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Metal-ligand bonds / Bond strength / Bond length / Since then, the notion of a strict division has gradually
MOF / Coordination compounds disappeared as the grey zone in-between the two extremes
is large, important and expanding. Thus the view has
Abstract. Structure data on metal-alkoxides, metal-alco- evolved that such distinction, regardless of its scientific
hol, metal-carboxylates, metal-carboxylic acid, metal-azo- merits, is indeed impossible to maintain for nomenclature
late and metal-azole coordination compounds from the and terminology purposes [3].
Cambridge Structural Database (CSD) were analysed in The present study will attempt to address the bond
terms of bond lengths. In general the anionic ligands form strength question by analysing in detail data from the
shorter metal-ligand bonds by about 0.02–0.05 Å com- Cambridge Structural Database, CSD [4]. In this corre-
pared to neutral ligands, a clear indication of a charge con- spondence bond energy, stability constants and bond va-
tribution to the bonding interactions. This small difference lences will be used to assess the bond strength.
is not, however, deemed as sufficient to generate two dis- Although there seems to be no similar detailed study
tinct classes of metal-ligand bonding. Instead, the anionic focusing on the metal-ligand bond, a general survey on
ligands can be viewed as having “charge assisted” metal- bond lengths in coordination compounds was recently
ligand bonding, corresponding to the same term used for published [5].
“charge-assisted hydrogen bonding”.
1.1 IUPAC recommendations
1. Introduction and background As noted above, for terminology purposes a distinction ac-
cording to charge of the ligand is not practical, and the dis-
While carbon-carbon bond lengths and bond strengths in agreement over this issue has in fact been resolved by
terms of bond enthalpies are well established and can be IUPAC. Recently provisional recommendations, defining co-
found in 1st year university chemistry textbooks, useful ordination polymers as an overall substance class, coordina-
and accurate data of the same type for metal-ligand bond tion networks as a subclass and metal-organic frameworks as
strengths are notoriously difficult to find in the same type special case of coordination networks, the definition relying
of literature. on structure rather than on bonding, were published [6].
In light of the recent proposition that bonds in coordi-
nation compounds can be divided into two classes based
on bond strengths, namely those with neutral ligands and 1.2 Coordination bonds and valence bond theory
weak bonds, such as ammonia in the classical Werner The scientific question, however, remains challenging and
complex [PtCl2(NH3)2], and those with anionic ligands deserves a detailed study in order to be answered. Are
and strong bonds that can also be thought of as salts, such carboxylate coordination entities and pyridine coordination
as [Cu2(O2CCH3)4] [1], it seemed important to investigate entities indeed so different in bonding that a clear distinc-
if there is any structural evidence supporting this sugges- tion can be made between them?
tion. This classification has especially concerned materials The argument usually put forward to support their dif-
with metal-ligand bonding extending in 1, 2, or 3 dimen- ference is based on bond valence theory [7]. Formal bond
sions, thus dividing these into less stable coordination valence values are assigned according to the valence of
polymers and highly stable metal-organic frameworks, a the atoms and the total charge of the ligand.
view contested by Robson [2]. A metal has a valence of þn and an imidazolate ligand
a valence of 1, they can thus form a bond of valence,
1 see Fig. 1. An imidazole or pyridine ligand is neutral
* Correspondence author (e-mail: ohrstrom@chalmers.se) and has thus valence zero and the total metal-ligand bond
For supplementary information see online version. valence becomes zero [8].
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312 A. Nimmermark, L. hrström and J. Reedijk
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Metal-ligand bond strengths: A CSD study 313
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314 A. Nimmermark, L. hrström and J. Reedijk
2.2 Metal carboxylic acid and carboxylate systems The imidazolate systems have a great advantage in that
there is no possible protonation state ambiguity for the
In this case only few data are available on the protonated N-substituted metal-imidazole-R compounds, and as the N
systems. What we can clearly state is that for copper, has only one directed lone pair, therefore also hydrogen
where we have at least 7 structures fulfilling all our quality bonding effects are hardly present. For four-coordinated
criteria, the shortest Cu––O(H) bond is 1.93 Å (bis(m-asparta- zinc we found a good number of data in the CSD which
me)tetrakis(aspartame)diaquatricopper(II) pentahydrate, are plotted in Fig. 6. Total number of hits are for Zn-Him
MAZSAI) [20], which is actually shorter than the peak ¼ 318, Zn-Rim ¼ 656, and Zn-im-Zn ¼ 60. The complete
copper-carboxylate distance, 1.95 Å (Fig. S.2). However, data collection is found in Table S.5.
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Metal-ligand bond strengths: A CSD study 315
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316 A. Nimmermark, L. hrström and J. Reedijk
these to the imidazolates and carboxylates. In Fig. 8 we energy, the charge-dipole interaction and the ionic interac-
have plotted the Zn––N distances for four-coordinated tion. Assuming a net charge of þ1 on the metal and using
Zn(II) for both pyridine and imidazole, as well as for imi- either the measured dipole moment of simple model li-
dazolates and Zn––O for carboxylates. The number of hits gands or a charge of 1, we can calculate the absolute
was 752 for pyridine, 1549 for carboxylates, 318 for imi- interaction energy and the change if we increase the bond
dazoles and 60 for the imidazolates. length. For a distance difference of 0.05 Å such data are
First we note that the carboxylate distances are the presented in Table 1.
shortest, 1.96 Å compared to 1.99 for the imidazolates, but We note first that the charge-dipole estimates come clo-
considering that the covalent radius of nitrogen is 0.05 Å ser to the expected metal-ligand bond energies than the
longer than for oxygen (0.71 Å versus 0.66 Å) this differ- charge-charge model that gives very high values indeed.
ence is hardly significant. More interesting, and more rele- This does not mean the former is necessarily a better de-
vant for the aim of this study, is the pronounced difference scription, but just that for the Coulombic interaction we
between the most probable bond distances for pyridines need at least to include some repulsion between ligands to
and imidazoles: 2.05–2.01 ¼ 0.04 Å, i.e. of the same or- make reasonable bond energy estimates. The changes on
der as observed between ligands with similar looking an- extending the bonds 0.05 Å are not dramatically different,
ions and neutral forms. however, and amounts to about a 5% loss of bond energy
The fact that the pyridine group is slightly more steri- for the charge-dipole model and 2.5% for the ionic model,
cally demanding may perhaps be the simplest explanation the difference being consistent with their different depen-
for this small difference, and could suggest that steric bulk dencies on r.
can give effects of the same order of magnitude as a neu- While this may not sound dramatic, we should bear in
tral versus a charged ligand. Moreover, we cannot comple- mind that in chemical reactions bonds are both broken and
tely rule out that the difference between carboxylate and formed and it is the bond energy difference that will ulti-
pyridine, 0.09 Å, is the product of a similar steric effect. mately affect the thermodynamic outcome.
As can also be clearly seen, the difference between pyri-
dine and imidazole complexes is greater than that between
imidazoles and imidazolates.
3. Conclusions
2.6 Correlation of bond strengths and lengths We observe a decrease in bond length of 0.02–0.05 Å
when a neutral ligand binding with N or O becomes
Apart from bond valence calculations another way to cor-
charged minus one, the smaller values corresponding to
relate bond lengths and bond strengths is to use the har-
the Zn-imidazolates. A difference of the same order of
monic oscillator approximation for a single bond vibra-
magnitude can be observed also between neutral pyridine
tion, although relative numbers will be hard to extract this
and neutral imidazole ligands and in that particular case
way. One also has to assume that both bonds are on the
the difference may be attributed to steric effects.
same potential surface, which might not be true.
The absolute effect of a difference of this order is hard
Nevertheless, as the increase in potential energy in this
to estimate, but it seems that a significant increase in bond
approximation is proportional to the square of the distance
energy is present for the charged systems and that this
difference between the equilibrium and an extended bond,
difference may play a role in the overall stability of the
the important conclusion is that a small change in length
materials.
will be magnified in terms of strength, thus a 2.5% bond
There are no clear indications, however, that any funda-
length increase could indicate a much larger decrease in
mental differences between a metal-carboxylate and a me-
bond energy.
tal-pyridine bond exist, that would merit their division into
Two other simple models can also be used where we
two different classes, “salts” and “coordination com-
can easily get estimates of the absolute value of the bond
pounds”, respectively. Instead, anionic ligands can probably
better be thought of as having an extra “charge assisted”
Table 1. The absolute interaction energies and the energy change if component, just as has been coined in crystal engineering
we increase the bond length 0.05 Å for some model compounds (kJ/mol) for “charge assisted hydrogen bonds” [24, 25].
calculated by the charge-dipole and Coulombic interaction (assuming
a charge of þ1 and 1). In the calculations r corresponds to the
most probable bond length for each class as reported above. Acknowledgements. JR and L thank IUPAC for providing funds for
the project Coordination polymers and metal organic frameworks:
at r (kJ/mol) at r þ 0.05 Å (kJ/mol) terminology and nomenclature guidelines, and all the group members
Edipole Ecoul DEdipole DEcoul for fruitful and constructive discussions. We also thank the Swedish
(% diff) (% diff) Chemical Society for providing additional funds for the 2012 Trends
in Inorganic Chemistry meeting on Metal-Organic Frameworks, Coor-
imidazole a 283 ––14 (5%) dination Polymers and Zeolites in Stockholm. AN and L thank the
Swedish Research Council for support.
imidazolate 691 ––17 (2.5%)
pyridine a 166 ––8 (5%)
benzoic acid a 130 ––6 (5%) References
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Metal-ligand bond strengths: A CSD study 317
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