Polyhedron 29 (2010) 470–476

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Polyhedron
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Equilibrium and kinetic studies of reactions of [MnN(H2O)(CN)4]2 with

monodentate ligands and the molecular structure of [MnN(NCS)(CN)4]3
Hendrik J. van der Westhuizen a,1, Andreas Roodt b,*, Reinout Meijboom a,*
a
Department of Chemistry, University of Johannesburg, P.O. Box 524, Auckland Park 2006, South Africa
b
Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein 9300, South Africa

a r t i c l e i n f o a b s t r a c t

Article history:
Available online 23 June 2009
This article is dedicated to Professor
Stephen S. Basson on the occasion of his
retirement.
The dissolution of [(CH3)N]2Na[MnN(CN)5]H2O in water results in the dissociation of the labile trans-CN
ligand to form [MnN(H2O)(CN)4]2(aq). The formed aqua complex reacts rapidly with a number of nucle-
ophiles such as NCS and N3. Here we report the single crystal X-ray structure of the reaction products
of as well as the equilibrium and kinetic behaviour of [MnN(H2O)(CN)4]2 in solution.
Ó 2009 Elsevier Ltd. All rights reserved.

Keywords:
Manganese
Nitrido complex
X-ray structure
Kinetics

1. Introduction With the exception of crystallographic studies of (Ph4P)2

In-depth studies have shown that the iso-electronic [MX(H2O)-
(CN)4]n complexes (M = Mo(IV), W(IV), Tc(V), Re(V); X = O2, N)
are all labile towards monodentate ligand substitution [1–3]. The
rates of substitution depend on the pH of the solution, the type
of terminal ligand, the central metal atom and, to lesser extend,
on the type of incoming ligand.
Detailed crystallographic and kinetic studies of the various
complexes [MO2(CN)4](n+2) at different pH indicated that one of
the O ligands can be protonated to form [MO(H2O)(CN)4]n [4].
In contrast to the oxotetracyano complexes, however, a relatively
small amount of nitridotetracyano complexes have been isolated.
The protonation behaviour observed for the nitrido complexes
[MN(H2O)(CN)4]n, (M = Re(V) and Os(VI)) [5,6] showed similar
behaviour to the oxo complexes, with the exception that the parent
[MN(O)(CN)4]n complex was never observed. These kinetic stud-
ies have shown that the complexes [MN(H2O)(CN)4]n, (M =
Re(V) and Os(VI)) can undergo anation reactions with monoden-
tate ligands like CN and N3 [5]. These kinetic studies have also
shown that the aqua complexes can be deprotonated to form the
hydroxo complexes and that these are relatively inert towards sub-
stitution reactions.
* Corresponding authors. Tel.: +27 11 559 2367; fax: +27 11 559 2819.
E-mail address: rmeijboom@uj.ac.za (R. Meijboom).
1
Present address: Sasol Technology, P.O. Box 1, Sasolburg 1947, South Africa.
[MnN- (CN)4]2H2O [7], (Ph4P)2[MnN(py)(CN)4]pyH2O [7] and
[Rh(en)3]- [MnN(CN)5]H2O [8], hardly any studies of manganese
nitridotetracyanide complexes were reported. Results from these
structure determinations showed that the complexes have very
short terminal nitrido–metal bonds (1.5–1.6 Å). This indicates
the significant p-bond character of the metal–nitrogen bond;
the nitrido ligand being the strongest p-donor known to date.
The Mn„N bond in the five-coordinated [MnN(CN)4]2 anion of
1.507(2) Å is the shortest nitrido–metal bond reported to date [7].
With the above in mind we investigated the behaviour of
[MnN(CN)5]2 with respect to the anation reaction with CN, NCS,
N3 and OH. Here, we report the synthesis of [MnN(NCS)(CN)4]3,
3a, [MnN(OH)(CN)4]3, 3b, [MnN(N3)(CN)4]3, 3c, as well as the
equilibrium and kinetic evaluation of the reactions involved.
2. Experimental
2.1. General
All chemicals were obtained from Merck or Sigma–Aldrich and
used as obtained. [(CH3)4N]2Na[MnN(CN)5]H2O, 2a, (kmax = 287,
370(sh), 493 nm) and (PPh4)2[MnN(CN)4], 2b, (kmax = 351,
495 nm) were prepared with a slight modification to the published
procedure [7]. The UV–Vis spectra were recorded on either a Var-
ian Cary 50 or Varian Cary 100 spectrophotometer. The IR spectra
were recorded on a Bruker Equinox 55 FT-IR spectrometer and ana-
lysed with Bruker Opus-NT software.

0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.06.030
 H.J. van der Westhuizen et al. / Polyhedron 29 (2010) 470–476 471

2.2. Syntheses of the complexes
2.2.1. [Rh(en)3][MnN(NCS)(CN)4] H2O, 3a H2O
A solution of 2a (0.06 g, 0.15 mmol) in aqueous 1 M NaNCS
(2 cm3) was added to a solution of [Rh(en)3]Cl33H2O (0.120 g,
0.27 mmol) dissolved in aqueous 1 M NaNCS (1.5 cm3). This solu-
tion was filtered and left at ambient temperature to give red crys-
tals suitable for X-ray determination after ca. 3 days. Yield:
0.0729 g (89%). IR(KBr)/cm1: m(Mn„N) 1056, m(C„N, NCS ) 2068,
m(C„N) 2126, m(CS) 874.
2.2.2. [Rh(en)3][MnN(OH)(CN)4] 3b
A solution of 2a (0.075 g, 0.19 mmol) in aqueous 1 M NaOH
(2 cm3) was added to a solution of [Rh(en)3]Cl33H2O (0.130 g,
0.29 mmol) dissolved in aqueous 1 M NaOH (1.5 cm3). The remain-
ing solution was filtered and left at ambient temperature to give
purple crystals of the title compound after ca. 4 days. Yield:
0.085 g (95%). IR(KBr)/cm1: m(Mn„N) 1002, m(C„N) 2117.
2.2.3. [Rh(en)3][MnN(N3)(CN)4] 3c
A solution of 2a (0.06 g, 0.15 mmol) in aqueous 1 M NaN3
(2 cm3) was added to a solution of [Rh(en)3]Cl33H2O (0.120 g,
0.27 mmol) dissolved in aqueous 1 M NaN3 (1.5 cm3). The resulting
solution was filtered and left at ambient temperature to give or-
ange crystals after ca. 2 days of the title compound. Yield:
0.0709 g (92%). IR(KBr)/cm1: m(Mn„N) 1057, m(N„N, N3 ) 2043,
m(C„N) 2125.
2.3. Kinetics
All reagents and chemicals were of analytical grade and double
distilled water was used in all experiments. All the kinetic runs
were performed under pseudo first-order conditions in a carbon-
ate/hydrogen carbonate buffer medium with the ionic strength ad-
justed to l = 1.0 M using KNO3. No reaction between KNO3 and
[MnN(H2O)(CN)4]2 could be detected. All pH measurements were
recorded on a Hanna pH211 bench-top pH meter equipped with a
HI1043B refillable combination glass pH electrode using standard
buffer solutions for calibration. The UV/Visible spectral and absor-
bance changes for the fast kinetic reactions were measured on a Hi
Tech SF61DX2 Stopped Flow System with a thermostatted
SHU61DX sample handling unit and an attached Jalabu MPV
thermostatted water bath (accurate within ±0.05 °C). The rate con-
stants were determined using the KinetAsyst 3.10 [9] software
package supplied with the stopped-flow instrument. The UV/Vis
spectral and absorbance changes for the slow kinetic reactions
were measured on Varian Cary 50 Conc and Varian 100 spectro-
photometers with 1.000 ± 0.001 cm path length tandem quartz
cells. All the spectrophotometers were equipped with constant
temperature cell holders (accurate within 0.1 °C) and Jalabu MPV
thermostatted water baths (accurate within 0.05 °C) fitted with
circulators and all the temperatures are reported to ±0.1 °C accu-
racy. Least-squares analyses were performed using MicroMath Sci-
entist [10] on the absorption versus time data obtained from the
kinetics runs and the spectral changes, respectively.
2.4. Crystallography
Intensity data were collected on a Bruker SMART 1K CCD area
detector diffractometer (University of the Witwatersrand) with
graphite monochromated Mo Ka radiation (50 kV, 30 mA) at
273(2) K. The collection method involved x-scans of width 0.5°.
Data reduction was carried out using the program SAINT+ [11] and
absorption corrections were made using the program SADABS [11].

Table 1
Crystal data and structure refinement for (PPh4)2[MnN(CN)4] H2O, 2b and [Rh(en)3][MnN(NCS)(CN)4]H2O, 3a.

2b 3a
Empirical formula C52H44N5O2P2Mn C11H26N12OSMnRh
Formula weight 887.80 532.25
T (K) 273.0(2) 273.0(2)
Wavelength (Å) 0.71073 0.71073
Crystal system triclinic orthorhombic
Space group P1 P212121
Unit cell dimensions
a (Å) 12.103(2) 8.749(2)
b (Å) 12.337(2) 12.904(3)
c (Å) 16.781(2) 17.854(4)
a (°) 97.511(3) 90
b (°) 108.993(3) 90
c (°) 90.560(3) 90
V (Å3) 2345.1(6) 2015.8(8)
Z 2 4
Dexp (Mg m3) 1.24 1.76
Dcalc (Mg m3) 1.257 1.754
Absorption coefficient (mm1) 0.395 1.578
F(0 0 0) 924 1080
Crystal size (mm3) 0.44  0.28  0.26 0.50  0.24  0.20
h Range for data collection (°) 1.67–26.00 1.95–28.31
Index ranges 14 6 h 6 14, 9 6 k 6 15, 20 6 l 6 20 11 6 h 6 11, 17 6 k 6 14, 23 6 l 6 22
Reflections collected/unique/observed 13 960/9125/5979 12 757/4904/4667
Independent reflections [Rint] [0.0274] [0.0214]
Completeness to 2h (°, %) 26.00, 99.0 28.31, 99.1
Absorption correction semi-empirical from equivalents semi-empirical from equivalents
Maximum and minimum transmission 0.902, 0.876 0.729, 0.641
Refinement method full-matrix least-squares on F2 full-matrix least-squares on F2
Data/restraints/parameters 9125/0/571 4904/0/250
Goodness-of-fit (GOF) on F2 1.037 1.148
Final R indices [I > 2r(I)] R1 = 0.0456, wR2 = 0.0963 R1 = 0.0283, wR2 = 0.0611
R indices (all data) R1 = 0.0849, wR2 = 0.1094 R1 = 0.0312, wR2 = 0.0619
Largest difference in peak and hole (e Å3) 0.261 and 0.286 0.941 and 0.744
472 H.J. van der Westhuizen et al. / Polyhedron 29 (2010) 470–476
The structures were solved by the Patterson method and refine-
ments through full-matrix least-squares cycles using the SHELXL-97
P
[12] software package with (/Fo//Fc/)2 being minimized. Non-
hydrogen atoms were first refined isotropically, followed by aniso-
tropic refinement. The hydrogen atoms of the water molecules of
crystallization were determined geometrically from difference
Fourier maps. The program DIAMOND [13] was used to produce
molecular diagrams of each of the respective complexes. The den-
sities of the crystals were determined by flotation in benzene/
diiodomethane. Crystal data and details of refinement are given
in Table 1.
3. Results and discussion
3.1. Synthesis
It is somewhat surprising that the nitridotetracyano complexes
of Mn(V) [7,8] have received little attention, whereas the corre-
sponding analogues of Tc(V), Re(V) and Os(VI) are known. Thus,
[TcN(OH2)(CN)4]2 [14], [ReN(OH2)(CN)4]2 [15], [ReN(CN)5]3
[16], [ReN(N3)(CN)4]3 [17] and [OsN(OH)(CN)4]2 [18] have been
synthesized and the PPh4+ or AsPh4+ salts of these anions have been
crystallographically characterized.
Fairly simple synthetic routes are available for the synthesis of
the complexes [MN(CN)4]n (M = Tc, Re, Os). It seems, however,
that only a limited number of synthetic routes are available for
the synthesis of the nitridotetracyano complexes of manganese(V)
[19]. We followed the route reported a decade ago which synthe-
sized of the nitridotetracyano complexes of Mn(V) by ligand sub-
stitution of the salen ligand of [MnVN(salen)], 1, by CN in
aqueous solutions of NaCN [7] (Scheme 1).
The IR stretching frequencies of the products show a behaviour
similar to that of the corresponding Re complexes. The m(Mn„N)
stretching frequency for the parent complex [MnN(CN)4]2 is
1105 cm1 (1094 reported for solution [7]). This is significantly dif-
ferent from the value of 1011 cm1 obtained for the [MnN(CN)5]3
anion [8]. The m(Mn„N) stretching frequency is sensitive to the
trans-influence of entering ligands. The m(Mn„N) stretching fre-
Scheme 1. Synthesis of compounds.
quencies for the N3, NCS and the OH ligands are 1057, 1056
and 1002 cm-1, respectively. These m(Mn„N) values indicate that
the trans-influences (and probably the bond strengths) decrease
in order of H2O (or no ligand)  N3 > NCS > py [7] > CN > OH.
The m(CN) stretching frequencies of all reported compounds are
around 2125 cm1, except for the OH complex 3b which shows
a considerable shift to 2117 cm1 for the m(CN). The shift of the
m(CN) in the hydroxide complex 3b is a clear sign of the inert nat-
ure of the hydroxide complexes (see Section 3.3).
3.2. Molecular structure
Since the structures of the aqua complexes of the various iso-
electronic metal tetracyanides are known, we attempted to crystal-
lise the elusive [MnN(H2O)(CN)4]2 anion. Unfortunately the ques-
tion of the existence of the [MnN(H2O)(CN)4]2 in solution as well
as in the solid state remains unanswered, since the crystals ob-
tained from aqueous solutions after numerous careful crystalliza-
tions contained only the [MnN(CN)4]2 anion. Here, we report
the redetermination of this anion (figure not shown). For the
description of this structure we refer to the original publication [7].
A molecular diagram showing the numbering scheme of the ti-
tle compound [Rh(en)3][MnN(NCS)(CN)4] H2O, 3a, is presented in
Fig. 1, with selected bond lengths and angles in Table 2 [NB: extend
Table 2 to include much more bond distances, angles and torsion
angles]. Comparative bond distances and angles for selected re-
lated compounds are given in Table 3. Compound 3a crystallizes
in the orthorhombic space group, P212121, with Z = 4. The chiral
center of the molecule is situated on the cation and the conforma-
tion of the cation was determined as Kkkd [20]. The rhodium metal
center of the trivalent cation is octahedrally coordinated to the six
nitrogen atoms of three 1,2-diaminoethane ligands. The average
Fig. 1. Molecular diagram showing the numbering scheme and displacement
ellipsoids (30% probability) of the [MnN(NCS)(CN)4]3 anion. The cations and
solvent molecules are omitted for clarity.
Table 2
Selected interatomic bond distances (Å) and angles (°) for 3a. Expand table more with
bond distance, angles and torsion angles.
Distances
Mn–N(10) 1.540(3) Mn–N(5) 2.298(3)
N(5)–C(5) 1.154(5) C(5)–S 1.664(4)
Angles
N(10)–Mn–N(5) 174.60(13) N(5)–C(5)–S 177.6(3)
 H.J. van der Westhuizen et al. / Polyhedron 29 (2010) 470–476 473

Table 3
Comparison of structural parameters (Å, °) in related [MNX(CN)4]n (M = Mn, Tc, Re, Os; X = NCS, CN) anions.

Anion M„N (Å) M–Ca (Å) M–Lb (Å) Dc (Å) m(M„N) (cm1) Ref.
3
[MnN(NCS)(CN)4] 1.540(3) 2.006(3) 2.298(3) 0.196(2) 1056 TW
[MnN(CN)4]2 1.497(2) 1.970(3) 0.435(1) 1105 TW
[MnN(CN)4]2 1.507(2) 1.983(2) 0.436 1094 [7]
[MnN(py)(CN)4]2 1.525(4) 1.997(4) 2.472(4) 0.246(2) 1041 [7]
[MnN(CN)5]3 1.499(8) 1.990(6) 2.243(7) 0.222(1) 1011 [8]
[TcN(H2O)(CN)4]2 1.596(10) 2.11(2) 2.559(9) 0.35 1100 [14]
[ReN(CN)5]3 1.68(1) 2.12(1) 2.39(1) 0.31 1040 [16]
[ReN(H2O)(CN)4]2 1.64(1) 2.11(1) 2.496(7) 0.35 1060 [15]
[ReN(N3)(CN)4]3 1.65(2) 2.11(1) 2.36(2) 0.34 1074 [17]
[OsN(OH)(CN)4]2 1.606(5) 2.068(9) 2.123(5) 0.26 1050 [18]

Refer also here to Refs. [2,3].

TW = this work.
a
Equatorial M–CN bonds.
b
trans to M„N.
c
Displacement of metal from the best plane formed by the four CN ligands.

Rh–N bond distance of 2.087(3) Å corresponds well with the same
bond distances found in the [Rh(en)3]3+ cation of the [Rh(en)3]
[MnN(CN)5]H2O complex [8] [average Rh–N = 2.079(5) Å]. The
N–Rh–N bond angles range from 82.9(1)° to 94.9(1)° and are
comparable to those found for the [Rh(en)3]3+ cation of the
[Rh(en)3][MnN(CN)5]H2O complex [8].
The Mn(V) metal center is octahedrally coordinated to the nitr-
ido ligand, four cyano ligands and the thiocyanate ligand trans to
the nitrido ligand. The Mn„N bond distance of 1.540(3) Å is longer
than the corresponding bond distance of 1.499(8) Å in the
[MnN(CN)5]3 complex [8]. The average Mn–C bond distance be-
tween the central metal atom and the carbon atoms of the cyano
ligands of 2.006(3) Å and the average C„N bond distance of
1.156(4) Å are comparable to the same bond distances found in
[MnN(CN)4]2 of 1.983(2) and 1.160(2) Å, respectively [7]. The
average Mn–C–N bond angle is 175.5(3)° and is nearly linear as ex-
pected for this type of moiety. The Mn–N bond distance of
2.298(3) Å between the Mn(V) and the thiocyanate ligand is
slightly longer than the Mn–C bond distance of 2.243(7) Å between
the Mn(V) and the cyano ligand coordinated trans to the nitrido in
the [MnN(CN)5]3 anion [8]. The manganese(V) metal center can
be considered as a hard acid due to the high formal charge on
the metal atom and will preferably bind to the hard base part of
the thiocyanate ion, i.e. the nitrogen atom. The N(5)–C(5) bond dis-
tance is 1.154(5) Å and the C(5)–S bond distance is 1.664(4) Å. The
Mn–N(5)–C(5) angle is 158.3(3)° and the N(5)–C(5)–S angle is
177.6(3)°. Similar results were reported for the [ReO(NCS)(CN)4]2
complex [21].
The Mn(V) atom is displaced by 0.196(2) Å from the best plane
formed by the four carbon atoms of the cyano ligands. This large
distortion of the coordination polyhedron is also reflected in the
deviations from the expected rectangular values for the N(10)–
Mn–C and C–Mn–N(5) bond angles which range from 99.26(15)°
to 93.68(14)° and 88.31(13)° to 81.52(13)°, respectively. The dis-
placement of the Mn atom towards the nitrido ligand along the
N(10)„Mn–N(5) axis forces the cis-bonded cyano ligands and
the N(5) atom of the NCS ligand closer together as indicated by
smaller than 90° C–Mn–N(5) bond angles. A similar displacement
was found for the [MnN(CN)5]3 anion [8].
The [Rh(en)3]3+ cation forms three weak intermolecular hydro-
gen-bonding contacts [N(12)N(4) = 3.017(4) Å, N(31)N(3) =
3.309(4) Å and N(32)N(10) = 3.223(5) Å] with two nitrogen
atoms of the equatorial cyano ligands and the axial nitrido ligand.
Normally the nitrido ligand does not form any intermolecular con-
tacts, except in the case when potassium was the counter ion in the
[ReN(CN)4]2 complex. In the latter case infinite chains of Re-
NRe„NRe were observed. The water molecule of crystallization
forms a weak hydrogen-bond [O(1 W)N(2) = 2.893(4) Å] with one
of the nitrogen atoms of an equatorial cyano ligand. The hydrogen-
bonding between a water molecule of crystallization and an
equatorial cyano ligand seems to be a frequently occurring phe-
nomenon for this type of transition metal complex. The water of
crystallization links two anions in a zig-zagging pattern, with the
cations suspended between three anions forming one bend (see
Fig. 2).
Interestingly, the two water molecules of crystallization in the
[MnN(CN)4]2 anion, 2b, are not located near the vicinity of the va-
cant sixth coordination site of [MnN(CN)4]2, but instead they form
weak intermolecular hydrogen-bonding contacts with two nitro-
gen atoms [O1 WN2 = 2.984(3) Å, O2 WN4 = 3.054(4) Å] of
two of the cyano ligands. Here, the anions and the water molecules
form an infinite chain structure in the solid state. In contrast to the
structure of 3a, the nitrido ligand is not involved in any hydrogen-
bonding.
A root-mean-square (r.m.s.) calculation is one way to compare
similar structures. The calculated r.m.s. deviations between the an-
ions [MnN(CN)4]2, 2b, and [MnN(NCS)(CN)4]3, 3a, is calculated to
be 0.226 Å. This small r.m.s. errors confirms that the general orien-
tation is similar in the two anions. In addition, the differences be-
tween the two compounds can be seen from the overlay of these
two structures (Fig. 3). It is clear from Fig. 3 that the main differ-
ences between the anions is the change from the central Mn atom
out of the plane formed by the four CN ligands, as indicated by the
larger N–Mn–CN angles in the [MnN(CN)4]2 anion.
3.3. Kinetics
Results from previous kinetic studies of the reactions of
[MN(H2O)(CN)4]n [M = Re(V), Os(VI)] with monodentate ligands
have shown that only the aqua ligand is substituted in these com-
plexes [5]. These studies have also shown that the hydroxo com-
plex is formed upon deprotonation of the aqua complex and that
the hydroxo complex is inert towards monodentate substitution
reactions. A dissociative mechanism for the substitution of the
aqua ligand in [MN(H2O)(CN)4]n by monodentate nucleophiles
was proposed.
Previous research has shown that the [MN(H2O)(CN)4]n aqua
complexes [M = Re(V); Os(VI)] are the only complexes reactive to-
wards substitution reactions and that the hydroxo ligand in
[MN(OH)(CN)](n+1) is not substituted by entering nucleophiles,
i.e., the hydroxo complex is inert towards substitution reactions
[5]. These observations enabled the construction of the reaction
scheme as represented in Scheme 2 for the substitution reactions
with monodentate nucleophiles as well as the deprotonation reac-
tions of the [M(H2O)(CN)4]n complexes in solution.
474 H.J. van der Westhuizen et al. / Polyhedron 29 (2010) 470–476

Scheme 2. The dissociation and solution behaviour of the [MnN(CN)5]3 complex

in aqueous medium.

For the nucleophilic reactions of the Re(V) and Os(VI) analogues,

Fig. 2. Hydrogen-bonding pattern for 3a.
Fig. 3. Overlay of [MnN(CN)4]2, 2b (hashed) and [MnN(NCS)(CN)4]3, 3a (solid).
the aqua compound [MN(H2O)(CN)4]n could be used [5,6]. How-
ever, for the Mn(V) analogues, the pentacyano complex
[(CH3)N]2Na[MnN(CN)5]H2O was used. The trans-bonded cyano li-
gand dissociates in solution (even at [CN] 0.3 M) to form the
aqua complex (reaction A, Scheme 2) in situ, and this aqua complex
reacts with monodentate, or even bidentate, nucleophiles.
Due to the high concentration of the aqua ligand in solution (ca.
55 M) it is presumed that the [MnN(H2O)(CN)4]2 anion exists in
solution after the dissociation of the trans-bonded ligand (CN)
or that the aqua ligand is at least in the very near vicinity of the va-
cant coordination site. Unfortunately, the molecular structure of
the [MnN(H2O)(CN)4]2 complex has not been determined as of
yet, and thus, the crucial question of whether the aqua ligand is
bonded trans to the nitrido ligand remains unanswered for now,
although it is assumed to be.
Unfortunately, the corresponding acid dissociation constant
(pKa1) of the aqua complex could also not be determined due to
the relatively small difference in the UV–Vis absorbance spectra
of the aqua and hydroxo complexes (see reaction B, Scheme 2).
However, results from the kinetic studies of the monodentate sub-
stitution reactions of the [MN(H2O)(CN)4]n complexes [M = Re(V),
Os(VI)] have shown that the hydroxo complexes do not react with
monodentate nucleophiles [5]. Therefore, the value of the forward
reaction between the [MN(OH)(CN)4]3 and monodentate ligands
(k2) is assumed to be zero within experimental error (reaction D,
Scheme 2). The same tendency is expected for the substitution
reactions of the [MnN(OH)(CN)4]3 with monodentate
nucleophiles.
The UV–Vis spectrum of the reaction between
[MnN(H2O)(CN)4]2 and added CN ions showed only one maxi-
mum in the spectrum at k = 285 nm. In the spectrophotometric
determination of the stability constant of the [MnN(CN)5]3 com-
plex the concentration of the CN was varied from 0.005 to
0.10 M. The plot of absorbance versus concentration of the entering
ligand (Fig. 2) shows that under these conditions [MnN(H2O)-
(CN)4]2 reacts with CN in a 1:1 ratio which is in agreement with
the formulation of the product as [MnN(CN)5]3 [7].
The equilibrium constant for the reaction between
[MnN(H2O)(CN)4]2 and CN was determined by a least-squares
fit of the absorbance versus [CN] to Eq. (1) and is illustrated in
Fig. 4. This equation is derived using Beer0 s law, mass balance as
well as the definition of the stability constant, K1, for the reaction
A in Scheme 2. The stability constant for the [MnN(CN)5]3 com-
plex was determined as 168(20) M1.
 H.J. van der Westhuizen et al. / Polyhedron 29 (2010) 470–476 475

second- to third-row element suggests that the metal–aqua bond is

Fig. 4. Plot of absorbance vs. [CN] at 25.2 °C, [MnN]T = 5.05  104 M, l = 1.0 M
(NaCl), pH 11.01 and k = 285 nm.
AM þ AML K 1 ½CN 
Aobs ¼
1 þ K 1 ½CN 
In the above equation, AM and AML represents the absorbance of
the [MnN(H2O)(CN)4]2 and [MnN(CN)5]3 complexes, Aobs, the ob-
served absorbance and K1 the equilibrium constant of the reaction,
respectively.
The forward reactions of the [MnN(H2O)(CN)4]2 with mono-
dentate ligands (CN, NCS and N3) were extremely rapid. Unfor-
tunately, these reaction rates of the substitution reactions could
not be determined, even on our third generation stopped-flow
spectrophotometer. This spectrophotometer has a mixing time of
less than 1 ms before the measurement of the absorbance versus
time data starts. When the standard equation for the calculation
of the half-life of pseudo first-order reactions is used, a value larger
than 1000 s1 is obtained for the observed rate constant, kobs, at
[CN] = 0.05 M. If the forward rate constant is calculated using
the minimum value of the observed rate constant and the concen-
tration of the entering ligand, a value of k1 > 20 000 M1 s1 is ob-
tained, which indicates that the substitution reactions of the
[MnN(H2O)(CN)4]2 complex are extremely rapid. When compar-
ing the stability constants for the known monodentate substituted
[MO(L)(CN)4]n complexes (for M = Mo(IV), L = CN, N3, NCS:
95(5), 1.5(1), 0.2(1) M1 and M = W(IV), L = CN, N3, NCS:
1.1(1)  103, 4.8(11), 2.0(1) M1) it can be predicted that the stabil-
ity constants (reaction C, Scheme 1) for the [MnN(NCS)(CN)4]3
and [MnN(N3)(CN)4]3 complexes will be smaller than the stability
constant for [MnN(CN)5]3 [K1 = 168(20) M1].
Comparable kinetic studies of the reactions between
[MX(H2O)(CN)4]n (M = Mo(IV) [22], W(IV) [23–25], Tc(V) [26],
Re(V) [27] and Os(VI); X = O, N) and different monodentate ligands
are shown in Table 4. The increase in reaction rate upon going from
stronger in the third-row elements. Conversely, the aqua substitu-
tion reactions for the first-row elements are expected to be even
faster in a dissociative mechanism, i.e., when the rate is dependent
on the dissociation of the aqua ligand. These results also indicate
that the rate of the reverse reaction (k1) or the dissociation of
the CN ligand has a significant contribution in the overall process.
The very large difference found for the values of k1 for the com-
plexes of the second- and third-row and possibly the first-row ele-
ments may also point towards a dissociative mechanism for the
substitution reactions. A weaker metal–aqua bond for the second
and possibly the first-row elements is also evident from the higher
pKa values for the second- and third-row complexes. A weaker me-
tal–oxygen bond will strengthen the oxygen–hydrogen-bonds in
the aqua ligand with a resulting higher pKa value.
Upon comparing the values of the k1 in Table 4 for the reactions
of the oxo and nitrido complexes of Re(V) an even more spectacu-
lar effect of bond strength on the relative reactivity of these com-
ð1Þ plexes is observed. The nitrido complex with the weak metal–aqua
bond [Re–OH2 = 2.496(7) Å] [15] reacts about 106 times faster than
the oxo with the much stronger metal–aqua bond [Re–
OH2 = 2.142(7) Å] [28]. The effect of the Re–aqua bond strengths
in the oxo and nitrido complexes is also evidenced by the very
large increase in the pKa value of 1.4 for the oxo complex to about
12 for the nitrido complex. This very high pKa value for the nitrido
complex points to a very weakly bonded aqua ligand and this is in
agreement with the two above-mentioned Re–aqua bond distances
found in the crystal structure determinations of the oxo and nitrido
complexes. The large dependency of the rate of substitution on the
Re–aqua distance, as well as the high reactivity of the nitrido com-
plex also suggests a dissociative mechanism.
Thus it is expected that the [MnN(H2O)(CN)4]2 complex will
have a higher pKa value compared to the [ReN(H2O)(CN)4]2 com-
plex, due to the fact that upon going from the third to the second-
row and then the first-row elements the metal–aqua bond is ex-
pected to weaken significantly. The [MnN(H2O)(CN)4]2 complex
should also have a much higher reactivity compared to the [Re-
N(H2O)(CN)]2 complex and the substitution reactions of the aqua
ligand in [MnN(H2O)(CN)4]2 is expected to proceed via a dissocia-
tive mechanism.
4. Conclusions
The dissolution of [(CH3)N]2Na[MnN(CN)5]H2O in water re-
sulted in the dissociation of the labile trans-CN ligand to form
[MnN(H2O)(CN)4]2(aq). The formed aqua complex was reacted
with X = OH, NCS and N3 to form the [MnN(X)(CN)4]3 com-
plexes. Despite several attempts the parent [MnN(H2O)(CN)4]2
anion could not be crystallized, and a redetermination of the
[MnN(CN)4]2 anion resulted. The single crystal X-ray structure

Table 4
Kinetic data for the reaction of [MX(H2O)(CN)4]n complexes with monodentate ligands (L) at 25 °C.

Anion L pKa1 k1 (M1 s1) K1 (M1) DS– (J K1 mol1) Ref.

[MoO(H2O)(CN)4] CNa 10.0 116(2) 95(5) 53(14) [22]
[WO(H2O)(CN)4] CN 7.8 1.15(3) 1.1(1)  103 12(20) [23]
NCS 2.9(1) 2.0(1) 8(9) [24]
N3c 4.2(1) 4.8(11) 10(8) [25]
[TcO(H2O)(CN)4]3 NCS 2.9 22.2(3) 54(2) 9(12) [26]
[ReO(H2O)(CN)4] NCS 1.4 3.48(4)  103 87(7) 46(20) [27]
[MnN(H2O)(CN)4]2 CN 13 >20 000 168(20) TW
[ReN(H2O)(CN)4]2 CNb 11.7 7.2(4)  103 600(100) 40(6) [5a]
[OsN(H2O)(CN)4] N3 7.43 1.89(7) 189(8) 45(3) [5b]
a
At 20 °C.
b
At 15 °C.
c
DV– = 10.6(5) cm3 mol1.
476 H.J. van der Westhuizen et al. / Polyhedron 29 (2010) 470–476
of [MnN(NCS)(CN)4]3 shows an octahedral coordination around
the Mn atom, with the nitrido ligand trans to the thiocyanate. Ini-
tial kinetic investigations indicated that the reaction of
[MnN(H2O)- (CN)4]2(aq) with NCS and N3 were too fast to ob-
tain suitable data. The kinetic investigation with CN revealed a
stability constant of 168(20) M1 for [MnN(CN)5]3.
Acknowledgements
Financial assistance from the Research Funds of the Universities
of Johannesburg and the Free State, SASOL, THRIP, and the NRF is
gratefully acknowledged. Part of this material is based on work
supported by the South African National Research Foundation.
Opinions, findings, conclusions or recommendations expressed in
this material are those of the author and do not necessarily reflect
the views of the NRF.
Appendix A. Supplementary data
CCDC 730581 and 730582 contain the supplementary crystallo-
graphic data for 2b and 3a. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: de-
posit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.poly.2009.06.030.
References
[1] J.G. Leipoldt, S.S. Basson, A. Roodt, Adv. Inorg. Chem. 40 (1993) 297.
[2] A. Roodt, A. Abou-Hamdan, H.P. Engelbrecht, A.E. Merbach, in: A.G. Sykes, (Ed),
Advances in Inorganic Chemistry, vol. 49, 1999; published 2000, p. 59.
[3] J.M. Botha, A. Roodt, Metal-Based Drugs, vol. 2008, Article ID 745989, 2008, 9
pages, doi:10.1155/2008/745989.
[4] (a) V.W. Day, J.L. Hoard, J. Am. Chem. Soc. 90 (1968) 3374;
(b) S.J. Lippard, B.J. Russ, Inorg. Chem. 6 (1967) 1943;
(c) K. Weighardt, G. Backes-Dahmann, W.J. Holzbach, W.J. Swiridoff, J. Weiss,
Z. Anorg. Allg. Chem. 499 (1983) 44.
[5] (a) L.J. Damoense, W. Purcell, J.G. Leipoldt, Transition Met. Chem. 19 (1994)
619;
(b) H.J. van der Westhuizen, S.S. Basson, J.G. Leipoldt, W. Purcell, Polyhedron
13 (1994) 717.
[6] T.N. Mtshali, W. Purcell, H.G. Visser, S.S. Basson, Polyhedron 25 (2006) 2415.
[7] J. Bendix, K. Meyer, T. Weyhermüller, E. Bill, N. Metzler-Nolte, K. Wieghardt,
Inorg. Chem. 37 (1998) 1767.
[8] J. Bendix, R.J. Deeth, T. Weyhermüller, E. Bill, K. Wieghardt, Inorg. Chem. 39
(2000) 930.
[9] KinetAsyst 3.10 Software Package, Hi-Tech Ltd., Salisbury, UK, 2002.
[10] MicroMath Scientist Software for Windows, Version 2.01, Micromath Inc.,
1995.
[11] Bruker SAINT+. Version 6.02 Includes XPREP and SADABS, Bruker AXS Inc., Madison,
WI, USA, 1999.
[12] G.M. Sheldrick, SHELX-97, Program for the Refinement of Crystal Structures,
University of Göttingen, Germany, 1997.
[13] K. Brandenburg, DIAMOND (Ver. 2.1e), Crystal Impact GbR, Bonn, Germany, 2001.
[14] J. Baldas, J.F. Boas, S.F. Colmanet, M.F. Mackay, Inorg. Chim. Acta 170 (1990)
233.
[15] W. Purcell, I.M. Potgieter, L.J. Damoense, J.G. Leipoldt, Transition Met. Chem. 17
(1992) 387.
[16] W. Purcell, I.M. Potgieter, L.J. Damoense, J.G. Leipoldt, Transition Met. Chem. 16
(1991) 473.
[17] W. Purcell, L.J. Damoense, J.G. Leipoldt, Inorg. Chim. Acta 195 (1992) 217.
[18] H.J. van der Westhuizen, S.S. Basson, W. Purcell, Transition Met. Chem. 19
(1994) 582.
[19] (a) S.I. Arshankov, A.L. Poznjak, Z. Anorg. Allg. Chem. 481 (1981) 201;
(b) J.W. Buchler, C. Dreher, K.-L. Lay, Z. Naturforsch., B: Anorg. Chem. Org.
Chem. 37B (1982) 1155;
(c) C.L. Hill, F.J. Hollander, J. Am. Chem. Soc. 104 (1982) 7318;
(d) J.W. Buchler, C. Dreher, K.-L. Lay, Y.J.A. Lee, W.R. Scheidt, Inorg. Chem. 22
(1983) 888;
(e) J. Du Bois, C.S. Tomooka, J. Hong, E.M. Carreira, M.W. Day, Angew. Chem.,
Int. Ed. Engl. 36 (1997) 1645;
(f) A. Niemann, U. Bossek, G. Haselhorst, K. Wieghardt, B. Nuber, Inorg. Chem.
35 (1996) 906;
(g) J. Du Bois, C.S. Tomooka, J. Hong, E.M. Carreira, Acc. Chem. Res. 30 (1997)
364.
[20] K.F. Purcell, J.C. Kotz, Inorganic Chemistry, W.B. Sanders Company, 1977.
[21] W. Purcell, A. Roodt, S.S. Basson, J.G. Leipoldt, Transition Met. Chem. 14 (1989)
369.
[22] (a) P.R. Robinson, E.O. Schlemper, R.K. Murmann, Inorg. Chem. 14 (1975)
2035;
(b) J.P. Smit, W. Purcell, A. Roodt, J.G. Leipoldt, Polyhedron 12 (1993) 2271.
[23] (a) E. Heijmo, A. Kanas, A. Samotus, Bull. Acad. Polon. Sci. Ser. Sci. Chim. 21
(1973) 311;
(b) J.P. Smit, Ph.D. Thesis, University of the Free State, Bloemfontein, South
Africa, 1995.
[24] A. Roodt, J.G. Leipoldt, S.S. Basson, I.M. Potgieter, Transition Met. Chem. 13
(1988) 336.
[25] J.G. Leipoldt, R. van Eldik, S.S. Basson, A. Roodt, Inorg. Chem. 25 (1986) 4639.
[26] A. Roodt, J.G. Leipoldt, E.A. Deutsch, J.C. Sullivan, Inorg. Chem. 31 (1992) 1080.
[27] W. Purcell, A. Roodt, S.S. Basson, J.G. Leipoldt, Transition Met. Chem. 14 (1989)
224.
[28] W. Purcell, A. Roodt, S.S. Basson, J.G. Leipoldt, Transition Met. Chem. 15 (1990)
239.