Studies on Zn(II) and Cd(II) heteroligand complexes with RC(S)NHP(O)(OiPr)2 (R = Ph, NH2, PhNH) and α-diimine (bpy and phen) ligands. C-Cl bond cleavage of CH2Cl2 by [Zn(phen){PhC(S)NP(O)(OiPr)2}

Article abstract of DOI:10.1016/j.ica.2010.10.001

The reaction of [ZnL^I,II₂] (L^I = [NH ₂C(S)NP(O)(OiPr)₂]^-; L^II = [PhNHC(S)NP(O)(OiPr)₂]^-) or [Cd₂L ^IV₄] (L^IV = [P

Full text of DOI:10.1016/j.ica.2010.10.001

Inorganica Chimica Acta 366 (2011) 19–26
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Studies on Zn(II) and Cd(II) heteroligand complexes with RC(S)NHP(O)(OiPr)2
(R = Ph, NH2, PhNH) and
a-diimine (bpy and phen) ligands. C–Cl bond cleavage
of CH2Cl2 by [Zn(phen){PhC(S)NP(O)(OiPr)2}2]
a
c
d
b
Damir A. Safin a,b, , Maria G. Babashkina , Michael Bolte , Dmitriy B. Krivolapov , Maxim L. Verizhnikov ,
⇑
Airat R. Bashirov b, Axel Klein a,
⇑
a Institut für Anorganische Chemie, Universität zu Köln, Greinstrasse 6, D-50939 Köln, Germany
b JSC ‘‘DANAFLEX”, Rodina Str. 7, 420087 Kazan, Russian Federation
c Institut für Anorganische Chemie J.-W.-Goethe-Universität, Frankfurt/Main, Germany
d Arbuzov Institute of Organic and Physical Chemistry, Arbuzov Str. 8, 420088 Kazan, Russian Federation
a r t i c l e i n f o
a b s t r a c t
The reaction of [ZnLI,II
] L ]
(LI = [NH2C(S)NP(O)(OiPr)2]ꢀ; II = [PhNHC(S)NP(O)(OiPr)2]ꢀ) or [Cd2LIV
4
Article history:
2
(LIV = [PhC(S)NP(O)(OiPr)2]ꢀ) with 2,20-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to the het-
eroligand complexes [Zn(bpy)LI,II2], [Zn(phen)LI,II2], [Cd(bpy)LIV2] or [Cd(phen)LIV2], respectively. The
introduction of the diimine ligands into the coordination sphere of the metal cation provokes a change
from 1,5-O,S- to 1,3-N,S-coordination of the anionic ligands for Zn but not for the Cd species. The reaction
of [Zn(phen)LIV2] (LIV = PhC(S)NP(O)(OiPr)2ꢀ) with CH2Cl2 cleaves the chlorine atoms from CH2Cl2 and
leads to the formation of [Zn(phen)LIVCl] and S,S0-bis(benzimidothio-N-diisopropoxyphosphoryl)meth-
ane (LIV–CH2–LIV) in high yields. Using CHCl3 or CCl4 instead of CH2Cl2 does not lead to the formation
of chlorine substituted products even under reflux conditions. The new compounds were investigated
by 1H and 31P{1H} NMR, IR spectroscopy and microanalysis. Crystal structures of [ZnLII2], [Cd(phen)-
LIV2]ꢁCH2Cl2, [Zn(bpy)LI2] and [Zn(phen)LIVCl] were elucidated by X-ray diffraction.
Received 5 March 2010
Received in revised form 14 September
2010
Accepted 3 October 2010
Available online 4 November 2010
Keywords:
a-Diimine
Cadmium
Zinc
Thiourea
Complex
Crystal structure
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
papers Zn(II) and Cd(II) complexes of dithio HL ligands were de-
scribed (X = Y = S) [12–17]. It was found that this type of HL is al-
In the last decade there has been a number of reports on the
complexation properties of carbamoylthioureas and 2-thiobiuret
RC(O)NHC(S)NR0R00 (R = MeO, R0 = H, R00 = 2–NO2–C6H4 [1]; R = Ph,
R0 = H, R00 = 2–NO2–4–MeO–C6H3 [2]; R = Ph, R0 = H, R00 = 3-triazolyl
[3]; R = Ph, R0 = R00 = iBu [4]; R = Me2N, R0 = R00 = Me [5]; R = Ph,
R0 = H, R00 = PhC(O)NH or PhC(O)NH(CH2)2 [6]; R = Ph, R0 = R00 = Et
[7]) towards Zn(II) and Cd(II). For imidodiphosphinate
R2P(O)NHP(S)R02 ligands Zn(II) and Cd(II) complexes are also known
(R = EtO, R0 = Ph [8]; R = R0 = iPr [9]; R = Me, R0 = Ph [10]). Our scien-
tific groups have extensively studied the complexation properties
ways coordinated through the sulfur atoms of the C@S and P@S
groups with Zn(II) and Cd(II). By contrast, complexes of Zn(II) and
especially Cd(II) with HL ligands, containing donor atoms of sulfur
and oxygen (X = S, Y = O) simultaneously, still remain poorly
explored.
The overwhelming majority of our preceding investigations was
carried out on Zn(II) complexes with RC(S)NHP(O)(OiPr)2 ligands
[13,14,17–21], while there are only few examples of Cd(II) analogs
[18,19,21]. The properties of complexes of the ‘‘soft”’, easily polar-
izable Cd(II) cation differ considerably from analogs containing
Zn(II). The complex core CdO2S2 occurs to be considerably less sta-
ble than CdS4 and ZnO2S2. As a result, such Cd complexes are
hydrolytically unstable and tend to increase the coordination num-
ber of the central atom. Hence, the attempted synthesis of Cd(II)
complexes of the thioureas RC(S)NHP(O)(OiPr)2 (R = NH2 (HLI),
iPrNH, tBuNH, c-C6H11NH, Et2N, c-C5H10N, c-OC4H8N, PhNH (HLII),
p-MeOPhNH (HLIII), p-BrPhNH) in an aqueous ethanol medium
failed [18]. Instead of the corresponding complexes the starting
thioureas or their decomposition products were isolated from the
reaction mixture [18]. We suggest that the reason for the failure
of
N-(thio)phosphorylated
(thio)amides
and
(thio)ureas
RC(X)NHP(Y)R02 (X = O, S) (HL), which can be considered as interja-
cent compounds between carbamoylthioureas and imidodiphosph-
inates concerning the chelate backbone [11]. In our preceding
⇑
Corresponding authors at: Institut für Anorganische Chemie, Universität zu
Köln, Greinstrasse 6, D-50939 Köln, Germany. Tel.: +49 221 4702913; fax: +49 221
4705196 (D.A. Safin).
E-mail addresses: damir.safin@ksu.ru (D.A. Safin), axel.klein@uni-koeln.de
(A. Klein).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.10.001

20
D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
of the synthesis is hydrolysis of the complexes in aqueous ethanol.
Carrying out the reaction of KLII and KLIII with Cd(OAc)2 in
anhydrous DMF, to exclude hydrolysis, leads to hexacoordinated
stable solvent complexes [Cd(DMF)2LII,III2] [18]. So far, we were
successful in the isolation of Cd(II) complexes of only two N-phos-
phorylated thiobenzamide ligands RC(S)NHP(O)(OiPr)2 (Ph (HLIV),
p-BrC6H4 (HLV)) in an aqueous ethanol medium [19,21,22]. In each
case two different types of complexes were obtained. Using HLIV
leads to the simultaneous formation of [Cd(HLIV)2LIV)] and
[Cd2LIV4] [19], while the reaction of the potassium salt of HLV with
Cd(II) leads exclusively to [Cd(HLV)2LV2], which is isostructural to
while the bpy derivative fails to do so [31]. Interestingly, the com-
pound LIV–CH2–LIV had been previously synthesized by the reac-
tion of the potassium salt KLIV with CH2I2 in an acetonitrile
solution under reflux [32]. The yield of LIV–CH2–LIV in this reaction
was 69%, while the reaction of [Zn(phen)LIV2] with CH2Cl2 yields
98 and 96% for [Zn(phen)LIVCl] and LIV–CH2–LIV, respectively.
Using CHCl3 or CCl4 instead of CH2Cl2 did not lead to the formation
of chlorine substituted products. In order to explore this very inter-
esting reaction we extended the study on related complexes
including further ligands and also corresponding Cd(II) derivatives.
In this contribution, we report on the complexes [Zn(bpy)-
LI,II,IV2], [Zn(phen)LI,II,IV2], [Cd(bpy)LIV2] and [Cd(phen)LIV2] and
their analytical, spectroscopic and structural characterization. A fo-
cus will be put on the impact of the pending NHR0 (R0 = H or Ph)
functions in complexes of LIꢀ and LIIꢀ (in contrast to LIVꢀ) on the
molecular and crystal structures. Also the C–Cl bond activation of
the complexes [Cd(HLIV)2LIV2], and [Cd(p-BrC6H4C(S)NH2)LV
]
2
[21,22]. It is noteworthy that the complex [Cd2LIV4] is binuclear
in the solid state while in solutions exclusively the monomeric
form is observed [19].
On the other hand, a promising strategy for inorganic crystal
engineering through combination of noncovalent bonds such as
[Zn(phen)LIV
] towards CH2Cl2 and related experiments are
2
van der Waals,
p
ꢁ ꢁ ꢁ
p
stacking and hydrogen bonds with coordina-
discussed.
tion chemistry has attracted increasing attention in recent years
[23–25]. In contrast to the thioamide ligands LIVꢀ and LVꢀ the thio-
urea ligands LIꢀ and LIIꢀ contain a pendant amino function NHR0
(R0 = H or Ph) allowing either the formation of intermolecular
hydrogen bonds (with impact on the crystal structure) or intramo-
lecular N–Hꢁ ꢁ ꢁO@P bonds. The latter might provoke the blocking of
the P@O coordination site and lead to a 1,3-N,S coordination as re-
cently shown for related square planar complexes of Ni(II), Pd(II)
and Cu(II) [26–30]. In the presence of chelate ligands as 2,20-bipyr-
idine (bpy) or 1,10-phenanthroline (phen) Zn(II) and Cd(II) might
thus form three different coordination modes for LI,IIꢀ: 1,5-O,S-,
1,3-N,S- (both hexacoordinate) or monodentate N-coordination
(tetracoordinate).
2. Results and discussion
The complexes [ZnLI,II,IV2], [Cd2LIV4], [Zn(bpy)LII,IV
] and
2
[Zn(phen)LII,IV2] were prepared according to the previously de-
scribed methods [18–20]. The complexes [Zn(bpy)LI2], [Zn(phen)-
LI2], [Cd(bpy)LIV2] and [Cd(phen)LIV2] were synthesized by the
same procedure: a benzene solution of [ZnLI2] or [Cd2LIV4] was
added dropwise to a benzene solution of bpy or phen (Scheme
1). The obtained compounds are microcrystalline solids soluble in
most polar solvents. Concerning the symmetry of the presumably
hexacoordinated heteroligand complexes, two different stereoiso-
mers were expected for both 1,3-N,S- or 1,5-O,S-coordination. If
the S atoms of the two thiourea/thioamide ligands both lie in trans
orientation to the two diimine N atoms, a pseudo C2v symmetry is
given, for an idealized octahedral geometry. In this case the N
(1,3-N,S) or O (1,5-O,S) atoms of the thiourea/thioamide ligand lie
in the axial positions. If one of the S atoms lies instead in the axial
position, the symmetry is lost (C1). In reality, all of these stereoiso-
mers are chiral, since the N^S or O^S chelate breaks the C2v sym-
Therefore, the combination of the thiourea ligands LIꢀ and LIIꢀ
and
a-diimine ligands as bpy or phen in corresponding Zn(II) or
Cd(II) complexes seemed to be interesting and recently we could
report on the reaction of the Zn(II) complexes [ZnLII,IV2] with bpy
and phen leading to complexes of the type [Zn(N^N)LII,IV
]
2
(N^N = bpy or phen) [20]. Within this study we also found that
the complex [Zn(phen)LIV2] is able to activate the C–Cl bond in
CH2Cl2 leading to the products [Zn(phen)LIVCl] and LIV–CH2–LIV
,
Scheme 1. Preparation of [Zn(bpy)LI2], [Zn(phen)LI2], [Cd(bpy)LIV2] and [Cd(phen)LIV2] and possible stereoisomers of the products.

D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
21
Ph
N
OiPr
OiPr
Ph
N
OiPr
OiPr
P
P
S
O
S
O
CH2Cl2
2 [Zn(phen)LIV
]
2
2
+
CH2
S
Zn
N
N
Cl
O
P
OiPr
OiPr
Ph
N
[Zn(phen)LIVCl]
LIV-CH2-LIV
Scheme 2. Preparation of [Zn(phen)LIVCl] and LIV–CH2–LIV
.
metry and thus for each conformer a pair of enantiomers should be
expected.
LIV–CH2–LIV, respectively. Recrystallization of the other Zn(II) or
Cd(II) complexes described in this study from CH2Cl2 lead to micro-
crystalline precipitates of the starting complexes without noticable
C–Cl activation. Trying to attempt the C–Cl activation by
[Zn(phen)LIV2] using CHCl3 or CCl4 instead of CH2Cl2 also failed
(even under reflux conditions).
In the IR spectra of [Zn(bpy)LI2] and [Zn(phen)LI2] the charac-
teristic absorption for the P@O group is found at around
1145 cmꢀ1, slightly red-shifted compared to the band in the spec-
trum of [ZnLI2] (
mP@O = 1132 [20]). The absorption bands for the
P@O group in the spectra of [Cd(bpy)LIV2] and [Cd(phen)LIV2] are
In the 31P{1H} spectrum of [Zn(phen)LIVCl] a singlet signal, with
a chemical shift characteristic for the amidophosphate environ-
ment of the phosphorus nucleus [11], was observed at 6.6 ppm.
This signal is low-field shifted in comparison to the corresponding
resonance of the parent complex [Zn(phen)LIV2] (d = 6.1 ppm [20]).
observed at about 1240 cmꢀ1, essentially at the same energy as ob-
served for the parent ligand HLIV
(mP@O = 1252 [19]). This strongly
indicates the formation of intramolecular hydrogen bonds in the
structures of [Zn(bpy)LI2] and [Zn(phen)LI2]. The corresponding
bands for the phosphoryl groups in [Zn(phen)LIVCl] and LIV
–
There is a singlet at ꢀ3.2 ppm in the 31P{1H} NMR spectrum of LIV
–
CH2–LIV were found at 1141 and 1246 cmꢀ1, respectively. The
absorption band at 1504–1562 cmꢀ1 corresponds to the SCN frag-
ment, while for the POC group an absorption is observed at
997–1014 cmꢀ1. Besides these bands, a number of characteristic
bands for the NH2 group were found in the spectra of [Zn(bpy)LI2]
CH2–LIV (d = ꢀ3 ppm in CCl4 + CD3C6D5 [32]).
The 1H NMR spectrum of [Zn(phen)LIVCl] contains the expected
sets of signals for the iPrO and Ph protons of the LIVꢀ ligand and
also signals corresponding to the diimine chelate ligand. Unfortu-
nately, the latter two signal sets largely overlap preventing conclu-
sions on the complex symmetry. Analysis of the integral intensities
of the proton signals testifies the constitution of the complex
[Zn(phen)LIVCl], which was further supported by the elemental
analysis. In the 1H NMR spectrum of LIV–CH2–LIV besides a set of
signals for the iPrO and Ph protons there is a singlet for the CH2
protons at 4.49 ppm. A very remarkable finding is, that both 31P
and 1H NMR spectra are far better resolved for [Zn(phen)LIVCl]
and [Zn(phen)LI2] at about 1620, 3130, 3265 and 3390 cmꢀ1
.
In the 31P{1H} NMR spectra of the hexacoordinated complexes
[Zn(bpy)LI2], [Zn(phen)LI2], [Cd(bpy)LIV and [Cd(phen)LIV
]
2
]
2
each one singlet signal is observed at 6.4–6.6 ppm for the Zn com-
plexes and at 3.8–4.2 ppm for the Cd derivatives. Either only one of
the possible stereoisomers (compare Scheme 1) is present in solu-
tion or the spectral resolution is too bad to allow discrimination
between C2v and C1 isomers (and their enantiomers).
than for the four heteroligand complexes [M(a
-diimine)LI,IV2].
In the 1H NMR spectra of [Zn(bpy)LI2], [Zn(phen)LI2], [Cd(bpy)-
LIV2] and [Cd(phen)LIV2] each a set of signals for the iPrO protons
were found at 1.03–1.35 (CH3) and 4.38–4.73 (CH) ppm, respec-
tively. The NH2 group protons in the spectra of [Zn(bpy)LI2] and
[Zn(phen)LI2] were observed as two broad singlets at 6.11–
6.68 ppm. The broadening of the signals is very probably due to
the formation of the intramolecular hydrogen bond. The proton
signals for the aromatic rings were found at 6.82–8.46 ppm, par-
tially overlapping with the solvent signal (CDCl3). Generally all
This supports our idea that the dissociation of the diimine ligands
might be the reason for the broad resonances of the latter. For the
pentacoordinated complex [Zn(phen)LIVCl] such dissociation is far
less likely.
Single crystals suitable for XRD have been obtained from the
complexes [ZnLII2], [Cd(phen)LIV2], [Cd(bpy)LIV2], [Zn(bpy)LI2]
and [Zn(phen)LIVCl] by crystallization from CH2Cl2 solutions. The
compounds [ZnLII2], [Cd(phen)LIV2] and [Zn(bpy)LI2] crystallize
in the monoclinic space groups C2/c or P21/c, while [Cd(bpy)LIV
]
2
1H NMR signals in the spectra of [M(bpy)LI,IV2] and [M(phen)LI,IV
]
2
and [Zn(phen)LIVCl] were solved in the triclinic space group P1
(see Section 3).
ꢀ
are markedly broadened and we tentatively assign this either to
the presence of several stereoisomers (Scheme 1) or to fast
exchange between free and bound bpy or phen in solutions. An ex-
The complex [ZnLII2] in the crystal is located in a special posi-
tion at the axis 2. It exhibits a spirocyclic chelate with a distorted
tetrahedral ZnO2S2 core with the deprotonated ligand LIIꢀ showing
a 1,5-O,S coordination (Fig. 1). The endocyclic angle O–Zn–S is re-
duced and the exocyclic counterpart is increased in comparison
with an ideal tetrahedral angle of 109.5° (Table 1). The six-mem-
bered chelate rings are essentially planar in the molecule of
[ZnLII2]. The maximum deviation from the mean-square plane
Zn–O–P–N–C–S is observed for P(1) phosphorus and O(1) oxygen
atoms. The H(2)–N(2)–C(1)–S(1) moieties in the ligands are in a
cis-conformation (torsion angle is 0(2)°). In the crystal structure
change equation can be written as follows: [M(
a-diimine)-
LI,IV2] M [MLI,IV2] +
a-diimine.
Thus, unfortunately, neither 1H or 31P NMR nor IR data allow
unequivocal assignment of the coordination mode of LI,IVꢀ in the
heteroligand complexes [M(bpy)LI,IV2] and [M(phen)LI,IV2]. There-
fore we tried to obtain single crystals for an XRD study by recrys-
tallizing the new complexes from various solvents. Surprisingly,
recrystallization of [Zn(phen)LIV2] from a CH2Cl2 solution led to
the formation of the complex [Zn(phen)LIVCl] and S,S0-bis(benzim-
idothio-N-diisopropoxyphosphoryl)methane LIV–CH2–LIV (Scheme
2). As mentioned in the introdcution, LIV–CH2–LIV was previously
synthesized by the reaction of the potassium salt KLIV with CH2I2
of [ZnLII
] there are intermolecular hydrogen bonds N(2)–
2
H(2)ꢁ ꢁ ꢁS(1)a between neighboring molecules (Table 2), leading to
a polymeric chain along the b axis.
in an acetonitrile solution under reflux [27]. The yield of LIV
–
The complex [Zn(bpy)LI2] contains a distorted ZnN4S2 core with
an overall pseudo C2v symmetry (compare Scheme 1) and the LIꢀ
ligand binding to Zn in the 1,3-N,S coordination mode (Fig. 2).
CH2–LIV in this reaction was 69%, while the reaction of [Zn(phen)-
LIV2] with CH2Cl2 yields 98% and 96% for [Zn(phen)LIVCl] and

22
D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
cycle is distorted (torsion angle N–C–C–N is –9.5(6)°). As expected,
there are intramolecular hydrogen bonds of the type N–HꢁꢁꢁO@P in
the crystal of [Zn(bpy)LI2] (Table 2), which very probably have pro-
voked the formation of the 1,3-N,S coordination mode [33]. Fur-
thermore, there are intermolecular hydrogen bonds of the type
N–Hꢁ ꢁ ꢁS@C (Table 2). These bonds are formed between the other
H-atom of the NH2 group of a molecule and the C@S sulfur atoms
of two neighboring molecules. Additionally to this 3D network of
H-bridges
p p stacking interactions between the bpy rings (Ta-
ꢁ ꢁ ꢁ
ble 3) were found in the crystal of [Zn(bpy)LI2], highlighting the
suitability of this combination of ligands (deprotonated
thioureas + a-diimines) in Zn(II) complexes for the formation of
supramolecular networks in the crystal phase.
Fig. 1. Molecular structure of [ZnLII2]. H-atoms, not involved in hydrogen bonding,
Both complexes [Cd(bpy)LIV2] and [Cd(phen)LIV2]ꢁCH2Cl2 con-
tain a distorted CdN2O2S2 core with the LIVꢀ ligand coordinating
in the 1,5-O,S coordination mode (Figs. 3 and 4). However, while
for [Cd(bpy)LIV2] a pseudo C2v symmetry can be stated, the phen
derivative has only C1 symmetry. The C@S bond lengths are de-
creased, while the P@O and C–N distances are increased (Table 1)
in comparison with the corresponding distances reported for
are omitted.
The Cꢁ ꢁ ꢁS and Pꢁ ꢁ ꢁO bonds are shortened, and the P–N, C–N(P) and
Zn–S distances are increased (Table 1) in comparison with the cor-
responding distances reported for [ZnLI2] [20]. The bond lengths
Zn–N(P) (2.096(3) Å) are shorter than the Zn–N (2.150(3) Å) bonds
with bpy. The N–Zn–Sendo angles (65.10(9)°) are much smaller
compared to the O–Zn–Sendo angles (102.00(6) and 109.53(6)°) in
the parent complex [ZnLI2] [20]. The four-membered Zn–S–C–N
metallocycles are flat, while the five-membered Zn–N–C–C–N
[Cd2LIV
]
4
(d(C@S) = 1.744(5), 1.761(5) Å; d(P@O) = 1.444(2),
1.468(2) Å; d(C–N) = 1.278(7), 1.283(7) Å) [19]. In both com-
pounds, the Cd–O bonds are slightly shorter than the Cd–N bonds
pointing to a reasonable binding of the P@O donor. The O–Cd–Sendo
Table 1
Selected bond lengths (Å), and bond angles (°) for [ZnLII2], [Cd(bpy)LIV2], [Cd(phen)LIV2]ꢁCH2Cl2, [Zn(bpy)LI2] and [Zn(phen)LIVCl].
[ZnLII
]
2
[Zn(bpy)LI2
]
[Cd(bpy)LIV
]
2
[Cd(phen)LIV2]ꢁCH2Cl2
[Zn(phen)LIVCl]
C@S
P@O
P–N
C–N(P)
M–O
M–S
M–N
M–Cl
1.750(3)
1.495(2)
1.601(2)
1.288(3)
2.286(1)
1.947(2)
1.711(4)
1.464(3)
1.636(3)
1.338(4)
1.729(3), 1.734(3)
1.480(2), 1.482(2)
1.634(3), 1.637(2)
1.296(4), 1.306(4)
2.327(2), 2.358(2)
2.582(1), 2.630(1)
2.390(3), 2.400(2)
1.713(4), 1.725(4)
1.462(3), 1.473(4)
1.598(4), 1.616(4)
1.307(5), 1.308(6)
2.304(3), 2.328(3)
2.592(1), 2.634(1)
2.369(3), 2.422(3)
1.4800(2)
1.723(2)
1.629(2)
1.291(3)
2.073(2)
2.387(1)
2.121(2), 2.229(2)
2.258(1)
2.648(1)
2.096(3)a 2.150(3)
S@C–N(P)
S@C–N(C, H)
N–C–N
C–N–P
129.4(2)
116.1(2)
127.1(3)
128.2(3), 129.1(3)
129.4(2)
110.9(2)
119.7(2)
131.7(2)
120.6(1)
108.6(1)
126.6(1)
120.3(3)
123.7(4)
124.8(2)
116.76(18)
74.66(10)
125.1(2), 125.9(2)
118.6(1), 118.8(1)
105.0(1), 105.1(1)
121.4(1), 122.8(1)
129.3(3), 131.8(3)
119.4(2), 122.7(2)
110.7(1), 113.8(1)
123.4(2), 128.0(2)
129.5(2)
117.3(1)
112.2(1)
128.6(1)
N–P@O
M–S@C
M–O@P
M–N–P
M–N–C
O–M–Sendo
N–M–Sendo
N–M–Nendo
O–M–Cl
S–M–Cl
N–M–Cl
131.2(2)
104.0(2)
101.52(5)
86.12(5), 88.38(6)
67.75(9)
85.72(9), 85.92(9)
69.8(1)
93.28(6)
65.1(1)
76.8(1)
76.3(1)
100.72(7)
117.13(4)
98.58(7), 107.00(7)
a
The bond length in the four-membered metallocycle Zn–S–C–N.
Table 2
Hydrogen bond lengths (Å) and angles (°) for [ZnLII2], [Cd(phen)LIV2]ꢁCH2Cl2, [Zn(bpy)LI2] and [Zn(phen)LIVCl].
D–Hꢁ ꢁ ꢁA
D–H
Hꢁ ꢁ ꢁA
2.74(2)
2.58
Dꢁ ꢁ ꢁA
D–Hꢁ ꢁ ꢁA
167(3)
159
a
[ZnLII
]
2
N(2)–H(2)ꢁ ꢁ ꢁS(1)a
0.74(3)
0.97
0.97
0.83(3)
0.86(5)
0.93
3.466(2)
3.501(10)
3.263(10)
2.773(6)
3.521(4)
3.041(2)
3.561(4)
[Cd(phen)LIV2]ꢁCH2Cl2
C(50)–H(50A)ꢁ ꢁ ꢁO(2A)
C(50)–H(50B)ꢁ ꢁ ꢁO(1B)
N(2)–H(21)ꢁ ꢁ ꢁO(1)
2.32
164
[Zn(bpy)LI2
]
2.06(3)
2.75(5)
2.64
143(3)
151(4)
107
b
N(2)–H(22)ꢁ ꢁ ꢁS(1)#1
C(6A)–H(6A)ꢁ ꢁ ꢁCl(1)#1
C(10A)–H(10A)ꢁ ꢁ ꢁCl(1)#2
[Zn(phen)LIVCl]c
0.93
2.74
147
a
b
c
Symmetry codes: 1/2 ꢀ x, 1/2 ꢀ y, 1 ꢀ z.
Symmetry codes: #1 2 ꢀ x, ꢀy, ꢀz.
Symmetry codes: #1 2 ꢀ x, 1 ꢀ y, 2 ꢀ z; #2 1 ꢀ x, ꢀy, 2 ꢀ z.

D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
23
Fig. 2. Molecular structure of [Zn(bpy)LI2]. H-atoms, not involved in hydrogen
bonding, are omitted.
Table 3
Selected
p
ꢁ ꢁ ꢁ
p
interactions for [Cd(bpy)LIV2], [Cd(phen)LIV2]ꢁCH2Cl2, [Zn(bpy)LI2
]
and [Zn(phen)LIVCl].
Fig. 3. Molecular structure of [Cd(bpy)LIV2]. H-atoms are omitted.
Cg(I)a Cg(J)
Cg–Cgb (Å) Dihedral
Betac
angles (°) (°)
d
[Cd(bpy)LIV
]
Cg(5)
Cg(5)
Cg(4)
Cg(4)
Cg(4)
Cg(5)
Cg(5)
Cg(8)
Cg(8)
Cg(4)
Cg(3)
Cg(6)
Cg(4)#1 3.864(2)
8.81(18)
0
0
0.8(3)
0.2(2)
0.8(3)
0.8(3)
0.2(2)
0.8(3)
0
19.39
47.48
45.22
38.42
18.82
37.67
47.08
19.01
47.55
39.49
26.15
18.71
2
Cg(5)#1 5.017(2)
Cg(4)#1 4.888(3)
Cg(5)#1 4.361(3)
Cg(8)#1 3.626(3)
Cg(4)#1 4.361(3)
Cg(8)#1 5.055(3)
Cg(4)#1 3.626(3)
Cg(5)#1 5.055(3)
Cg(4)#1 4.557(3)
[Cd(phen)LIV2]ꢁCH2Cl2
e
[Zn(bpy)LI2
]
f
[Zn(phen)LIVCl]g
Cg(6)#1 3.8687(19) 0.79(15)
Cg(6)#1 3.679(2)
0
a
Cg refers to the ring center of gravity and the numbers represent the rings
involved in the interactions.
b
Cg–Cg: distance between ring centroids.
Beta: angle Cg(I) ? Cg(J) vector and normal to plane I.
Symmetry codes: #1 ꢀ x, ꢀy, 1 ꢀ z. Cg(4): N(1C)–C(2C)–C(3C)–C(4C)–C(5C)–
c
d
C(6C), Cg(5): N(7C)–C(8C)–C(9C)–C(10C)–C(11C)–C(12C).
e
Symmetry codes: #1 2 ꢀ x, 1 ꢀ y, 1 ꢀ z. Cg(4): N(1C)–C(2C)–C(11C)–C(12C)–
C(13C)–C(14C), Cg(5): N(4C)–C(3C)–C(8C)–C(7C)–C(6C)–C(5C), Cg(8): C(2C)–C(3C)–
C(8C)–C(9C)–C(10C)–C(11C).
f
Symmetry codes: #1 2 ꢀ x, 1 ꢀ y, ꢀz. Cg(4): N(1A)–C(2A)–C(3A)–C(4A)–C(5A)–
C(6A).
g
Symmetry codes: #1 1 ꢀ x, ꢀy, 2 ꢀ z. Cg(3): N(4A)–C(3A)–C(8A)–C(7A)–C(6A)–
Fig. 4. Molecular structure of [Cd(phen)LIV2]ꢁCH2Cl2. H-atoms, not involved in
C(5A), Cg(6): N(1A)–C(2A)–C(3A)–C(8A)–C(9A)–C(10A)–C(11A)–C(12A)–C(13A)–
C(14A).
hydrogen bonding, are omitted.
The structure of the complex [Zn(phen)LIVCl] exhibits a dis-
torted tetragonal-pyramidal ZnClN2OS core (Fig. 5). The bond
lengths (S)C–N and P–N are shortened (Table 1) and the C@S and
P@O distances are considerably lengthened in comparison with
the corresponding interatomic distances reported for HLIV [11].
The six-membered Zn–O–P–N–C–S cycle has an asymmetrical boat
conformation. The maximal deviation of atoms from the least
angles are smaller compared to the terminal ligands in the parent
complex [Cd2LIV4], which is due to the presence of the additional
donor ligand. The six-membered Cd–O–P–N–C–S metallocycles
are distorted boats, while the five-membered Cd–N–C–C–N cycles
are flat. Remarkably, the CdN2O2S2 cores of the two complexes dif-
fer only marginally concerning these binding parameters and it
seems that the two stereoisomers (C2v versus C1) have almost the
same binding energy and might thus coexist in solution. Only sub-
tle differences in energy and/or solubility might lead to a final dis-
crimination during the crystallization. There are intermolecular
hydrogen bonds of the type C–Hꢁ ꢁ ꢁO–P in the crystal of [Cd(phen)-
LIV2]ꢁCH2Cl2 (Table 2), which are formed between the H atoms of
the solvent molecule (CH2Cl2) and the O atoms of the iPrO groups
square plane (LSP) of the cycle is observed for the
O
(ꢀ0.178(2) Å) and P (0.2051(9) Å) atoms. The five-membered Zn–
N–C–C–N cycle is almost planar. The maximal deviation of atoms
from the LSP of the cycle is observed for the Zn (0.0628(10) Å)
and the N (ꢀ0.057(2) and ꢀ0.045(2) Å) atom. There are intermo-
lecular hydrogen bonds of the type C–Hꢁ ꢁ ꢁCl–Zn in the crystal of
[Zn(phen)LIVCl] (Table 2). These bonds are formed between two
H atoms of the phenanthroline ligand of one complex, and the Cl
atoms of two neighboring complexes, while the Cl atom of the first
complex forms two intermolecular hydrogen bonds with protons
of the phen ligands in the same two neighboring complexes.
of the anionic thiobenzamide ligand. There are also
pꢁ ꢁ ꢁp stacking
interactions between bpy or phen rings (Table 3), which, together
with the H bridges, give rise to polymeric chains in the crystal
structures of [Cd(bpy)LIV2] and [Cd(phen)LIV2]ꢁCH2Cl2.

24
D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
3.2.3. [Cd(bpy)LIV
]
2
Yield: 0.357 g (82%). M.p. 126–128 °C. 1H NMR: d = 1.16–1.32
(m, 24H, CH3), 4.48–4.69 (m, 4H, OCH), 7.02–8.46 (m, overlapping
with the solvent signal, Ph + bpy) ppm. 31P{1H} NMR: d = 3.8 ppm.
IR:
36H46CdN4O6P2S2 (869.26): C, 49.74; H, 5.33; N, 6.45. Found: C,
49.93; H, 5.26; N, 6.50%.
m
= 1004 (POC), 1240 (P@O), 1504 (SCN) cmꢀ1. Anal. Calc. for
C
3.2.4. [Cd(phen)LIV
]
2
Yield: 0.323 g (88%). M.p. 135–137 °C. 1H NMR: d = 1.13–1.35
(m, 24H, CH3), 4.38–4.73 (m, 4H, OCH), 7.08–8.39 (m, overlapping
with the solvent signal, Ph + phen) ppm. 31P{1H} NMR: d = 4.2 ppm.
Fig. 5. Molecular structure of [Zn(phen)LIVCl]. H-atoms, not involved in hydrogen
bonding, are omitted.
IR:
m
= 1014 (POC), 1244 (P@O), 1512 (SCN) cmꢀ1. Anal. Calc. for
C38H46CdN4O6P2S2 (893.28): C, 51.09; H, 5.19; N, 6.27. Found: C,
51.25; H, 5.11; N, 6.32%.
Additionally to the intermolecular H bonds,
p p stacking interac-
ꢁ ꢁ ꢁ
3.3. Synthesis of [Zn(phen)LIVCl] and LIV–CH2–LIV
tions between the phenanthroline rings (Table 3) produce centro-
symmetric dimers in the crystal structure of [Zn(phen)LIVCl].
A suspension of [Zn(phen)LIV2] (0.1 g, 0.12 mmol) in CH2Cl2
(10 mL) was stirred for 3 h. After 2 days colorless crystals of
[Zn(phen)LIVCl] appeared. The mixture was left for 2 days more.
Then the solution was decontated. Crystals of [Zn(phen)LIVCl]
were isolated, washed by n-hexane and dried in vacuo. The solvent
from the mother solution was removed in vacuo and the resulting
precipitate of LIV–CH2–LIV was washed with n-hexane. The yields
are calculated relative to [Zn(phen)LIV2].
3. Experimental
The complexes [ZnLI,II,IV2], [Cd2LIV4], [Zn(bpy)LII,IV
] and
2
[Zn(phen)LII,IV2] were synthesized according to the previously de-
scribed methods [18–20].
3.1. General procedures
3.3.1. [Zn(phen)LIVCl]
Infrared spectra (Nujol) were recorded using a Specord M-80
spectrometer in the range range 400–3600 cmꢀ1. NMR spectra
were obtained on a Bruker Avance 300 MHz spectrometer at
25 °C. 1H and 31P{1H} NMR spectra (CDCl3) were recorded at
299.948 and 121.420 MHz, respectively. Chemical shifts are re-
Yield: 0.067 g (98%). M.p. 163–165 °C. 1H NMR: d = 1.18 (d,
3JH,H = 6.1 Hz, 12H, CH3), 4.66 (d sept, 3JPOCH = 7.7 Hz, 3JH,H = 6.2 Hz,
2H, OCH), 7.32–7.50, 7.87–8.04, 8.23–8.37, 8.46–8.60, 9.45–9.57
(m, 13H, Ph + phen) ppm. 31P{1H} NMR: d = 6.6 ppm. IR:
m
= 1004
Anal. Calc. for
25H27ClN3O3PSZn (581.37): C, 51.65; H, 4.68; N, 7.23. Found: C,
(POC), 1141 (P@O), 1536 (SCN) cmꢀ1
C
.
ported with reference to SiMe4 (1H) and 85% H3PO4 31P{1H}). Ele-
(
mental analyses were performed on a CHNS HEKAtech EuroEA
3000 analyzer.
51.84; H, 4.49; N, 7.38%.
3.3.2. LIV–CH2–LIV
3.2. Synthesis of [Zn(bpy)LI2], [Zn(phen)LI2], [Cd(bpy)LIV2] and
Yield: 0.070 g (96%). M.p. 126–127 °C (126 °C [32]). 1H NMR:
[Cd(phen)LIV
]
2
3
d = 1.12 (d, JH,H = 6.3 Hz, 24H, CH3), 4.74 (m, 4H, OCH), 4.49 (s,
2H, CH2), 7.06–7.18, 7.25–7.49, 7.61–8.04 (m, 10H, Ph) ppm.
A solution of the complexes [ZnLI2] (0.35 g, 0.5 mmol) or
[Cd2LIV4] (0.36 g, 0.25 mmol) in benzene (10 mL) was added drop-
wise to a solution of bpy (0.08 g, 0.5 mmol) or phen (0.09 g,
0.5 mmol) in benzene (10 mL). After complete addition, the solu-
tion was stirred for an hour. The solvent was then removed in va-
31P{1H} NMR: d = ꢀ3.2 ppm (ꢀ3 ppm in CCl4 + CD3C6D5 [32]). IR:
m
= 1007 (POC), 1246 (P@O), 1512 (S–C@N) cmꢀ1. Anal. Calc. for
C27H40N2O6P2S2 (614.69): C, 52.76; H, 6.56; N, 4.56. Found: C,
52.89; H, 6.47; N, 4.45%.
cuo. The residue was recrystallized from
a CH2Cl2/n-hexane
3.4. X-ray crystallography
mixture. The complexes [Zn(bpy)LI2], [Zn(phen)LI2], [Cd(bpy)LIV
and [Cd(phen)LIV2] were isolated as colorless powders.
]
2
The X-ray data for [ZnLII2], [Cd(bpy)LIV2], [Cd(phen)LIV2],
[Zn(bpy)LI2] and [Zn(phen)LIVCl] were collected on a Bruker Smart
Apex II diffractometer. Data were corrected for absorption using
the SADABS program [34]. The structure was solved by direct method
using the SHELXS97 [35] program and refined by the full matrix
least-squares using SHELXL97 [35]. All non-hydrogen atoms were re-
fined anisotropically. The hydrogen atoms were located on differ-
ence map and refined isotropically.
3.2.1. [Zn(bpy)LI2]
Yield: 0.301 g (86%). M.p. 144–146 °C. 1H NMR: d = 1.19–1.30
(m, 24H, CH3), 4.53 (br. s, 4H, OCH), 6.11 (br. s, 2H, NH2), 6.38
(br. s, 2H, NH2), 6.97–8.37 (m, overlapping with the solvent signal,
bpy) ppm. 31P{1H} NMR: d = 6.4 ppm. IR:
m = 1001 (POC), 1147
(P@O), 1557 (SCN), 1624, 3130, 3267, 3387 (NH2) cmꢀ1. Anal. Calc.
for C24H40N6O6P2S2Zn (700.07): C, 41.18; H, 5.76; N, 12.00. Found:
C, 41.33; H, 5.71; N, 11.94%.
3.4.1. [ZnLII
]
2
C
26H42N4O6P2S2Zn, Mr = 696.09 g molꢀ1
group C2/c, a = 14.4074(13), b = 20.3270(19), c = 13.6135(13) Å,
b = 121.030(1)°, V = 3416.3(6) Å3, Z = 4, = 1.353 g cmꢀ3
(Mo
) = 0.977 mmꢀ1
reflections: 14 311 collected, 4033 unique,
,
monoclinic, space
3.2.2. [Zn(phen)LI2]
Yield: 0.329 g (91%). M.p. 172–174 °C. 1H NMR: d = 1.03–1.27
(m, 24H, CH3), 4.40–4.61 (m, 4H, OCH), 6.25 (br. s, 2H, NH2), 6.68
(br. s, 2H, NH2), 6.82–8.40 (m, overlapping with the solvent signal,
q
, l
Ka
,
Rint = 0.023.
phen) ppm. 31P{1H} NMR: d = 6.6 ppm. IR:
m = 997 (POC), 1143
(P@O), 1562 (SCN), 1618, 3127, 3261, 3393 (NH2) cmꢀ1. Anal. Calc.
for C26H40N6O6P2S2Zn (724.09): C, 43.13; H, 5.57; N, 11.61. Found:
C, 43.01; H, 5.60; N, 11.58%.
3.4.2. [Cd(bpy)LIV
]
2
C
36H46CdN4O6P2S2,
Mr = 869.26 g molꢀ1
,
triclinic,
space
ꢀ
group P1, a = 10.6690(11), b = 14.5907(15), c = 14.775(3) Å,
a
=

D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
25
107.050(1), b = 93.975(2),
c
= 109.560(1)°, V = 2035.9(5) Å3, Z = 2,
To date we can only speculate on the quite selective character
of this reaction and why the very similar bpy-containing com-
plex [Zn(bpy)LIV2] does not show the same reaction. The latter
might be explained by the rigidity of the phen ligand compared
to bpy and will be further explored in the future by applying
other a-diimine ligands. Further future work will also be devoted
to the application of the C–Cl bond cleavage reaction to other
substrates.
q
= 1.418 g cmꢀ3 ) = 0.764 mmꢀ1, reflections: 15 022 col-
,
l
(Mo Ka
lected, 7792 unique, Rint = 0.026.
3.4.3. [Cd(phen)LIV2]ꢁCH2Cl2
C38H46CdN4O6P2S2ꢁCH2Cl2, Mr = 978.20 g molꢀ1
,
monoclinic,
space group P21/c, a = 19.844(2), b = 10.0204(10), c = 24.155(2) Å,
b = 108.201(1)°, V = 4562.8(7) Å3, Z = 4,
q , l(Mo
= 1.424 g cmꢀ3
Ka
) = 0.804 mmꢀ1, reflections: 26 072 collected, 10 587 unique,
Appendix A. Supplementary material
Rint = 0.038.
CCDC 730814, 730810, 73081, 7308113 and 730812 contain the
supplementary crystallographic data for ([ZnLII2]), ([Cd(bpy)LIV2]),
([Cd(phen)LIV2]ꢁCH2Cl2), ([Zn(bpy)LI2]) and ([Zn(phen)LIVCl]).
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/j.ica.2010.
10.001.
3.4.4. [Zn(bpy)LI2]
C
24H40N6O6P2S2Zn, Mr = 700.09 g molꢀ1
,
monoclinic, space
group C2/c, a = 25.597(6), b = 9.460(2), c = 15.493(4) Å, b =
113.126(2)°, V = 3450.1(14) Å3, Z = 4, = 1.348 g cmꢀ3
(Mo
) = 0.969 mmꢀ1
reflections: 12 650 collected, 3387 unique,
Rint = 0.062.
q
, l
Ka
,
3.4.5. [Zn(phen)LIVCl]
25H27ClN3O3PSZn, Mr = 581.38 g molꢀ1, triclinic, space group
C
References
ꢀ
P1, a = 7.8780(16), b = 10.525(2), c = 17.167(3) Å,
93.51(3),
= 108.20(3)°, V = 1323.4(5) Å3, Z = 2,
(Mo K
) = 1.200 mmꢀ1, reflections: 11 923 collected, 6208 un-
a
q
= 99.61(3), b =
c
= 1.459 g cmꢀ3
,
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4049.
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The reaction of [ZnLI,II2] (LI = [NH2C(S)NP(O)(OiPr)2]ꢀ; LII = [Ph-
NHC(S)NP(O)(OiPr)2]ꢀ) or [Cd2LIV4] (LIV = [PhC(S)NP(O)(OiPr)2]ꢀ)
with 2,20-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to
the heteroligand complexes [Zn(bpy)LI,II2], [Zn(phen)LI,II2],
[Cd(bpy)LIV2] or [Cd(phen)LIV2], respectively. The introduction of
the diimine ligands into the coordination sphere of the metal cat-
ion provokes a change from the initial 1,5-O,S- to 1,3-N,S-coordina-
tion of the anionic ligands for the Zn(II) complexes, confirming that
the formation of intramolecular hydrogen bonds N–Hꢁ ꢁ ꢁO@P is a
necessary condition for the stabilization of the 1,3-N,S-isomer. In
the corresponding Cd(II) complexes the initial 1,5-O,S-coordination
was conserved. At the moment we can only speculate on the rea-
son for this different behavior, since, while the softer character of
Cd(II) might favor a N- over a O-coordination, the larger size of
Cd(II) should prefer the larger bite angle of the 1,5-O,S chelate over
the small bite angle of the 1,3-N,S coordination. Interestingly, the
crystal structure of the Zn(II) derivative exhibits the higher sym-
metric stereoisomer (pseudo C2v) having both N(ligand) atoms in
the axial position of the octahedral coordination sphere, while both
S(ligand) and N(diimine) atoms form the equatorial donor atom
set. For the corresponding Cd(II) complexes both this stereoisomer
and a less symmetric isomer (C1), having one S equatorial and one
axial, is found. The binding parameters let us assume that the dif-
ferences in energy are rather small and both forms might coexist in
solution. The broad resonance in NMR spectra at ambient temper-
ature might be an indication for this. However, another reason
might be the (partial and reversible) dissociation of the diimine li-
gands. This is supported by the rather sharp and resolved NMR
spectra of the pentacoordinated complex [Zn(phen)LIVCl] which
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was successfully synthesized from the precursor [Zn(phen)LIV
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2
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instead of CH2Cl2 do not lead to the formation of chlorine substi-
tuted products even under reflux conditions. Also the other Zn(II)
and Cd(II) complexes described herein did not show the same reac-
tion with CH2Cl2.

26
D.A. Safin et al. / Inorganica Chimica Acta 366 (2011) 19–26
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