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Novel mono- and bimetallic organotin(IV)

Cite this: Dalton Trans., 2019, 48,
compounds as potential linkers for coordination
6527 polymers†
Adrian-Alexandru Someşan, Ioana Barbul, Sabina-Mădălina Vieriu,
Richard A. Varga * and Cristian Silvestru

The reaction of [2-(OvCH)C6H4]Me2SnCl (2), obtained by the hydrolysis of [2-{(CH2O)2CH}C6H4]-

Received 23rd February 2019,
Accepted 11th April 2019
DOI: 10.1039/c9dt00817a
rsc.li/dalton
Me2SnCl (1), with the appropriate diamine, in a 2 : 1 molar ratio, in the absence of a solvent or catalyst,
resulted in the bimetallic species ClSnMe2[2-C6H4(4-CHvN-1,1’-C6H4C6H4-4’-NvCH)-2’-C6H4]-
Me2SnCl (4) and ClSnMe2[2-C6H4(CHvNCH2CH2NvCH)-2’-C6H4]Me2SnCl (5). The reaction of 2 and 5
with KSCN gave the corresponding isothiocyanates [2-(OvCH)C6H4]Me2Sn(NCS) (3) and (SCN)SnMe2-
[2-C6H4(CHvNCH2CH2NvCH)-2’-C6H4]Me2Sn(NCS) (6). Treating 3 with H2NCH2CH2NH2 also
resulted in the corresponding bimetallic compound 6. The reaction of 2 with sodium isonicotinate gave
[2-(OvCH)C6H4]Me2SnO(O)CC5H4N-4 (7) and the subsequent treatment with ZnTPP (TPP = tetraphenyl-
porphyrinate) led to the isolation of the heterobimetallic complex [{2-(OvCH)C6H4}Me2SnO(O)-
CC5H4N-4]ZnTPP (8). The compounds were characterized by multinuclear NMR spectroscopy and mass
spectrometry in solution and IR spectroscopy in the solid state. The molecular structures for compounds
1–6 and 8 were established by single-crystal X-ray diffraction. For all compounds intramolecular O→Sn or
Nimine→Sn coordination results in hypercoordinated species with a distorted trigonal bipyramidal
(C,E)C2SnX core (E = O, Nimine; X = Cl, Nisothiocyanato, Oisonicotinato). In the heterobimetallic complex 8 the
zinc atom has a distorted square pyramidal geometry with the Npyridyl atom at the apical position.

Introduction
Organotin(IV) compounds with aromatic C,E-pendant arm
ligands (E = N, O) have been well studied over the last years.
Derivatives with sp3 hybridized nitrogen in the pendant arm,
i.e. 2-(Me2NCH2)C6H4,1 2-(Et2NCH2)C6H4,2 or 2-[Me2NCH(R)]
C6H4 (R = Me,3 tBu4), have been characterized both in solution
and solid states. Recent reports discussed several organotin(IV)
species with sp2 hybridized nitrogen as the intramolecular
coordinating atom, as part of an imine function5 or oxazoline
ring,6 and underlined their potential applications. Oxygen-
bearing ligands consist mostly of ether function-containing
Department of Chemistry, Supramolecular Organic and Organometallic Chemistry
Centre (SOOMCC), Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai
University, 11 Arany Janos, 400028 Cluj-Napoca, Romania.
E-mail: richy@chem.ubbcluj.ro; Fax: (+40) 264-590818; Tel: (+40) 264-593833
† Electronic supplementary information (ESI) available: Numbering scheme for
NMR resonance assignments and NMR spectra; figures representing the optical
isomers as well as the supramolecular architectures in the crystal; X-ray crystal
data and structure refinement for compounds. CCDC 1860608 (1), 1860615 (2),
1860609 (3′), 1860614 (3″), 1860611 (4), 1860610 (5), 1860612 (6) and 1860613
(8·CH2Cl2). For ESI and crystallographic data in CIF or other electronic format
see DOI: 10.1039/c9dt00817a
organic fragments, but the majority of the examples have two
pendant arms, i.e. 2,6-(ROCH2)2C6H3 (R = Me,7a–f,k,m,o Et,7f
i
Pr,7a,f tBu,7a–d,f–j,l,n), except the ones containing a 1,3-dioxolane
ring,5 as well as systems with CvO,5,8a PvO8b,c and SvO8d
donor sites.
Apart from compounds containing a direct single or mul-
tiple tin-M bond (M = Sn, transition metal), discrete systems
are usually obtained by bridging the tin centres from two orga-
notin(IV) fragments with aromatic substituents bearing C,E-
pendant arms via dianionic inorganic (e.g. chalcogenide,1a,c,2,7i,j,9
carbonate,9b,f,n sulfate,9l selenite,10 phosphite or organophos-
phonate,11 etc.), organometallic (e.g. dimethylsilandiolato,9f,p
1,1′-ferrocenedicarboxylate,12 etc.) or organic (e.g. organodio-
lato,13 ethene-1,1,2,2-tetrathiolato,9e dicarboxylato,14 etc.)
ligands. The lack of an aromatic substituent with a pendant
arm able to provide an intramolecular E→Sn interaction
might result in either discrete dinuclear species, e.g. a 1,1′-
ferrocenedicarboxylate unit bridging triphenyltin(IV) moieties,15
or polymeric species, e.g. built by connecting triorgantin(IV)
moieties by fumarato units.16 Surprisingly, to the best of our
knowledge, there are extremely few discrete bimetallic systems
in which organotin(IV) fragments with aromatic substituents
bearing C,E-pendant arms or related systems with hypercoordi-

This journal is © The Royal Society of Chemistry 2019 Dalton Trans., 2019, 48, 6527–6538 | 6527
Paper
Scheme 1 Model triorganotin(IV) linkers and potential coordination
polymers [E = donor atom of the functional group FG (in a C,E-ligand)
which remains coordinated to the metal center following a reaction in
which the FG group is converted to either a pendant “E-connecter-FG*”
or a bridging “E-connecter-E” system].
nated metal centres are connected by a bridge through Sn–C
bonds.8b,17 In the search for new linear organometallic
linkers5c,d,18 our attention was attracted by hypercoordinated
triorganotin(IV) species containing one aromatic C,E-pendant
arm ligand, i.e. [2-(FG-CH2)C6H4]R2SnX (I, FG = functional
group) (Scheme 1). They exhibit a trigonal bipyramidal coordi-
nation geometry around the metal centre, with axial positions
occupied by an anionic X ligand and a donor atom E from the
FG group of the pendant arm. If such a compound is designed
to have an X group able to provide a bridge and/or a donor
atom to connect to another metal centre (Scheme 1, structures
II and III), discrete heterobimetallic species or coordination
polymers (Scheme 1, structures IV and V) could be obtained.
We report here on the synthesis, characterization and
crystal structure of some new monometallic and bimetallic
triorganotin(IV) species which are precursors or potential
organometallic linkers for preparing discrete heterometallic
complexes or coordination polymers.
Results and discussion
Synthesis
The dimethyl(aryl)tin(IV) derivative 1 was prepared by reacting
Me2SnCl2, in a 1 : 1 molar ratio, with the lithium salt obtained
from 2-(2-bromophenyl)-1,3-dioxolane and n-BuLi, under an
inert atmosphere. Removal of the acetal group protecting the
carbonyl function in 1 by hydrolysis in an acetone/water
mixture, using p-toluene sulfonic acid ( p-TsOH) as the catalyst,
resulted in the isolation of the chloride 2 in good yield.
Condensation reactions to obtain compounds 4 and 5 were
performed by mixing compound 2 with diamines, in a
2 : 1 molar ratio, without a solvent or catalyst, as described pre-
viously for related tetra-5a and di(imino)aryltin(IV) species.5b
The reaction of 2 with KSCN resulted in the corresponding iso-
thiocyanato derivative 3. The condensation of 3 with ethylen-
diamine in a 2 : 1 molar ratio quantitatively gave 6, which was
also obtained by reacting 5 with excess KSCN (Scheme 2). The
1
H NMR spectra of the crude condensation products indicated
practically total conversion to the desired bimetallic species.
The reaction of 2 with sodium isonicotinate gave the corres-
ponding triorganotin(IV) isonicotinate 7. Mixing derivative 7
6528 | Dalton Trans., 2019, 48, 6527–6538
Dalton Transactions
Scheme 2 Preparation of compounds 1–6.
Scheme 3 Preparation of compounds 7 and 8.
with one equivalent of ZnTPP (TPP = tetraphenylporphyrinate)
afforded the heterobimetallic complex 8 (Scheme 3).
The compounds were isolated as colourless (1–3, 6, 7),
yellow (4, 5) or purple (8) air-stable solids. The monochlorides
1 and 2, isothiocyanato derivative 3 and isonicotinato com-
pounds 7 and 8 show good solubility in chlorinated solvents
(CH2Cl2, CHCl3), while the imine species 4–6 exhibit a very low
solubility in common solvents.
The compounds were characterized by multinuclear (1H,
13
C, 119Sn) NMR spectroscopy in solution and IR spectroscopy
in the solid state. Satisfactory analytical results and HRMS
data were obtained. For compounds 1–3, 7 and 8 the base peak
in the HRMS APCI+ or ESI+ mass spectra was assigned to
[RMe2Sn+] fragments. For the bimetallic derivatives 4–6 frag-
ments of a lower m/z relative intensity were also assigned to
[M+ − Cl] and [M+ − NCS] ions. Elemental analysis was per-
formed for compounds 2 and 3 to clearly establish their iden-
tity, given that the base peak in the HRMS mass spectra was
assigned to the same [RMe2Sn+] fragment (C9H11OSn). In the
IR spectra strong bands were assigned to the stretching
vibration of the CvO double bond (region 1660–1630 cm−1)
for compounds 2, 3, 7 and 8, and to the stretching vibration of
the imine CvN double bond (region 1640–1610 cm−1) for
derivatives 4–6. Very strong bands assigned to ν(CN) (2065 and
2070 cm−1 for 3 and 6, respectively) and medium to weak
bands attributed to ν(CS) (860 and 876 cm−1 for 3 and 6,
respectively) are consistent with the presence of monodentate
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Dalton Transactions Paper

isothiocyanato (–NvCvS) groups in these compounds.19 For

compound 7 and its ZnTPP complex 8 strong to very strong IR
bands were assigned to asymmetric νa(CO2) (1652 and
1651 cm−1 for 7 and 8, respectively) and symmetric νs(CO2)
(1348 and 1340 cm−1 for 7 and 8, respectively) stretching
vibrations. For both these compounds the magnitude of the
difference Δ = νa(CO2) − νs(CO2) (304 and 311 cm−1 for 7 and
8, respectively) is indicative of a monodentate isonicotinato
ligand.19b

Solid state structures

The molecular structures for compounds 1–6 and 8 were estab- Fig. 3 Molecular structure of 3a’. Thermal ellipsoids are drawn at the
30% probability [hydrogen atoms, except H(7), are omitted for clarity].
lished by single-crystal X-ray diffraction and are depicted in
Fig. 1–7. Selected interatomic distances and bond angles are
summarized in Tables 1 and 2. For compound 3 two poly-
ˉ) and 3″
morphs, i.e. 3′ (crystal system: triclinic; space group: P1
(crystal system: monoclinic; space group: I2/m) were isolated
under different crystallization conditions.
The unit cell of compounds 2 and 3 (in the case of both 3′
and 3″) contains two different molecules, with very similar
molecular parameters, and therefore only data for molecules
2a, 3a′ and 3a″ are included in Table 1 and indicated in the
subsequent discussion (molecular parameters for molecules
2b, 3b′ and 3b″ are listed in Table S3 in the ESI†).
All these triorganotin(IV) derivatives contain a distorted tri-
gonal bipyramidal (C,E)C2SnX core (E = O, N; X = Cl, N, O) as a

Fig. 4 Molecular structure of 4. Thermal ellipsoids are drawn at the

30% probability [hydrogen atoms, except H(7), are omitted for clarity].

Fig. 1 Molecular structure of isomer pSO(1)-SC(7)-1. Thermal ellipsoids

are drawn at the 30% probability [hydrogen atoms, except H(7), are
omitted for clarity].

Fig. 5 Molecular structure of 5. Thermal ellipsoids are drawn at the

30% probability [hydrogen atoms, except H(7), are omitted for clarity].

result of intramolecular O→Sn or Nimine→Sn interactions

Fig. 2 Molecular structure of 2a. Thermal ellipsoids are drawn at the
30% probability [hydrogen atoms, except H(7), are omitted for clarity].
established trans to the chlorine, nitrogen from the isothio-
cyanato ligand or oxygen from the isonicotinato moiety [E–Sn–X
range: 166.97(18)–172.6(2)°]. The tin-oxygen distances within
the OC3Sn chelate ring in 1 [2.486(4) Å], 2a [2.466(5) Å], 3a′
[2.442(5) Å], 3a″ [2.468(4) Å] and 8 [2.528(5) Å], respectively, are

This journal is © The Royal Society of Chemistry 2019 Dalton Trans., 2019, 48, 6527–6538 | 6529
Paper
Fig. 6 Molecular structure of 6. Thermal ellipsoids are drawn at the
30% probability [hydrogen atoms, except H(7), are omitted for clarity].
Fig. 7 Molecular structure of 8. Thermal ellipsoids are drawn at the
20% probability [hydrogen atoms, except H(7), are omitted for clarity].
similar to those observed for [2-{(CH2O)2CH}C6H4]2SnCl2
[2.500(5)/2.475(5) Å], [2-(OvCH)C6H4]2SnCl2 [2.431(7)/2.480(7) Å]5d
and the triorganotin(IV) derivatives with an ester function
[2,6-(tBuOCH2)2C6H3]SnMe2Cl [2.573(3) Å],7n [2,6-(MeOCH2)2C6H3]
SnPh2Cl [2.567(2) Å],7a [2,6-(EtOCH2)2C6H3]SnPh2Cl [2.454(1) Å],7f
which contain an organic ligand with a pendant arm involved
in an intramolecular O→Sn interaction. The increase in
Lewis acidity of the metal atom, due the presence of the chlor-
ine atom in the triorganotin(IV) derivatives 1 and 2, is
obvious when comparing the length of the interatomic O→Sn
distances with those present in the tetraaryltin(IV) derivatives
containing the same pendant arm ligands [O→Sn 2.825(6)/
2.853(10) Å for [2-{(CH2O)2CH}C6H4]4Sn; O→Sn 2.989(8)/3.006(7) Å
for [2-(OvCH)C6H4]4Sn, respectively;5c cf. ∑rvdW(Sn,O) 3.60 Å,
∑rcov(Sn,O) 2.06 Å].20 Substitution of the chlorine atom in 2 by
a NCS group has no noticeable effect on the interatomic
6530 | Dalton Trans., 2019, 48, 6527–6538
Dalton Transactions
distance observed for the intramolecular O→Sn interaction
[cf. Sn–O 2.466(5) Å in 2a vs. 2.442(5) Å in 3a′ and 2.468(4) Å
in 3a″ in Table (1)].
In the bimetallic derivatives described in this work, i.e. 4–6,
strong intramolecular Nimine→Sn interactions are present
(cf. ∑rcov(Sn,N) 2.15 Å, ∑rvdW(Sn,N) 3.74 Å).20 The tin-nitrogen
distances [range 2.398(4)–2.479(4) Å; see Table 2] are similar
to those found in the related [2-(Me2NCH2)C6H4]Me2SnCl
[N→Sn 2.485(3)/2.488(3) Å for the two polymorphs, respec-
tively],21 with no obvious difference due to the hybridization
nature of the donor atom [better donor properties of a N(sp2)
vs. a N(sp3) atom, respectively] as found for the related R2SnCl2
[R = (imino)aryl or 2-(Me2NCH2)C6H4] compounds.5d
Moreover, the change in Lewis acidity of the metal atom
expected by replacing chlorine in 5 by NCS in 6 results in a
very small, if any, influence on the magnitude of the intra-
molecular Nimine→Sn distances [2.432(6) Å in 5 vs. 2.398(4) Å
in 6], a similar situation being observed previously for the
related [2-(Me2NCH2)C6H4]Me2SnX derivatives [N→Sn 2.485(3)
for X = Cl21 vs. 2.456(4) for X = NCS1f ].
The Sn–NNCS distances [2.174(6) Å in 3a′, 2.164(5) Å in 3a″
and 2.227(4) Å in 6, respectively] are in agreement with values
observed for other tin-isothiocyanato bonds.1f
The NCS ligand is almost linear [N–C–S 178.0(7) Å in 3a′,
178.3(6) Å in 3a″, and 178.3(5) Å in 6], while the tetraatomic
Sn–NCS system is bent at nitrogen [Sn–N–C(S) angles of
154.5(6)° in 3a′, 176.6(5)° in 3a″, and 165.2(4)° in 6]. The inter-
atomic distances in the isothiocyanato groups in the molecules
of 3a′, 3a″ and 6 [range: C–N 1.106(6)–1.156(7) Å; C–S 1.578(7)–
1.616(6) Å] are similar to the values reported for [2-(Me2NCH2)
C6H4]Me2Sn(NCS) [C–N 1.158(6) Å, C–S 1.595(6) Å].1f
The molecule of 1 exhibits several types of chiralities
induced by the intramolecular O→Sn interaction. Thus, the
oxygen atoms of the 1,3-dioxolan-2-yl ring are nonequivalent
and consequently the methyne C(7) atom of the corresponding
heterocycle becomes chiral. The five-membered SnC3O chelate
ring is not planar, but slightly folded along the Sn(1)⋯Cmethyne
axis [dihedral angle SnC3/SnCO of 8.3° and O(1) deviated
−0.14 Å out from the best SnC3 plane], resulting in planar chir-
ality (with the aromatic ring and the oxygen atom as the chiral
plane and pilot atom, respectively; isomers given as pRO and
pSO).22 Indeed, the crystal of 1 contains a 1 : 1 mixture of
pRO(1)-RC(7)-1 and pSO(1)-SC(7)-1 isomers (see the ESI†). In the
case of compounds 2, 3′, 3″ and 8 the presence of the CvO
double bond results, as expected, in a planar five-membered
SnC3O ring. Similarly, the C3SnN chelate rings in compounds
4–6 are basically planar due to the presence of the CvN
double bond in the pendant arm of the ligand.
The structure of the heterobimetallic complex 8 shows an
isonicotinate moiety bridging a triorganotin(IV) fragment
through an oxygen atom of the carboxyl function and a ZnTPP
moiety via the nitrogen atom of the pyridyl ring. The Zn center
is pentacoordinated with a distorted square pyramidal geome-
try, the four nitrogen atoms of the TPP ligand forming the
base of the pyramid. The Zn atom is out of the best plane
defined by the four nitrogen atoms of the TPP by 0.35 Å
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Table 1 Selected interatomic distances (Å) and bond angles (°) for compounds 1, 2a, 3a’ and 3a’’

1 2a 3a′ 3a″ a

Sn(1)–C(1) 2.127(5) Sn(1)–C(1) 2.135(5) Sn(1)–C(1) 2.131(6) Sn(1)–C(1) 2.150(6)

Sn(1)–C(8) 2.101(6) Sn(1)–C(8) 2.110(7) Sn(1)–C(8) 2.114(6) Sn(1)–C(8) 2.107(4)
Sn(1)–C(9) 2.109(6) Sn(1)–C(9) 2.106(6) Sn(1)–C(9) 2.112(6) Sn(1)–C(8a)i 2.107(4)
Sn(1)–Cl(1) 2.4571(18) Sn(1)–Cl(1) 2.4434(17)
Sn(1)–O(1) 2.486(4) Sn(1)–O(1) 2.466(5) Sn(1)–O(1) 2.442(5) Sn(1)–O(1) 2.468(4)
Sn(1)–N(1) 2.174(6) Sn(1)–N(1) 2.164(5)
C(7)–O(1) 1.393(7) C(7)–O(1) 1.205(8) C(7)–O(1) 1.206(8) C(7)–O(1) 1.193(8)
C(7)–O(2) 1.387(6)
C(10)–N(1) 1.152(7) C(9)–N(1) 1.156(7)
C(10)–S(1) 1.578(7) C(9)–S(1) 1.602(6)
Cl(1)–Sn(1)–O(1) 168.69(11) Cl(1)–Sn(1)–O(1) 169.65(13) N(1)–Sn(1)–O(1) 169.2(2) N(1)–Sn(1)–O(1) 166.97(18)
C(1)–Sn(1)–C(8) 119.0(2) C(1)–Sn(1)–C(8) 117.5(3) C(1)–Sn(1)–C(8) 118.3(2) C(1)–Sn(1)–C(8) 118.31(13)
C(1)–Sn(1)–C(9) 114.6(2) C(1)–Sn(1)–C(9) 119.5(3) C(1)–Sn(1)–C(9) 119.0(2) C(1)–Sn(1)–C(8a)i 118.32(13)
C(8)–Sn(1)–C(9) 121.2(3) C(8)–Sn(1)–C(9) 117.5(3) C(8)–Sn(1)–C(9) 119.5(3) C(8)–Sn(1)–C(8a)i 118.7(3)
Cl(1)–Sn(1)–C(1) 97.41(13) Cl(1)–Sn(1)–C(1) 95.94(16) N(1)–Sn(1)–C(1) 94.7(2) N(1)–Sn(1)–C(1) 93.4(2)
Cl(1)–Sn(1)–C(8) 96.42(18) Cl(1)–Sn(1)–C(8) 98.1(2) N(1)–Sn(1)–C(8) 97.4(3) N(1)–Sn(1)–C(8) 99.09(14)
Cl(1)–Sn(1)–C(9) 99.2(3) Cl(1)–Sn(1)–C(9) 99.5(2) N(1)–Sn(1)–C(9) 95.8(2) N(1)–Sn(1)–C(8a)i 99.09(14)
O(1)–Sn(1)–C(1) 72.54(15) O(1)–Sn(1)–C(1) 73.73(19) O(1)–Sn(1)–C(1) 74.6(2) O(1)–Sn(1)–C(1) 73.54(18)
O(1)–Sn(1)–C(8) 84.4(2) O(1)–Sn(1)–C(8) 86.6(2) O(1)–Sn(1)–C(8) 88.0(2) O(1)–Sn(1)–C(8) 87.44(14)
O(1)–Sn(1)–C(9) 89.9(3) O(1)–Sn(1)–C(9) 86.3(3) O(1)–Sn(1)–C(9) 89.5(2) O(1)–Sn(1)–C(8a)i 87.44(14)
C(2)–C(7)–O(1) 111.3(4) C(2)–C(7)–O(1) 122.7(6) C(2)–C(7)–O(1) 123.3(7) C(2)–C(7)–O(1) 123.9(6)
C(2)–C(7)–O(2) 111.8(5)
C(7)–O(1)–Sn(1) 113.5(3) C(7)–O(1)–Sn(1) 109.5(4) C(7)–O(1)–Sn(1) 109.1(5) C(7)–O(1)–Sn(1) 108.9(4)
N(1)–C(10)–S(1) 178.0(7) N(1)–C(9)–S(1) 178.3(6)
Sn(1)–N(1)–C(10) 154.5(6) Sn(1)–N(1)–C(9) 176.6(5)
a
Symmetry codes: (i) x, −y, z, for 3a″.

Table 2 Selected interatomic distances (Å) and bond angles (°) for compounds 4, 5, 6 and 8·CH2Cl2

4a 5a 6a 8·CH2Cl2

Sn(1)–C(1) 2.134(6) Sn(1)–C(1) 2.139(7) Sn(1)–C(1) 2.143(4) Sn(1)–C(1) 2.159(7) Zn(1)–N(1) 2.163(5)
Sn(1)–C(8) 2.105(5) Sn(1)–C(8) 2.151(9) Sn(1)–C(8) 2.101(4) Sn(1)–C(8) 2.131(8) Zn(1)–N(2) 2.089(5)
Sn(1)–C(9) 2.112(6) Sn(1)–C(9) 2.112(9) Sn(1)–C(9) 2.115(5) Sn(1)–C(9) 2.123(8) Zn(1)–N(3) 2.087(5)
Sn(1)–Cl(1) 2.4854(18) Sn(1)–Cl(1) 2.499(2) Zn(1)–N(4) 2.094(5)
Sn(1)–N(1) 2.479(4) Sn(1)–N(1) 2.432(6)
Sn(1)–N(1) 2.398(4) Sn(1)–O(1) 2.528(5) Zn(1)–N(5) 2.092(6)
Sn(1)–N(2) 2.227(4) Sn(1)–O(2) 2.124(5)
C(7)–N(1) 1.259(6) C(7)–N(1) 1.270(11) C(7)–N(1) 1.273(6) C(7)–O(1) 1.209(10)
C(10)–N(1) 1.431(6) C(10)–N(1) 1.458(10) C(10)–N(1) 1.477(6)
C(13)–C(13a)i 1.488(9) C(10)–C(10a)i 1.502(17) C(10)–C(10a)i 1.470(10)
C(11)–N(2) 1.106(6) C(10)–O(2) 1.312(8)
C(11)–S(1) 1.616(6) C(10)–O(3) 1.233(8)
Cl(1)–Sn(1)–N(1) 169.68(11) Cl(1)–Sn(1)–N(1) 169.67(17) N(2)–Sn(1)–N(1) 167.41(15) O(1)–Sn(1)–O(2) 172.6(2) N(1)–Zn(1)–N(2) 102.2(2)
C(1)–Sn(1)–C(8) 118.7(2) C(1)–Sn(1)–C(8) 116.5(3) C(1)–Sn(1)–C(8) 117.18(16) C(1)–Sn(1)–C(8) 113.6(3) N(1)–Zn(1)–N(3) 101.5(2)
C(1)–Sn(1)–C(9) 117.3(2) C(1)–Sn(1)–C(9) 118.7(3) C(1)–Sn(1)–C(9) 121.94(17) C(1)–Sn(1)–C(9) 119.1(3) N(1)–Zn(1)–N(4) 97.4(2)
C(8)–Sn(1)–C(9) 121.4(3) C(8)–Sn(1)–C(9) 121.7(4) C(8)–Sn(1)–C(9) 119.49(19) C(8)–Sn(1)–C(9) 121.6(4) N(1)–Zn(1)–N(5) 98.1(2)
Cl(1)–Sn(1)–C(1) 95.98(15) Cl(1)–Sn(1)–C(1) 95.7(2) N(2)–Sn(1)–C(1) 92.28(16) O(2)–Sn(1)–C(1) 101.4(2) N(2)–Zn(1)–N(3) 89.2(2)
Cl(1)–Sn(1)–C(8) 93.86(17) Cl(1)–Sn(1)–C(8) 98.0(3) N(2)–Sn(1)–C(8) 94.12(17) O(2)–Sn(1)–C(8) 91.0(3) N(3)–Zn(1)–N(4) 88.1(2)
Cl(1)–Sn(1)–C(9) 96.58(19) Cl(1)–Sn(1)–C(9) 94.0(3) N(2)–Sn(1)–C(9) 95.33(18) O(2)–Sn(1)–C(9) 101.2(3) N(4)–Zn(1)–N(5) 88.2(2)
N(1)–Sn(1)–C(1) 73.77(17) N(1)–Sn(1)–C(1) 74.2(2) N(1)–Sn(1)–C(1) 75.21(15) O(1)–Sn(1)–C(1) 72.8(2) N(5)–Zn(1)–N(2) 87.8(2)
N(1)–Sn(1)–C(8) 92.2(2) N(1)–Sn(1)–C(8) 84.8(3) N(1)–Sn(1)–C(8) 92.96(16) O(1)–Sn(1)–C(8) 87.3(3) N(2)–Zn(1)–N(4) 160.3(2)
N(1)–Sn(1)–C(9) 87.3(2) N(1)–Sn(1)–C(9) 92.9(3) N(1)–Sn(1)–C(9) 90.22(17) O(1)–Sn(1)–C(9) 85.8(3) N(3)–Zn(1)–N(5) 160.4(2)
C(2)–C(7)–N(1) 121.0(5) C(2)–C(7)–N(1) 120.5(7) C(2)–C(7)–N(1) 120.7(4) C(2)–C(7)–O(1) 123.6(7)
C(7)–N(1)–C(10) 119.5(4) C(7)–N(1)–C(10) 118.6(7) C(7)–N(1)–C(10) 118.7(4)
C(7)–N(1)–Sn(1) 108.9(3) C(7)–N(1)–Sn(1) 110.0(5) C(7)–N(1)–Sn(1) 109.9(3) C(7)–O(1)–Sn(1) 108.6(5)
C(10)–N(1)–Sn(1) 131.4(3) C(10)–N(1)–Sn(1) 130.7(6) C(10)–N(1)–Sn(1) 131.3(4)
N(2)–C(11)–S(1) 178.3(5) O(2)–C(10)–O(3) 123.8(6)
Sn(1)–N(2)–C(11) 165.2(4) Sn(1)–O(2)–C(10) 116.4(4)
a
Symmetry codes: (i) 2 − x, 1 − y, 2 − z, for 4; (i) −x, −y, 2 − z, for 5; (i) 0.5 − x, 1.5 − y, 2 − z, for 6.

towards the coordinating isonicotinate. The tin atom becomes 3.071(5) Å, respectively] resulting in a capped trigonal bipyra-
hexacoordinated if the intramolecular interaction with the midal geometry.
second oxygen atom of the isonicotinate ligand is taken No intermolecular interactions between heavy atoms were
into consideration [Sn(1)–O(2) 2.124(5) Å and Sn(1)⋯O(3) observed in the crystals of compounds 1–6 and 8. However,

This journal is © The Royal Society of Chemistry 2019 Dalton Trans., 2019, 48, 6527–6538 | 6531
Paper
both intra- and intermolecular C–H⋯Cl, C–H⋯O and C–H⋯π
interactions are present in the solid state for some of these
compounds. Thus, pRO(1)-RC(7)-1 and pSO(1)-SC(7)-1 isomers are
connected to a dimeric unit through two symmetric C–H⋯π
(Phcentroid) interactions [C(11a)–H(11Aa)methylene⋯Phcentroid{C(1)–
C(6)} 2.79 Å, γ = 7.9°] (i.e. H⋯Phcentroid contacts shorter than
3.1 Å, with an angle γ between the normal to the aromatic ring
and the line defined by the H atom and Phcentroid smaller than
30°).23 These dimeric units are further associated with a
honeycomb-type layer in which a dimer unit is surrounded by
six other dimers, but connected to only four through C–H⋯Cl
interactions [C(9b)–H(9Ab)methyl⋯Cl(1) 2.90 Å; cf. ∑rvdW(Cl,H)
3.01 Å],20 with no further contacts between parallel layers (for
details, see the ESI†). In the crystal of 2 the two independent
molecules are linked alternatively through intermolecular
C–H⋯Cl interactions [Cl(1)⋯H(16b)carbonyl 2.85 Å and Cl(2)⋯H
(7d)carbonyl 2.91 Å, respectively] in helicoidal M and P polymers
which are developed along the c axis. Chain polymers having
the same configuration are perfectly stacked along the a axis
and there are no further contacts between such polymers (for
details, see the ESI†). There are no significant intermolecular
interactions in either polymorphs of compound 3. Molecules
of 4 are connected through intermolecular C–H⋯Cl inter-
actions [Cl(1)⋯H(7b)imine 2.82 Å] in a zig-zag layer. The layers
are further linked by C–H⋯π (Phcentroid) interactions [C(8d)–H
(8Ad)methyl⋯Phcentroid{C(1)–C(6)} 3.04 Å, γ = 20.7°], resulting in
a 3D supramolecular architecture (for details, see the ESI†). In
the solid state, the molecules of 5 also form layers along
the (101) plane via intermolecular C–H⋯Cl interactions
[Cl(1)⋯ H(7c)imine 2.86 Å], but no further inter-layer contacts
are established (for details, see the ESI†). In the case of com-
pound 6, the molecules form ribbon-like polymers based on
intermolecular C–H⋯S contacts [S(1)⋯H(7b)imine 2.84 Å,
∑rvdW(S,H) 3.0 Å],20 with no other contacts between
different chains (for details, see the ESI†). In the crystal of
compound 8 dimer associations through C–H⋯O interactions
[O(3)⋯H(17a)TPP 2.44 Å] are formed. These dimers are
further connected by C–H⋯π (Phcentroid) interactions
[C(45b)–H(45b)Ph-TPP⋯Phcentroid{C(1)–C(6)} 2.79 Å, γ = 15.9°] in
a double layer supramolecular architecture developed along
the (101) plane (for details, see the ESI†).
Solution behaviour
All compounds were investigated by solution multinuclear
(1H, 13C, 119Sn) NMR (except 4–6 for which 13C NMR could not
be recorded due to low solubility even in DMSO-d6). The
spectra were recorded in CDCl3 and DMSO-d6 at room tem-
perature. The assignment of resonances in the 1H and 13C
NMR spectra was based on 2D NMR (HSQC, HMBC and COSY)
correlation spectra and tin-carbon coupling constants (for the
numbering schemes, see the ESI†). The room-temperature
NMR (1H, 13C) spectra for the reported compounds show one
set of characteristic resonance signals corresponding to the
organic groups bonded to tin with the expected patterns.
For all compounds in the aliphatic region of both 1H and
13
C NMR spectra a singlet resonance signal is observed for the
6532 | Dalton Trans., 2019, 48, 6527–6538
Dalton Transactions
methyl groups bonded to tin with the corresponding tin satel-
lites. For compounds 5 and 6 the 1H spectra show one reso-
nance signal (3.96 ppm and 3.92 ppm, respectively) assigned
to the aliphatic bridge linking the nitrogen atoms involved in
the imine bonds of a molecule.
The most important feature in the aromatic region of the 1H
NMR spectra is the resonance signal corresponding to H-7
[proton from the –CH(OCH2)2, –CHvO and –CHvN groups].
Thus, the resonance signal appears at 5.88 ppm for 1 (acetal
group), at 9.95 ppm for 2, 9.94 ppm for 3, 9.98 ppm for 7,
9.71 ppm for 8 (aldehyde-containing derivatives), 9.18 ppm for
4, 8.81 ppm for 5 and 8.90 ppm for 6 (imine derivatives), provid-
ing very useful information both about the deprotection of the
carbonyl function in 1 and the formation of the imine deriva-
tives 4–6. In the 13C NMR spectra the C-7 [the carbon from the
–CH(OCH2)2, –CHvO and –CHvN groups] resonance signal is
observed at 104.38 ppm for 1 (acetal group) and at 196.87 ppm
for 2, 197.32 ppm for 3, 197.01 ppm for 7, and 196.84 ppm for 8
(aldehyde derivatives). The same trends are observed as reported
before,5c–e i.e. a downfield shift of the resonance signals due to
the change in hybridization from sp3 to sp2 (acetal to aldehyde)
due to the deprotection of the carbonyl function and an upfield
shift due to the difference in electronegativity of the element
involved in the double bond (O or N), as a consequence of the
conversion of the aldehyde derivatives to imines.
A broad resonance was detected at 141.3 ppm in the 13C
NMR spectrum of 3 for the carbon atom of the NCS group,
similar to the chemical shifts reported for [2,6-(Me2N)2C6H3]
Me2Sn(NCS) and other related derivatives.1f,24
The NMR parameters indicate the same coordination geo-
metry around the tin centre as it was found in the solid state,
i.e. trigonal bipyramidal.25 The values of the calculated
C(8)–Sn–C(9) angles based on the relationships between
2 119
J ( Sn,1H) and 1J (119Sn,13C) coupling constants and the C(8)–
Sn–C(9) angle25,26 (Table 3) show a good correlation between
the structure found in solution and the trigonal bipyramidal
(C,E)C2SnX core with equatorial Sn–C bonds as determined in
the solid state.
In solution, at room temperature, the 119Sn NMR spectra
for all derivatives 1–5, 7 and 8 show one single resonance con-
Table 3 Correlations between 1H–119Sn and 13C–119Sn coupling con-
stants (Hz) and C–Sn–C angles (θ, °) in compounds 1–8
1 13
H C
Compound 2
J (119Sn1H) C(8)–Sn–C(9)a 1
J (119Sn13C) C(8)–Sn–C(9)b
1 67.1 117.3 483.8 119.2
2 69.4 119.3 513.2 121.7
3 72.7 122.5 534 123.6
4 71.4 121.2
5 71.6 121.4
6 72.1 121.9 491.5 119.9
7 72.8 122.6 537.7 123.9
8 72.8 122.6 536.2 123.8
a
θ = 0.0161|2J|2 − 1.32|2J| + 133.4.25 b |1J| = 11.4θ − 875.26
This journal is © The Royal Society of Chemistry 2019
Dalton Transactions
sistent with the presence of only one species and with equi-
valent environments for tin atoms in the bimetallic com-
pounds 4 and 5. The magnitude of the 119Sn chemical shifts
(δ 13.8 ppm, 13.4 ppm, −50.2 ppm, −20.7 ppm, −19.2 ppm for
1, 2, 3, 7 and 8 in CDCl3, and −72.5 ppm and −84.5 ppm for 4
and 5 in DMSO-d6, respectively) is typical of five-coordinate
triorganotin(IV) species in solution, thus consistent with the
presence of E→Sn intramolecular interactions. The 119Sn
chemical shifts of 1 and 2 are similar showing no influence of
the hybridization of the intramolecular coordinating oxygen
atom, a behaviour also observed for the related [2-{(CH2O)2CH}-
C6H4]2SnCl2 and [2-(OvCH)C6H4]2SnCl2.5d The triplet 119Sn
resonance signal for 3 is due to nitrogen-tin coupling [δ −50.2,
1
J119Sn,14N 136.7 Hz], similar to other compounds with a
NCS fragment attached to tin via the nitrogen atom.1f,27
The resonances observed in the 119Sn NMR spectra for com-
pounds 4 and 5 appear at chemical shifts comparable with
those reported for the related [2-(Me2NCH2)C6H4]Me2SnCl
(δ −48.7 ppm, in CH2Cl2/acetone-d6)21 and [2-{Me2NCH2CH2N-
(Me)CH2}C6H4]Me2SnCl (δ −45 ppm, in CDCl3).28
Experimental
General measurements and analysis instrumentation
Multinuclear NMR spectra (1H, 13C and 119Sn) were recorded at
room temperature on Bruker Advance 300, Bruker Avance III
400 and 600 spectrometers. The 1H chemical shifts are
reported in δ units ( ppm) relative to the residual peak of the
deuterated solvent (CHCl3, 7.26 ppm; DMSO-d5, 2.50 ppm).
The 13C chemical shifts are reported in δ units ( ppm) relative
to the peak of the deuterated solvent (CDCl3, 77.16 ppm;
DMSO-d6, 39.43 ppm). The 1H and 13C resonances were
assigned using 2D NMR experiments (COSY, HSQC, HMBC).
For the 119Sn NMR spectra the chemical shifts are reported in
ppm relative to SnMe4 as the external standard. The NMR
spectra were processed using MestReC and MestReNova soft-
ware.29 Infrared spectra were recorded using KBr pellets in the
4000–400 cm−1 range on a JASCO FT/IR-615 instrument for
compound 1 and in the range 4000–550 cm−1 on a Bruker
Vector 22 spectrometer for compounds 2–8. Melting points
were measured with an Electrothermal 9200 apparatus and are
not corrected. HRMS APCI(+) and ESI(+) spectra were recorded
on a Thermo Scientific Orbitrap XL spectrometer equipped
with a standard ESI/APCI source. Elemental analyses were
carried out on a Flash EA 1112 analyser.
Crystal structure determination
Single crystals were obtained from hot hexane solutions of 1
and 3, hot DMSO solutions for 4, 5 and 6, and by slow evapor-
ation of a toluene solution of 2. For the heterobimetallic
complex single crystals were grown by hexane diffusion from a
CH2Cl2 solution of 8. The details of the crystal structure deter-
mination and refinement for compounds 1–6 and 8 are given
in Tables S1 and S2,† respectively (see the ESI†). The crystals
were mounted on cryoloops and data were collected on a
This journal is © The Royal Society of Chemistry 2019
Paper
Bruker SMART APEX diffractometer, using graphite-monochro-
mated Mo-Kα radiation (λ = 0.71073 Å) at room temperature
(297 K) except for 8 which was measured at 200 K. The struc-
tures were refined with anisotropic thermal parameters for
non-H atoms. Hydrogen atoms were placed at fixed, idealized
positions and refined with a riding model and a mutual iso-
tropic thermal parameter. For structure solving and refine-
ment the software package SHELX-2015 was used.30 In a final
difference Fourier map highly disordered electron density was
observed for compound 6. The residual electron density was
difficult to model and therefore, the SQUEEZE routine in
PLATON31 was used to eliminate this contribution of the elec-
tron density in the solvent region from the intensity data. The
solvent-free model was employed for the final refinement. It
was estimated that each cavity contains around 44 electrons
which can correspond to a solvent molecule of DMSO.
The drawings were created with the Diamond program.32
The CCDC reference numbers are 1860608 (1), 1860615 (2),
1860609 (3′), 1860614 (3″), 1860611 (4), 1860610 (5), 1860612
(6) and 1860613 (8·CH2Cl2).†
Materials and methods
The synthesis of 1 was carried out under an inert atmosphere
of argon using Schlenk techniques. Solvents were dried and
freshly distilled under argon prior to use. Starting materials
such as Me2SnCl2, KSCN, benzidine, and ethylenediamine,
were obtained from Aldrich or Merck, and were used as
received except the amines which were purified by distillation
or recrystallization prior to use. 2-[(CH2O)2CH]C6H4Br was pre-
pared according to a literature method, slightly modified by
using toluene as the reaction solvent instead of benzene.33
Synthesis of [2-{(CH2O)2CH}C6H4]Me2SnCl (1)
A solution of n-BuLi in hexane (1.23 g, 12 mL, 1.6 M,
19.2 mmol) was added dropwise to a solution of
2-[(CH2O)2CH]C6H4Br (4 g, 17.46 mmol) in hexane (40 mL), at
room temperature, under argon using Schlenk techniques.
The solution turned pale yellow and a white precipitate was
formed. The reaction mixture was stirred for 2 hours, and the
formed precipitate was separated and washed with hexane
(2 × 20 mL). The solid was dried in a vacuum, toluene
(40 mL) was added and the suspension was added dropwise
for one hour, under stirring, to a cooled (−78 °C) solution of
Me2SnCl2 (3 g, 13.66 mmol) in toluene (20 mL). The reaction
mixture was left to reach room temperature and was stirred
overnight. The solvent was removed to dryness using a rotary
evaporator, the remaining solid residue was dissolved in
CH2Cl2 (30 mL) and washed with saturated NaCl solution
(30 mL). The organic layer was separated, the aqueous solu-
tion was washed with CH2Cl2 (2 × 5 mL) and the combined
organic phases were dried on anhydrous Na2SO4. After fil-
tration and removal of the solvent under vacuum from the
clear filtrate, hexane was added to obtain 1 as colourless crys-
tals (2.98 g, 66%), m.p. 84–85 °C. 1H NMR (CDCl3, 400 MHz,
Dalton Trans., 2019, 48, 6527–6538 | 6533
Paper
20 °C): δ 0.77 (s, 6H, 2J117Sn,H = 64.1 Hz, 2J119Sn,H = 67.1 Hz,
CH3), 4.10 (m, 4H, H-8), 5.88 (s, 1H, 4JSn,H = 7.9 Hz, H-7), 7.47
(m, 3H, H-3–5), 8.15 (d, 1H, 3JH,H = 6.9 Hz, 3JSn,H = 62.7 Hz,
H-6). 13C{1H} NMR (CDCl3, 100.6 MHz, 20 °C): δ 1.29 (s,
1
J117Sn,C = 462.3 Hz, 1J119Sn,C = 483.8 Hz, CH3), 64.94 (s, C-8),
104.38 (s, 3JSn,C = 11.7 Hz, C-7), 126.71 (s, 3JSn,C = 55 Hz, C-3),
129.61 (s, 4JSn,C = 12.8 Hz, C-4), 129.63 (s, 3JSn,C = 58 Hz, C-5),
136.69 (s, 2JSn,C = 33.5 Hz, C-6), 137.17 (s, C-1), 140.89 (s, C-2).
119
Sn{1H} NMR (CDCl3, 149.2 MHz, 20 °C): δ 13.8 (s). IR (KBr
pellet, ν, cm−1): 2876 (w), 1706 (w), 1680 (m), 1646 (s), 1580
(w), 1559 (m), 1457 (w), 1455 (w), 1394 (w), 1383 (w), 1296 (w),
1206 (m), 1117 (w), 1053 (w), 855 (m), 766 (m), 751 (m), 667
(m), 538 (w), 420 (w). HRMS (APCI+, MeCN + CH2Cl2), m/z
(relative intensity, %): [M+ − Cl] calcd for C11H15O2Sn
299.00885. Found: 299.00901 (100%).
Synthesis of [2-(OvCH)C6H4]Me2SnCl (2)
Water (0.3 mL) and a catalytic amount of p-TsOH were added
to a solution of 1 (0.7 g, 2.1 mmol) in acetone (5 mL). The reac-
tion mixture was heated at 40 °C for 5 hours, then the solvent
was removed in a vacuum. The compound was obtained as an
oil and the removal of water traces afforded 0.52 g (86%).
Colourless crystals of 2 were obtained from toluene in two
months’ time, m.p. 64–66 °C. Elemental analysis calcd for
C9H11ClOSn (289.35): C, 37.36; H, 3.83%. Found C, 37.35; H,
3.77%. 1H NMR (CDCl3, 300 MHz, 20 °C): δ 0.75 (s, 6H, 2JSn,H =
69.4 Hz, CH3), 7.64 (ddd, 1H, 3JH,H = 7.5 Hz, 4JH,H = 1.2 Hz,
H-4), 7.80 (dd, 1H, 3JH,H = 7.3 Hz, H-5), 7.96 (dd, 1H, 3JH,H =
7.6 Hz, 4JH,H = 1.2 Hz, 4JSn,H 9 Hz, H-3), 8.30 (d, 1H, 3JH,H =
7.1 Hz, 3JSn,H = 28.8 Hz, H-6), 9.95 (s, 1H, 4JSn,H = 9.2 Hz, H-7).
13
C{1H} NMR (CDCl3, 75.5 MHz, 20 °C): δ −0.14 (s, 1J117Sn,C =
490.3 Hz, 1J119Sn,C = 513.2 Hz, CH3), 130.16 (s, 4JSn,C = 11.4 Hz,
C-4), 134.57 (s, 3JSn,C = 48 Hz, C-3), 136.21 (s, 3JSn,C = 55.5 Hz,
C-5), 137.54 (s, 2JSn,C = 30.4 Hz, C-6), 139.45 (s, 2JSn,C = 41.5 Hz,
C-2), 145.27 (s, 1J117Sn,C = 568 Hz, 1J119Sn,C = 595 Hz, C-1),
196.87 (s, 3JSn,C = 9.5 Hz, C-7). 119Sn{1H} NMR (CDCl3,
111.9 MHz, 20 °C): δ 13.4 (s, br). IR (KBr pellet, ν, cm−1):
3061 (w), 3000 (w), 2912 (w), 2871 (w), 1680 (w), 1643 (vs),
1579 (m), 1557 (m), 1454 (w), 1405 (w), 1384 (m), 1298 (m),
1260 (m), 1213 (s), 1189 (m), 1112 (m), 1047 (m), 1018 (w), 855
(s), 782 (s), 758 (s), 703 (m), 664 (s). HRMS (APCI+, MeCN), m/z
(relative intensity, %): [M+ − Cl] calcd for C9H11OSn 254.98264.
Found: 254.98268 (100%).
Synthesis of [2-(OvCH)C6H4]Me2Sn(NCS) (3)
An aqueous solution of KSCN (0.25 g, 2.63 mmol, 400%
excess) was added to a solution of 2 (0.19 g, 0.66 mmol) in
CH2Cl2 and stirred for 24 h at room temperature. The organic
layer was separated and the aqueous solution was washed with
CH2Cl2 (3 × 10 mL). The combined organic solutions were
dried over anhydrous Na2SO4. After filtration, the solvent was
removed under vacuum and hexane was added to obtain
0.195 g (95%) colourless crystals of the title compound,
m.p. 69–70 °C. Elemental analysis calcd for C10H11NOSSn
(311.97): C, 38.50; H, 3.55; N, 4.49%. Found C, 38.29; H, 3.55;
N, 4.62%. 1H NMR (CDCl3, 400 MHz, 20 °C): δ 0.69 (s, 6H,
6534 | Dalton Trans., 2019, 48, 6527–6538
Dalton Transactions
2
J117Sn,H = 69.4 Hz, 2J119Sn,H = 72.7 Hz, CH3), 7.68 (ddd, 1H,
3
JH,H = 7.5 Hz, 4JH,H = 1.2 Hz, H-4), 7.85 (ddd, 1H, 3JH,H = 7.4
Hz, 4JH,H = 1.3 Hz, H-5), 7.99 (dd, 1H, 3JH,H = 7.5 Hz, 4JH,H = 0.7
Hz, 4JSn,H = 19.0 Hz, H-3), 8.15 (dd, 1H, 3JH,H = 7.2 Hz, 4JH,H =
0.9 Hz, 3JSn,H = 56.7 Hz, H-6), 9.94 (d, 1H, 4JH,H = 1.2 Hz, 4JSn,H
= 9.6 Hz, H-7). 13C{1H} NMR (CDCl3, 100.6 MHz, 20 °C): δ 2.81
(s, 1J117Sn,C = 510.2 Hz, 1J119Sn,C = 534.0 Hz, CH3), 130.64
(s, 4JSn,C = 11.7 Hz, C-4), 134.82 (s, 3JSn,C = 50.7 Hz, C-3), 136.90
(s, 3JSn,C = 56.3 Hz, C-5), 137.34 (s, 2JSn,C = 26.3 Hz, C-6), 139.32
(s, 2JSn,C = 45.9 Hz, C-2), 141.32 (s, NCS), 144.03 (s, C-1), 197.32
(s, 3JSn,C = 11.3 Hz, C-7). 119Sn{1H} NMR (CDCl3, 149.2 MHz,
20 °C): δ −50.2 (t, 1J119Sn,14N = 136.7 Hz). IR (KBr pellet, ν,
cm−1): 3420 (w), 2390 (w), 2280 (w), 2065 (vs), 1635 (s), 1560
(w), 1450 (w), 1380 (w), 1295 (w), 1205 (m), 1120 (w), 860 (m),
770 (m), 665 (w). HRMS (APCI+, MeOH), m/z (relative intensity,
%): [M+ − NCS] calcd for C9H11OSn 254.98264. Found:
254.98282(100%).
Synthesis of ClSnMe2[2-C6H4(4-CHvN-1,1′-C6H4C6H4-4′-
NvCH)-2′-C6H4]Me2SnCl (4)
Compound 2 (0.25 g, 0.86 mmol) and benzidine (0.08 g,
0.43 mmol) were mixed in the absence of a solvent and the
reaction mixture was heated until a clear melt was obtained.
The temperature was maintained for 20 min and vacuum was
applied to remove the resulting water. After cooling, the title
compound was obtained as a white solid (0.31 g, 99%) which
was recrystallized from DMSO, m.p. >300 °C. 1H NMR (DMSO-
d6, 400 MHz, 20 °C): δ 0.72 (s, 12H, 2JSn,H = 71.4 Hz, CH3), 7.55
(d, 4H, 3JH,H = 8.1 Hz, H-10), 7.68 (dd, 2H, 3JH,H = 7.3 Hz, H-4
or H-5), 7.75 (dd, 2H, 3JH,H = 7.5 Hz, H-5 or H-4), 7.90 (d, 4H,
3
JH,H = 8.2 Hz, H-9), 7.98 (d, 2H, 3JH,H = 7.5 Hz, H-3), 8.20 (d,
2H, 3JH,H = 7.2 Hz, 3JSn,H = 62.2 Hz, H-6), 9.18 (s, 2H, H-7).
119
Sn{1H} NMR (DMSO-d6, 149.2 MHz, 20 °C): δ −72.5 (s).
IR (KBr pellet, ν, cm−1): 3058 (w), 3039 (w), 3000 (w), 2910 (w),
1979 (w), 1614 (s), 1594 (s), 1552 (s), 1491 (s), 1460 (w),
1437 (w), 1403 (w), 1371 (m), 1294 (w), 1261 (w), 1244 (w),
1195 (m), 1159 (w), 1112 (w), 1050 (w), 1002 (w), 905 (m),
823 (vs), 768 (vs), 718 (m), 664 (w). HRMS (APCI+, MeCN + DMSO),
m/z (relative intensity, %): [M+ − Cl] calcd for C30H30ClN2Sn2:
693.01360. Found: 693.01254 (60%); [Sn[2-C6H4(4-CHvN-1,1′-
C6H4C6H4-4′-NH2)+] calcd for C19H15N2Sn: 391.02517. Found:
391.02467 (100%).
Synthesis of ClSnMe2[2-C6H4(CHvNCH2CH2NvCH)-2′-C6H4]-
Me2SnCl (5)
A mixture of compound 2 (0.50 g, 1.7 mmol) and ethylenedi-
amine (0.052 g, 0.06 ml, 0.86 mmol) was heated in the absence
of a solvent until a clear melt was obtained. The temperature
was maintained for 15 min and vacuum was applied to remove
the resulting water. After cooling, the title compound was
obtained as a white solid (0.51 g, 98%) which was recrystallized
from DMSO, m.p. >300 °C. 1H NMR (DMSO-d6, 400 MHz,
20 °C): δ 0.68 (s, 12H, 2JSn,H = 71.6 Hz, CH3), 3.92 (s, 4H, H-8),
7.60 (dd, 2H, 3JH,H = 7.3 Hz, H-4 or H-5), 7.69 (dd, 2H, 3JH,H =
7.5 Hz, H-5 or H-4), 7.78 (d, 2H, 3JH,H = 7.6 Hz, H-3), 8.13 (d,
2H, 3JH,H = 7.2 Hz, 3JSn,H = 63.0 Hz, H-6), 8.81 (s, 2H, H-7).
This journal is © The Royal Society of Chemistry 2019
Dalton Transactions
119
Sn{1H} NMR (DMSO-d6, 149.2 MHz, 20 °C): δ −84.5 (s).
IR (KBr pellet, ν, cm−1): 3448 (w), 3068 (w), 3046 (w), 3001 (w),
2934 (w), 2871 (w), 2358 (w), 1710 (w), 1633 (vs), 1557 (m),
1463 (w), 1440 (w), 1383 (w), 1294 (w), 1223 (m), 1189 (w), 1160
(w), 1117 (w), 1043 (m), 1017 (w), 991 (m), 877 (w), 772 (vs),
715 (m), 660 (w), 645 (w), 549 (m), 524 (w), 433 (w), 409 (w).
HRMS (APCI+, MeCN + DMSO), m/z (relative intensity, %):
[M+ − Cl] calcd for C20H26ClN2Sn2: 568.98230. Found:
568.97960 (20%); [C6H4(CHvNCH2CH2NvCH)-2-C6H4]Me2Sn+]
calcd for C18H21N2Sn: 385.07212. Found: 385.07069 (3%).
Synthesis of (SCN)SnMe2[2-C6H4(CHvNCH2CH2NvCH)-
2′-C6H4]Me2Sn(NCS) (6)
Method A: KSCN (0.01 g, 0.103 mmol) was added to a solution
of 5 (0.05 g, 0.05 mmol) in deuterated DMSO in a NMR tube
and stirred for 10 minutes at room temperature. 1H and 119Sn
NMR showed total conversion to the desired product. Method
B: A mixture of compound 3 (0.135 g, 0.433 mmol) and ethyl-
enediamine (0.013 g, 0.216 mmol) was stirred together in the
absence of a solvent or a catalyst and then heated until a clear
melt was obtained. The temperature was maintained for
5 minutes and the resulting water was removed under vacuum.
After cooling and recrystallization from DMSO, the title com-
pound was obtained as colourless crystals (0.14 g, 99%),
m.p. 277–278 °C. 1H NMR (DMSO-d6, 400 MHz, 20 °C): δ 0.67
(s, 12H, 2JSn,H = 72.1 Hz, CH3), 3.95 (s, 4H, H-8), 7.65 (ddd, 2H,
3
JH,H = 7.5 Hz, 4JH,H = 1.3 Hz, H-4 or H-5), 7.75 (ddd, 2H, 3JH,H
= 7.4 Hz, 4JH,H = 1.3 Hz, H-5 or H-4), 7.85 (d, 2H, 3JH,H = 7.2
Hz, H-3), 7.90 (d, 2H, 3JH,H = 7.2 Hz, H-6), 8.90 (s, 2H, H-7). IR
(KBr pellet, ν, cm−1): 3000 (w), 2070 (vs), 1632 (m), 1555 (w),
1461 (w), 1437 (w), 1377 (w), 1294 (w), 1258 (w), 1218 (w), 1112
(w), 1041 (w), 982 (w), 876 (w), 764 (m), 709 (w). HRMS (APCI+,
MeCN + DMSO), m/z (relative intensity, %): [M+ − NCS] calcd
for C21H26N3SSn2 591.98859. Found: 591.98898 (93%).
Synthesis of [2-(OvCH)C6H4]Me2SnO(O)CC5H4N-4 (7)
To a solution of 2 (0.500 g, 1.728 mmol) in ethanol (30 mL)
sodium isonicotinate (0.251 g, 1.728 mmol) was added and
the reaction mixture was stirred for 24 h at room temperature.
The solvent was then removed in a vacuum, CH2Cl2 was
added over the remaining residue and the obtained solution
was filtered. Hexane was added to the clear filtrate to obtain
the title compound as colourless crystals (0.44 g, 68%),
m.p. 136–137 °C. 1H NMR (CDCl3, 400 MHz, 20 °C): δ 0.77 (s,
6H, 2J117Sn,H = 69.6 Hz, 2J119Sn,H = 72.8 Hz, CH3), 7.64 (ddd,
1H, 3JH,H = 7.5 Hz, 4JH,H = 1.2 Hz, H-4), 7.80 (ddd, 1H, 3JH,H =
7.3 Hz, 4JH,H = 1.3 Hz, H-5), 7.95 (m, 2H, H-10), 7.99 (m, 1H,
H-3), 8.13 (dd, 1H, 3JH,H = 7.1 Hz, 4JH,H = 0.9 Hz, 3JSn,H =
49.7 Hz, H-6), 8.76 (m, 2H, H-11), 9.98 (d, 1H, 4JH,H = 1.0 Hz,
H-7). 13C{1H} NMR (CDCl3, 100.6 MHz, 20 °C): δ −2.13
(s, 1J117Sn,C = 514.2 Hz, 1J119Sn,C = 537.7 Hz, CH3), 123.77
(s, C-10), 130.06 (s, 4JSn,C = 10.8 Hz, C-4), 134.73 (s, 3JSn,C =
46.8 Hz, C-3), 136.22 (s, 3JSn,C = 51.4 Hz, C-5), 137.33 (s,
2
JSn,C = 23.2 Hz, C-6), 139.77 (s, 2JSn,C = 41.5 Hz, C-2), 141.00
(s, C-9), 146.65 (s, C-1), 150.39 (s, C-11), 169.83 (s, 2JSnC =
9.5 Hz, C-8), 197.01 (s, 3JSn,C = 9.7 Hz, C-7). 119Sn{1H} NMR
This journal is © The Royal Society of Chemistry 2019
Paper
(CDCl3, 149.2 MHz, 20 °C): δ −20.7 (s). IR (KBr pellet, ν,
cm−1): 2866 (w), 2849 (w), 1652 (s), 1581 (w), 1559 (m), 1496
(w), 1458 (w), 1410 (w), 1348 (vs), 1314 (m), 1265 (w), 1215
(m), 1143 (w), 1048 (w), 990 (w), 859 (m), 754 (m), 709 (w),
684 (m), 664 (w), 580 (w). HRMS (ESI+, MeOH), m/z (relative
intensity, %): [M+ + H] calcd for C15H16NO3Sn: 378.01467.
Found: 378.01394 (83%); [M+ − O2CC5H4N] calcd for
C9H11OSn: 254.98264. Found: 254.98216 (100%).
Synthesis of [{2-(OvCH)C6H4}Me2SnO(O)CC5H4N-4]ZnTPP (8)
Compound 7 (0.0087 g, 0.024 mmol) and ZnTPP (0.016 g,
0.024 mmol) were mixed in CH2Cl2 until a clear solution was
obtained. Hexane was added slowly over the resulted solu-
tion and, after 2 days, purple crystals of the title complex
(0.02 g, 80%) deposited and were separated by filtration,
m.p. > 300 °C (dec). 1H NMR (CDCl3, 400 MHz, 20 °C):
δ 0.41 (s, 6H, 2J117Sn,H = 69.5 Hz, 2J119Sn,H = 72.7 Hz, CH3),
3.27 (s, 2H, H-11), 6.37 (d, 2H, 3JH,H = 5.8 Hz, H-10), 7.43 (m,
1H, H-4), 7.53 (m, 2H, H-5 and H-6), 7.71 (m, 1H, H-3), 7.75
(m, 12H, H-17 and H-18), 8.23 (m, 8H, H-16), 8.90 (8H, s,
H-12), 9.71 (d, 1H, 4JH,H = 0.7 Hz, 4JSn,H = 9.7 Hz, H-7).
C{ H} NMR (CDCl3, 100.6 MHz, 20 °C): δ −2.54 (s, 1J117Sn,C =
13 1
512.4 Hz, 1J119Sn,C = 536.2 Hz, CH3), 120.77 (s, C-14), 122.48
(s, C-10), 126.43 (s, C-17), 127.29 (s, C-18), 129.87 (s, 4JSn,C =
11.2 Hz, C-4), 131.8 (s, C-12), 134.51 (s, C-3), 134.74 (s,
C-16), 136.00 (s, 3JSn,C = 50.6 Hz, C-5), 136.84 (s, 2JSn,C = 23.9
Hz, C-6), 139.52 (s, C-2), 140.67 (s, C-9), 143.61 (s, C-15),
144.30 s (C-11), 146.09 (s, C-1), 150.17 (s, C-13), 167.88 (s,
C-8), 196.84 (s, 3JSn,C = 9.4 Hz, C-7). 119Sn{1H} NMR (CDCl3,
149.2 MHz, 20 °C): δ −19.2 (s). IR (KBr pellet, ν, cm−1):
3744 (w), 3052 (w), 1651 (s), 1591 (w), 1551 (w), 1517 (w),
1482 (w), 1436 (w), 1413 (w), 1340 (vs), 1257 (w), 1204 (m),
1171 (w), 1065 (m), 995 (s), 851 (w), 797 (s), 744 (s), 696 (vs),
659 (m). UV-Vis (CHCl3 , λ max , nm): 418. HRMS
(ESI+, MeOH), m/z (relative intensity, %): [ZnTPP +]
calcd for C44H28N4Zn: 676.16000. Found: 676.15552 (1%);
[M+ − O2CC5H4N − ZnTPP] calcd for C9H11OSn: 254.98264.
Found: 254.98204 (100%).
Conclusions
The synthesis of hypercoordinated monometallic or homobi-
metallic (2-substituted aryl)dimethyltin(IV)-containing com-
pounds is reported. Their characterization in solution and
solid states indicated the presence of rigid distorted trigonal
bipyramidal (C,E)C2SnX (E = O, N; X = Cl, N, O) cores. The
compound [2-(OvCH)C6H4]Me2SnCl (2) was shown to be a
useful precursor for potential organometallic ligands by reac-
tions at the level of the OvCH– functional group and/or of the
halide atom attached to tin. Thus, condensation of 2 with
different diamines, using a solvent and catalyst free method,
afforded the isolation of homobimetallic derivatives
ClSnMe2[2-C6H4(4-CHvN-1,1′-C6H4C6H4-4′-NvCH)-2′-C6H4]-
Me2SnCl (4) and ClSnMe2[2-C6H4(CHvNCH2CH2NvCH)-2′-
C6H4]Me2SnCl (5). On the other hand, the exchange of chlor-
Dalton Trans., 2019, 48, 6527–6538 | 6535
Paper
ide by isothiocyanato or isonicotinato groups provided mono-
metallic or homobimetallic species with terminal sulfur or
nitrogen which can act as donor atoms towards a coordi-
nation-deficient metal center. Thus, such compounds can act
as organometalloligands as proved by the isolation of the dis-
crete heterobimetallic complex [{2-(OvCH)C6H4}Me2SnO(O)
CC5H4N-4]ZnTPP (8) in which the isonicotinate moiety of
[2-(OvCH)C6H4]Me2SnO(O)CC5H4N-4 (7) is bridging the trior-
ganotin(IV) fragment to a ZnTPP moiety via the Npyridyl atom.
The use of related monometallic or bimetallic species, e.g.
(SCN)SnMe2[2-C6H4(CHvNCH2CH2NvCH)-2′-C6H4]Me2Sn(NCS)
(6), as symmetric or asymmetric ditopic linkers between neutral
or ionic metal complex nodes to afford coordination polymers of
different dimensionality is under investigation.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
This work was supported by the National University
Research Council of Romania CNCSIS (Research Projects
No. PN-II-RU-TE-2011-3-0033 and PN-II-ID-PCCE-2011-2-0050/
Partener 3). The support provided by The National Center for
X-Ray Diffraction (Babeş-Bolyai University, Cluj-Napoca,
Romania) for XRD determinations and refinement is highly
acknowledged.
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