystal structure (see Discussion in text). For structures of 12
mixture immediately turned green/brown and was allowed to and 13, only the hydrogen atomic coordinates were optimized.
stir for 12 h. The solvent was removed under vacuum at such a In the case of thermodynamic calculations, the hybrid func-
rate that the sample was kept very cold. A solid foam was tional (30% HF)19 of Becke (B88)18 was used for exchange and
obtained. A solid material was obtained upon treatment with that of Perdew and Wang (PW91)17 for the correlation. In
tetramethylsilane. The solid was dissolved in tetramethylsilane addition, all calculations were carried out using the Zero-Order
and stored at −35 °C to yield diffraction quality crystals. Yield: Regular Approximation (ZORA),52,53 in conjunction with the
1.45 g (63%, 1.20 mmol). 1H NMR (C6D6, δ ppm) 28.2, 10.1, SARC-TZV(2pf) basis set for the transition metal atoms, the
2
6.46, 5.5, 5.3, 3.14, 2.5, 1.86, 0.0 (SiMe4), −7.5, −9.6. H NMR SARC-TZV basis set for the hydrogen atoms, and SARC-TZV(p)
t
(C6H6, δ ppm) 10.5 (12H, Bu). μeff = 2.81μB (2H NMR, C6D6 in set for all other atoms.54 Spin-restricted and unrestricted
THF, 298 K, Evans method). IR 2960 m, 2916 m, 2859 m, 2219 Kohn–Sham determinants were chosen to describe the closed
w, 1633 s (N–N), 1583 s, 1487 m, 1455 m, 1285 m, 1178 m, shell and open shell wavefunctions respectively, employing
1151 m, 934 m, 846 w, 685 m cm−1. Anal. Calcd for the RI approximation and the tight SCF convergence criteria
C62H84D12MoVN9·(SiC4H12)2 (2SiMe4): C, 64.54; H, 9.37; N, provided by ORCA.
9.68. Found: C, 63.77; H, 8.42; N, 9.77.
NMR calculations were performed with the EPR and NMR
modules and the analysis to find the observed shift, δ was per-
formed as outlined by Bagno using eqn (5), where δo is deter-
Crystallography
Crystals were mounted on MiTGen mounts using Paratone-N mined according to eqn (6), δFC is determined from eqn (7)
oil (Hampton). The structure of β-5 was determined at 177 K. and δPC is considered to be negligible as it only is appreciable
All other structures were collected at 100 K. Preliminary frames within a few angstroms of the paramagnetic center.22,23 In eqn
were obtained in order to determine the unit cell. Diffraction (6), the orbital component, σorb, of the diamagnetic shielding
data (φ- and ω-scans) were collected on either a Siemens Plat- was determined by performing an NMR calculation on the
form three-circle diffractometer coupled to a Bruker-AXS Smart paramagnetic complex and the overall chemical shift, δorb was
Apex CCD detector with graphite-monochromated Mo Kα radi- determined using TMS as the reference material, σorb, and
ation (λ = 0.71073 Å), performing ω- and φ-scans or a Bruker- assuming that the diamagnetic shielding can be approximated
AXS X8 Kappa Duo diffractometer coupled to a Smart APEX II by the chemical shift. The Fermi contact term, δFC, was calcu-
CCD detector with Mo Kα radiation (λ = 0.71073 Å) from a IμS lated by performing an EPR calculation on the paramagnetic
microfocus source. Absorption and other corrections were complex and extracting the isotropic hyperfine coupling con-
applied using SADABS. The structures were solved by direct stant, A, in frequency units and applying it to eqn (7), where γI
methods using SHELXS and refined against F2 on all data by is magnetogyric ratio of element I, giso is the isotropic g-factor,
full-matrix least squares as implemented in SHELXL-97. All k is the Boltzmann constant, T is temperature, S is the spin
non-hydrogen atoms of the framework were refined anisotropi- and μB represents the Bohr magneton. Linewidths were calcu-
cally. Hydrogen atoms pertaining to the ligand were included lated according to the Solomon–Bloembergen equation using
in the model at geometrically calculated positions using a a rotational correlation time of 5 × 10−11 s estimated from the
riding model.
Debye equation (τr = ηVm/kT) with a molecular volume esti-
mated from the crystallographic structure and an electronic
relaxation correlation time (τS) of 5 × 10−12 s. The spin density
SQUID magnetometry
DC-SQUID data were obtained on a sample packed in a cellu- was assumed to reside on the metal atom, consistent with the
lose capsule. Data was collected from 2 K to 300 K at field calculated spin density.
strengths of 0.5 and 1 T. The data were corrected for the mag-
δ ¼ δo þ δFC þ δPC
ð5Þ
netic susceptibility of the sample holder and the diamagnetic
contribution from the sample. The data were fit to a spin
Hamiltonian using Julx.45
δorb ¼ σref ꢀ σorb ꢂ δo
ð6Þ
2π
γI
SðS þ 1Þ
2kT
Calculations
δFC
¼
g
isoμBA
ð7Þ
Calculations were performed using the ORCA 2.9 quantum
chemistry program package from the development team at the
TDDFT was used to calculate the 100 lowest energy singlet
Max Planck Institute for Bioinorganic Chemistry.51 For geome- and triplet excitations. The potential energy surfaces were con-
try optimizations the LDA and GGA functionals employed were structed by allowing all parameters to relax as a single
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parameter (the NC distance for reactions according to eqn (4)
and the Mo–NvC bond angle for the PES for the Mo–NvC
bond angle in 5) was varied.
5 P. M. Schalke, in Ullmann’s Encyclopedia of Industrial Chem-
istry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim,
Germany, 2000, pp. 669–672.
6 J. S. Silvia and C. C. Cummins, J. Am. Chem. Soc., 2009,
131, 446–447.
7 B. L. Tran, M. Pink, X. Gao, H. Park and D. J. Mindiola,
J. Am. Chem. Soc., 2010, 132, 1458–1459.
Conclusions
8 B. Askevold, J. T. Nieto, S. Tussupbayev, M. Diefenbach,
E. Herdtweck, M. C. Holthausen and S. Schneider, Nat.
Chem., 2011, 3, 532–537.
9 J. P. Reeds, B. L. Yonke, P. Y. Zavalij and L. R. Sita, J. Am.
Chem. Soc., 2011, 133, 18602–18605.
10 D. J. Knobloch, E. Lobkovsky and P. J. Chirik, Nat. Chem.,
2009, 2, 30–35.
11 D. J. Knobloch, E. Lobkovsky and P. J. Chirik, J. Am. Chem.
Soc., 2010, 132, 15340–15350.
12 C. E. Laplaza and C. C. Cummins, Science, 1995, 268,
861–863.
13 D. J. Knobloch, E. Lobkovsky and P. J. Chirik, J. Am. Chem.
Soc., 2010, 132, 10553–10564.
14 J. J. Curley, T. R. Cook, S. Y. Reece, P. Müller and
C. C. Cummins, J. Am. Chem. Soc., 2008, 130, 9394–9405.
15 J. C. Peters, A. L. Odom and C. C. Cummins, Chem.
Commun., 1997, 1995–1996.
16 M. J. A. Johnson, P. M. Lee, A. L. Odom, W. M. Davis and
C. C. Cummins, Angew. Chem., Int. Ed., 1997, 36, 87–91.
17 J. P. Perdew and Y. Wang, Phys. Rev. B: Condens. Matter,
1992, 45, 13244–13249.
We have explored an atom efficient cycle for the conversion of
ubiquitous small molecules, CO and N2, into the industrially
relevant cyanate ion. A variety of Mo and V complexes were
investigated with regard to their ability to mediate the various
steps in this cycle. Three-coordinate Mo complexes, which had
been shown previously to split N2 and form terminal nitrido
complexes, were found to be unreactive towards the two-elec-
tron reductant CO, despite the transformation being predicted
to be thermodynamically favorable by DFT calculations in one
of the cases. A new Mo–nitride complex was prepared (with
azide as the nitrogen source) that was similarly found not to
be reactive with CO, despite indications once more from
quantum chemical calculations that isocyanate formation
would be favorable. DFT calculations were used to rationalize
the difference between these systems and systems that are
known to participate in nitride–CO coupling to isocyanate. It
was found that the CO reduction of the vanadium nitride
model complex proceeded through a metal carbonyl inter-
mediate which isomerized to give the isocyanate. In this way, a
large reaction barrier was avoided. One possible approach,
then, is to design systems that maintain an accessible metal
center having CO affinity in order to mediate the reaction. This
will have to be balanced with a choice of ligands that do not
favor CO insertion into the metal–ligand bond. Additionally,
the origin of the thermochromism of a molybdenum isocya-
nate complex was elucidated and was found to be the result of
restricted vibrational motion in a denser low-temperature
phase leading to narrow absorption envelopes.
18 A. D. Becke, Phys. Rev. A, 1988, 38, 3098–3100.
19 A. D. Becke, J. Chem. Phys., 1993, 98, 5648–5652.
20 C. E. Laplaza, M. J. A. Johnson, J. C. Peters, A. L. Odom,
E. Kim, C. C. Cummins, G. N. George and I. J. Pickering,
J. Am. Chem. Soc., 1996, 118, 8623–8638.
21 A. R. Johnson, W. M. Davis, C. C. Cummins, S. Serron,
S. P. Nolan, D. G. Musaev and K. Morokuma, J. Am. Chem.
Soc., 1998, 120, 2071–2085.
22 F. Rastrelli and A. Bagno, Magn. Reson. Chem., 2010,
48(Suppl 1), S132–S141.
Acknowledgements
23 F. Rastrelli and A. Bagno, Chem.–Eur. J., 2009, 15, 7990–
8004.
24 J. C. Peters, L. M. Baraldo, T. A. Baker, A. R. Johnson and
C. C. Cummins, J. Organomet. Chem., 1999, 591, 24–35.
25 R. A. Eikey and M. M. Abu-Omar, Coord. Chem. Rev., 2003,
243, 83–124.
This material is based upon work supported by the National
Science Foundation under CHE-1111357 as well as the
National Science and Engineering Research Council of Canada
(NSERC-PDF – AFC).
26 J. Strähle, Z. Anorg. Allg. Chem., 2007, 633, 1757–1761.
27 A. L. Odom, C. C. Cummins and M. G. Fickes, Chem.
Commun., 1997, 1993–1994.
28 J. S. Silvia and C. C. Cummins, J. Am. Chem. Soc., 2010,
132, 2169–2171.
29 A. R. Fox, J. S. Silvia, E. M. Townsend and C. C. Cummins,
C. R. Chim., 2010, 13, 781–789.
30 F. Stoffelbach, D. Saurenz and R. Poli, Eur. J. Inorg. Chem.,
2001, 2001, 2699–2703.
Notes and references
1 J. J. Curley, E. L. Sceats and C. C. Cummins, J. Am. Chem.
Soc., 2006, 128, 14036–14037.
2 J. J. Curley, A. F. Cozzolino and C. C. Cummins, Dalton
Trans., 2011, 40, 2429–2432.
3 M. W. Chase Jr., J. Phys. Chem. Ref. Data Monogr., 1998, 9,
1–1951.
31 M. L. H. Green, J. Organomet. Chem., 1995, 500, 127–148.
4 C. E. Vanderzee and R. A. Myers, J. Phys. Chem., 1961, 65, 32 P. Berno, S. Hao, R. K. Minhas and S. Gambarotta, J. Am.
153–158.
Chem. Soc., 1994, 116, 7417–7418.
This journal is © The Royal Society of Chemistry 2014
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View Article Online
Paper
Dalton Transactions
33 J. J. H. Edema, A. Meetsma and S. Gambarotta, J. Am. 44 O. Kahn, in Molecular Magnetism, VCH Publishers Inc.,
Chem. Soc., 1989, 111, 6878–6880. Weinheim, Germany, 1993, p. 17.
34 I. Vidyaratne, P. Crewdson, E. Lefebvre and S. Gambarotta, 45 E. Bill, JulX: A Program for the Simulation and Ana-
Inorg. Chem., 2007, 46, 8836–8842.
35 B. L. Tran, B. Pinter, A. J. Nichols, F. T. Konopka,
R. Thompson, C.-H. Chen, J. Krzystek, A. Ozarowski,
lysis of Magnetic Susceptibility Data. V. 1.4, MPI for
Chemical Energy Conversion, Mülheim an der Ruhr,
2008.
J. Telser, M.-H. Baik, K. Meyer and D. J. Mindiola, J. Am. 46 M. Temprado, J. E. McDonough, A. Mendiratta, Y.-C. Tsai,
Chem. Soc., 2012, 134, 13035–13045.
G. C. Fortman, C. C. Cummins, E. V. Rybak-Akimova and
C. D. Hoff, Inorg. Chem., 2008, 47, 9380–9389.
47 A. Fürstner, C. Mathes and C. W. Lehmann, J. Am. Chem.
Soc., 1999, 121, 9453–9454.
36 G. K. B. Clentsmith, V. M. E. Bates, P. B. Hitchcock and
F. G. N. Cloke, J. Am. Chem. Soc., 1999, 121, 10444–10445.
37 M. J. A. Johnson, Synthesis and Reactivity of Early Transition
Metal Complexes Supported by Sterically Demanding Amido 48 K. Pogorzelec-Glaser, J. Kaszyńska, A. Rachocki, J. Tritt-Goc,
Ligands, PhD, Massachusetts Institute of Technology, 1998,
N. Piślewski and A. Pietraszko, New J. Chem., 2009, 33,
p. 240.
1894.
38 J. J. H. Edema, W. Stauthamer, F. Van Bolhuis, 49 B. K. Campion, R. H. Heyn and T. D. Tilley, J. Chem. Soc.,
S. Gambarotta, W. J. J. Smeets and A. L. Spek, Inorg. Chem.,
1990, 29, 1302–1306.
Chem. Commun., 1988, 278.
50 F. A. Miller and C. H. Wilkins, Anal. Chem., 1952, 24, 1253–
39 J. C. Peters, J.-P. F. Cherry, J. C. Thomas, L. Baraldo,
1294.
D. J. Mindiola, W. M. Davis and C. C. Cummins, J. Am. 51 F. Neese, ORCA – an ab initio, Density Functional and
Chem. Soc., 1999, 121, 10053–10067.
40 J. S. Figueroa, N. A. Piro, C. R. Clough and C. C. Cummins,
J. Am. Chem. Soc., 2006, 128, 940–950.
41 A. L. Odom, P. L. Arnold and C. C. Cummins, J. Am. Chem.
Soc., 1998, 120, 5836–5837.
42 A. S. Huss, J. J. Curley, C. C. Cummins and D. A. Blank,
J. Phys. Chem. B, 2013, 117, 1429–1436.
Semiempirical program package, Version 2.9.0, MPI for
Bioinorganic Chemistry, Mülheim an der Ruhr, 2013.
52 E. van Lenthe, J. Baerends Evert and J. G. Snijders, J. Chem.
Phys., 1993, 99, 4597–4610.
53 J. L. Heully, I. Lindgren, E. Lindroth, S. Lundqvist and
A. M. Maartensson-Pendrill, J. Phys. B: At. Mol. Phys., 1986,
19, 2799–2815.
43 M. H. Chisholm, C. E. Hammond and J. C. Huffman, 54 D. A. Pantazis, X.-Y. Chen, C. R. Landis and F. Neese,
Organometallics, 1987, 6, 210–211. J. Chem. Theory Comput., 2008, 4, 908–919.
Dalton Trans.
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