Hypervalent organotin(IV) derivatives containing [2-(Me2NCH2)C6H4]Sn moieties. Competition between nitrogen and chalcogen atoms for coordination to the metal centre

Article abstract of DOI:10.1016/S0022-328X(00)00871-8

[2-(Me₂NCH₂)C₆H₄]SnPh₂Cl (1) was prepared by reacting Ph₂SnCl₂ with [2-(Me₂NCH₂)C₆H₄]Li in toluene. The reactions of (1) with the ammonium salt of the appropriate thiophosphinato ligand in 1:1 molar ratio afford the isolation of [2-(Me₂NCH₂)C₆H₄]SnPh₂L [L=S(S)PPh₂ (2), O(S)PPh₂ (3)] as white crystalline solids. The molecular structure of 1-3 was determined by single-crystal X-ray diffraction. Their crystals contain monomeric units with the metal atom exhibiting a distorted trigonal bipyramidal coordination environment. The SnC₃ moiety is almost planar. The N atom of the pending CH₂NMe₂ arm is strongly coordinated to the metal centre (Sn(1)-N(1) 2.519(2), 2.548(3), 2.481(2) ? for 1, 2 and 3, respectively), trans to the Cl, O or S atoms (N(1)-Sn(1)-Cl(1) 170.49(6)°, N(1)-Sn(1)-S(1) 169.06(8)°, N(1)-Sn(1)-O(1) 168.58(8)°, respectively). The S atom double bonded to phosphorus is not involved in intra- or intermolecular coordination to tin.

Full text of DOI:10.1016/S0022-328X(00)00871-8

Journal of Organometallic Chemistry 623 (2001) 161–167
www.elsevier.nl/locate/jorganchem
Hypervalent organotin(IV) derivatives containing
[2-(Me2NCH2)C6H4]Sn moieties. Competition between nitrogen
and chalcogen atoms for coordination to the metal centre
Richard A. Varga a, Markus Schuermann b, Cristian Silvestru a,*
a Facultatea de Chimie, Uni6ersitatea Babes-Bolyai, RO-3400 Cluj-Napoca, Romania
b Lehrstuhl fu¨r Anorganische Chemie II der Uni6ersita¨t Dortmund, 44221 Dortmund, Germany
Received 1 September 2000; accepted 7 November 2000
Abstract
[2-(Me2NCH2)C6H4]SnPh2Cl (1) was prepared by reacting Ph2SnCl2 with [2-(Me2NCH2)C6H4]Li in toluene. The reactions of (1)
with the ammonium salt of the appropriate thiophosphinato ligand in 1:1 molar ratio afford the isolation of [2-
(Me2NCH2)C6H4]SnPh2L [L=S(S)PPh2 (2), O(S)PPh2 (3)] as white crystalline solids. The molecular structure of 1–3 was
determined by single-crystal X-ray diffraction. Their crystals contain monomeric units with the metal atom exhibiting a distorted
trigonal bipyramidal coordination environment. The SnC3 moiety is almost planar. The N atom of the pending CH2NMe2 arm
,
is strongly coordinated to the metal centre (Sn(1)ꢀN(1) 2.519(2), 2.548(3), 2.481(2) A for 1, 2 and 3, respectively), trans to the Cl,
O or S atoms (N(1)ꢀSn(1)ꢀCl(1) 170.49(6)°, N(1)ꢀSn(1)ꢀS(1) 169.06(8)°, N(1)ꢀSn(1)ꢀO(1) 168.58(8)°, respectively). The S atom
double bonded to phosphorus is not involved in intra- or intermolecular coordination to tin. © 2001 Elsevier Science B.V. All
rights reserved.
Keywords: Hypervalent organotin(IV) derivatives; Nitrogen; Chalcogen; Metal centre
C6H4]SnPh2[S(S)PPh2]
C6H4]SnPh2[O(S)PPh2] (3), as well as their crystal and
(2)
and
[2-(Me2NCH2)-
1. Introduction
molecular structure.
Several organotin(IV) compounds containing the [2-
(Me2NCH2)C6H4] group have been investigated so far
by single crystal X-ray diffraction and in all cases
hypervalent structures were obtained as a result of the
strong intramolecular N“Sn [1–7]. However, no
derivatives with anionic ligands containing a second
potential coordinating atom, to compete the nitrogen
atom of the CH2NMe2 pending arm for coordination to
the metal centre have been prepared so far. On the
other hand, thiophosphorus ligands of the type
[R2P(S)X]− (R=alkyl, aryl, alkoxy; X=O, S) are well
known to involve usually both chalcogen atoms in
coordination to the metal atom in organotin(IV)
derivatives [8–12].
2. Results and discussion
2.1. Preparation
The C,N-[2-(dimethylaminomethyl)phenyl]diphenyl-
tin(IV) chloride, [2-(Me2NCH2)C6H4]SnPh2Cl (1), was
prepared according to Eq. (1), by reacting [2-
(Me2NCH2)C6H4]Li with Ph2SnCl2, in toluene, at −
78°C:
[2-(Me2NCH2)C6H4]Li+Ph2SnCl2
“[2-(Me2NCH2)C6H4]SnPh2Cl+LiCl
(1)
Here we report on the synthesis and spectroscopic
characterisation of some new organotin(IV) derivatives,
i.e. [2-(Me2NCH2)C6H4]SnPh2Cl (1), [2-(Me2NCH2)-
1
The methatesis reaction between stoichiometric
amounts of 1 and the ammonium salt of the appropri-
ate organophosphorus ligand (Eq. (2)), affords the iso-
lation of compounds [2-(Me2NCH2)C6H4]SnPh2-
* Corresponding author. Fax: +40-64-190818.
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00871-8

162
R.A. Varga et al. / Journal of Organometallic Chemistry 623 (2001) 161–167
[S(S)PPh2] (2) and [2-(Me2NCH2)C6H4]SnPh2[O(S)-
PPh2] (3) as colorless, crystalline solids:
higher (1200 cm−1), which supports the bidentate coor-
dination of the ligand moiety as suggested by 31P
chemical shift (see subsequent discussion).
[2-(Me2NCH2)C6H4]SnPh2Cl+NH4[XSPPh2]
“[2-(Me2NCH2)C6H4]SnPh2[X(S)PPh2]+NH4Cl
X=S (2), O (3)
(2)
2.3. NMR spectra
The assignment of the 1H and 13C chemical shifts
according to the numbering scheme (a) was made using
literature data for related organotin compounds [4,8].
The NMR data indicate that in solution the com-
pounds 1 and 2 have structures comparable to that
found in solid state, i.e. a trigonal bipyramidal coordi-
nation geometry around the tin atom due to the in-
tramolecular N“Sn coordination. Although the
observed single resonances for the benzylic as well as
for the aminomethyl protons are compatible either with
a tetrahedral or with a pentacoordinate structure, the
presence of tin satellites for these signals is consistent
with an intramolecular N“Sn coordination. The mag-
nitude of these 117/119SnꢀH coupling constants (1.87s
All compounds are air-stable products and were
characterised by IR and multinuclear NMR (1H, 13C,
31P, 119Sn) spectroscopy and their crystal and molecular
structures have been determined by single crystal X-ray
diffraction.
2.2. IR spectra
The infrared spectra of 2 and 3 exhibit, in addition to
the expected strong absorptions due to the organic
groups bonded to tin, strong bands in the 660–530
cm−1 region and around 1020 cm−1 (for 3), which
were assigned to phosphorus–sulfur and phosphorus–
oxygen stretching vibrations. The presence of absorp-
tion bands corresponding to PꢁS double bond (645
cm−1) and PꢀO(Sn) single bond (1017 cm−1) in the
infrared spectrum of 3 indicates a primary coordination
of the phosphorus ligand through the oxygen atom (c.f.
the methyl esters: 1027 (PꢀO), 635 (PꢁS) cm−1 for
Ph2P(S)OMe [13]; 1200 (PꢁO), 568 (PꢀS) cm−1 for
Ph2P(O)SMe [13]; for a detailed discussion see Ref.
[11]). For both compounds the infrared data are consis-
tent with a monodentate behavior of the phosphorus
ligand in solid state. This behavior of a monothiophos-
phinato moiety contrasts with its ability to exhibit a
bridging pattern and thus to increase the coordination
number of the metal centre in a triorganotin(IV) group
from 4 to 5, leading to chain polymeric structures, e.g.
[Ph3SnOSPPh2]n [12]; [Me3SnOSPMe2]n [14]. However,
the coordination number of tin in 2 and 3, at least in
solid state, is increased to five through the intramolecu-
lar N“Sn, as proved by single-crystal X-ray diffrac-
tion (see below). The solution IR spectrum of 3 (in
CHCl3) exhibits a shift of the absorption bands corre-
sponding to phosphorus–sulfur and phosphorus–oxy-
gen stretching vibrations to lower (613 cm−1) and
3
3
(NꢀCH3, JSnH 38.7 Hz), 3.55s (ꢀCH2ꢀ, JSnH 38.9 Hz)
3
for 1, and 1.68s (NꢀCH3, JSnH 34.1 Hz), 3.45s (ꢀCH2ꢀ,
3JSnH 28.7 Hz) for 2, respectively) is comparable with
those observed for Ph3SnꢀNMe2 (3JSnH 41.5/43.5 Hz), a
compound containing a covalent tin–nitrogen bond
[15].
By contrast, no tin satellites were observed in the
1H-NMR spectrum of compound 3. On the other hand,
the magnitude of the 31P chemical shift (l 64.7 ppm) is
indicative for
a
monothiophosphinato moiety,
[OSPPh2]−, involving both chalcogen in coordination
to tin (c.f. l(31P) 83.5 ppm for Ph2P(S)OMe [16]; 42.8
ppm for Ph2P(O)SMe [16]; 64.9 ppm for Ph3SnOSPPh2
[11]; for a detailed discussion see Ref. [11]). This behav-
ior suggests that a competition for the metal centre
between the nitrogen atom of the pendant arm and the
sulfur double bonded to phosphorus can occur in solu-
tion, and for 3, at least at room temperature, the
intramolecular N“Sn bond is broken (Scheme 1).
The magnitude of the chemical shifts in the 119Sn-
NMR spectra of 1 and 3 is in the range for 5-coordi-
nated triaryltin(IV) derivatives, thus supporting the
proposed structures in solution [3,17]. For compound 3
the 119Sn resonance shows a doublet pattern due to
tin–phosphorus coupling (2JSnP 122.9 Hz).In addition
to the resonances due to organic groups attached to tin,
proton and carbon resonances corresponding to the
Scheme 1.

R.A. Varga et al. / Journal of Organometallic Chemistry 623 (2001) 161–167
163
Fig. 3. General view (SHELXTL-PLUS) of the molecular structure of 3
showing 30% probability displacement ellipsoids and the atom num-
bering scheme.
Fig. 1. General view (SHELXTL-PLUS) of the molecular structure of 1
showing 30% probability displacement ellipsoids and the atom num-
bering scheme.
Table 1
,
Relevant interatomic distance (A) and angles (°) in [2-
(Me2NCH2)C6H4]SnPh2Cl (1), [2-(Me2NCH2)C6H4]SnPh2[S(S)PPh2]
(2) and [2-(Me2NCH2)C6H4]SnPh2[O(S)PPh2] (3)
1, X=Cl
2, X=S
3, X=O
Bond distances
Sn(1)ꢀC(21)
Sn(1)ꢀC(11)
Sn(1)ꢀC(1)
Sn(1)ꢀN(1)
Sn(1)ꢀX(1)
Sn(1)···S(y) a
P(1)ꢀO(1)
2.125(3)
2.125(3)
2.126(3)
2.519(2)
2.4691(9)
2.123(4)
2.130(4)
2.130(4)
2.548(3)
2.5837(11)
4.0487(14)
2.124(3)
2.129(3)
2.124(3)
2.481(2)
2.1302(17)
4.7337(9)
1.5325(18)
1.9501(10)
P(1)ꢀS(1)
P(1)ꢀS(2)
2.0599(16)
1.9489(14)
Bond angles
C(21)ꢀSn(1)ꢀC(11)
C(21)ꢀSn(1)ꢀC(1)
C(11)ꢀSn(1)ꢀC(1)
122.05(10)
121.34(9)
114.15(10)
117.52(17)
118.87(16)
120.79(16)
123.73(10)
120.59(10)
114.16(10)
Fig. 2. General view (SHELXTL-PLUS) of the molecular structure of 2
showing 30% probability displacement ellipsoids and the atom num-
bering scheme.
C(21)ꢀSn(1)ꢀX(1)
C(11)ꢀSn(1)ꢀX(1)
C(1)ꢀSn(1)ꢀX(1)
93.35(7)
96.46(8)
95.96(8)
101.26(10)
87.66(10)
97.85(11)
96.03(8)
93.39(9)
92.69(9)
phenyl groups bonded to phosphorus are observed for
compounds 2 and 3; as expected, they are split into two
components of equal intensity, due to phosphorus–pro-
ton and phosphorus–carbon coupling, respectively.
C(21)ꢀSn(1)ꢀN(1)
C(11)ꢀSn(1)ꢀN(1)
C(1)ꢀSn(1)ꢀN(1)
89.22(9)
89.90(9)
74.92(9)
89.31(13)
89.93(13)
74.28(13)
90.36(8)
90.89(9)
75.91(9)
X(1)ꢀSn(1)ꢀN(1)
P(1)ꢀX(1)ꢀSn(1)
170.49(6)
169.06(8)
105.28(5)
168.58(8)
143.62(11)
2.4. Crystal and molecular structure of
[2-(Me2NCH2)C6H4]SnPh2Cl (1),
[2-(Me2NCH2)C6H4]SnPh2[S(S)PPh2] (2) and
[2-(Me2NCH2)C6H4]SnPh2[O(S)PPh2] (3)
X(1)ꢀP(1)ꢀC(41)
X(1)ꢀP(1)ꢀC(31)
C(41)ꢀP(1)ꢀC(31)
X(1)ꢀP(1)ꢀS(y)a
C(41)ꢀP(1)ꢀS(y)a
C(31)ꢀP(1)ꢀS(y)a
107.08(14)
104.17(15)
103.01(18)
117.59(7)
112.59(14)
111.11(15)
108.26(11)
104.03(12)
103.60(12)
117.11(8)
110.75(9)
112.06(10)
The molecular structure of compounds 1–3 with the
atom numbering scheme is shown in Figs. 1–3, respec-
tively, and selected interatomic distances and angles are
a For S(y) atom, y=2 for 2, and y=1 for 3, respectively.

164
R.A. Varga et al. / Journal of Organometallic Chemistry 623 (2001) 161–167
listed in Table 1. The crystal structure of all three
compounds consists of discrete monomeric molecular
units separated by normal van der Waals distances.
The structure of compounds 1–3 reveals some com-
mon trends. Thus, the coordination geometry around
the tin atom is distorted trigonal bipyramidal as result
of a strong intramolecular N“Sn interaction. The
axial positions are occupied by nitrogen and X(1)
atoms (N(1)ꢀSn(1)ꢀX(1) 170.49(6)° in 1 (X=Cl),
169.06(8)° in 2 (X=S), and 168.58(8)° in 3 (X=O)),
while the carbon atoms of the phenyl groups are in the
equatorial plane. The Sn(1) atom is displaced from the
equatorial C3 plane on the side of the axial X(1) atom
interaction is again reflected in a SnꢀS bond distance
,
ca. 0.13 A larger than in the above dithiophosphato
derivative. The tin–sulfur bond distance in 2 is also ca.
,
,
0.067 A larger than in Me3Sn[SPPh2NPPh2S] (2.517 A)
[23], for which a distorted trigonal bipyramidal trans-
S2SnC3 environment was described as a result of the
bridging nature of the phosphorus ligand (weak inter-
,
molecular Sn···S interaction, 3.627 A). The monoden-
tate behavior of the dithio ligand in 2 (P(1)ꢀS(1)
,
,
2.0599(16) A, P(1)ꢀS(2) 1.9489(14) A) is also reflected
in the phosphorus–sulfur bond distances within the
ligand moiety, which are consistent with PꢀS single and
,
PꢁS double bonds (cf. Ph2P(S)SH [24]: PꢀS 2.077(1) A
and PꢁS 1.954(1) A).
,
,
,
,
with 0.193 A (1), 0.208 A (2) and 0.152 A (3), thus
resulting in significant deviation of the XꢀSnꢀC
(93.35(7)–96.46(8)°) and NꢀSnꢀC (74.92(9)–89.90(9)°)
from the ideal value of 90°.
The monomeric nature of 3 is in contrast with the
polymeric structure established for the related
[Ph3SnOSPPh2]n [12], which can be considered as the
parent compound of 3. Both compounds contain 5-co-
ordinated metal centres as result of the different behav-
ior of the monothiophosphinato moiety. In the
triphenyltin(IV) derivative the phosphorus ligand ex-
The tin–nitrogen interatomic distances (Sn(1)ꢀN(1)
,
2.519(2), 2.548(3) and 2.481(2) A for 1, 2 and 3, respec-
tively) are similar to that observed in the related bromo
,
derivative, [2-(Me2NCH2)C6H4]SnPh2Br (2.511 A) [1],
,
and the longer Sn(1)ꢀN(1) distance in 2 reflects the
lower electronegativity of the sulfur atom placed in the
trans position relative to N in the N“SnꢀS fragment.
The resulting five-membered SnC3N rings are folded
along the Sn(1)···Cmethylene axis (SnC3/SnCN dihedral
angle: 40.5° in 1, 41.2° in 2 and 41.5° in 3, respectively),
hibit an O,S-bridging pattern (Sn(1)ꢀO(1) 2.172 A,
,
Sn(1)ꢀS(1%) 2.785 A), thus leading to a SnC3OS core. By
contrast, in the title compound 3 the monothiophosphi-
nato ligand is attached to tin through its oxygen atom
and the trans axial position is occupied by the nitrogen
atom of the CH2NMe2 pending arm, resulting in a
SnC3ON core. Thus, the competition for the coordina-
tion to the metal centre between the ‘hard’ nitrogen and
the ‘soft’ sulfur atoms is the driving force which results
in a monomeric structure of 3. Consequently, a O-
monodentate coordination pattern of the monothio-
phosphinato ligand is achieved in 3 and this behavior is
best reflected in the magnitude of the phosphorus–oxy-
gen and phosphorus–sulfur bond distances within the
,
,
with the nitrogen atom 0.736 A (1), 0.766 A (2) and
,
0.755 A (3) out from the best plane of the rest of the
atoms. The small bite of the C,N-bidentate ligand is
reflected in the magnitude of the N(1)ꢀSn(1)ꢀC(1) angle
(74.92(9)° in 1, 74.28(13)° in 2 and 75.91(9)° in 3,
respectively).
In 1 the Sn(1)ꢀCl(1) bond distance is significantly
,
larger (2.4691(9) A) than in the tetrahedral Ph3SnCl
,
,
(average 2.355 A, for the two independent molecules
ligand moiety: P(1)ꢀO(1) 1.5325(18) A, P(1)ꢀS(1)
, ,
1.9501(10) A in 3 versus P(1)ꢀO(1) 1.517(6) A,
present in the unit cell) [18], consistent with the trans
influence of the strong intramolecular N“Sn
interaction.
,
P(1)ꢀS(1) 2.002(4) A in [Ph3SnOSPPh2]n [12].
In both 2 and 3 the organophosphorus ligands act as
monodentate moieties, being connected to the tin atom
only through one of the chalcogen atoms, i.e.
3. Experimental
,
Sn(1)ꢀS(1) 2.5837(11)
A
in 2, and Sn(1)ꢀO(1)
2.1302(17) A in 3. The second chalcogen atom of the
1,1-dichalcogenophosphinato ligands (Sn(1)···S(2)
3.1. Materials and procedures
,
All manipulations were carried out under vacuum or
argon by Schlenk techniques. Solvents were dried and
freshly distilled prior to use. Diphenyltin(IV) dichlo-
ride, N,N-dimethylbenzylamine and butyllithium were
commercially available. The other starting materials
were prepared according to literature methods: [2-
(Me2NCH2)C6H4]Li [25], NH4[S2PPh2] [26], and
NH4[OSPPh2] [27,28]. Infrared spectra were recorded in
the range 4000–250 cm−1 as KBr pellets on a Jasco
FTIR-615 instrument. The 1H-, 13C- and 31P-NMR
spectra were recorded on a VARIAN GEMINI 300S
instrument operating at 299.5, 75.4 and 121.4 MHz,
,
,
4.0487(14) A in 2, and Sn(1)···S(1) 4.7337(9) A in 3) is
not involved in any intra- or intermolecular interaction
to metal centres.
The monodentate coordination pattern of the 1,1-
dithiophosphinato group in 2 might be considered nor-
mal since for related triorganotin(IV) derivatives,
R3SnS(S)PR%, a tetrahedral structure was suggested on
2
the basis of IR and Mo¨ssbauer data [19–21]. This is
also consistent with the structure of the related tetrahe-
dral Ph3SnS(S)P(OEt)2 (SnꢀS 2.458, Sn···S (non-bond-
,
ing) 5.326 A) [22]. The trans influence of the N“Sn

R.A. Varga et al. / Journal of Organometallic Chemistry 623 (2001) 161–167
165
respectively, using solutions in dried CDCl3. The chem-
ical shifts are reported in ppm relative to TMS and
H3PO4 85%, respectively. The 119Sn-NMR were
recorded on a RMN Bruker DPX-400 instrument and
the chemical shifts are reported in ppm relative to
SnMe4.
2.01. Calc. for C33H32NPS2Sn: C, 60.38; H, 4.91; N,
1
2.13%. IR (cm−1): 655vs [was(PS2)], 538vs [ws(PS2)]. H-
3
NMR: l 1.68s (6H, NꢀCH3, JSnH 34.1 Hz), 3.45s (2H,
3
ꢀCH2ꢀ, JSnH 28.7 Hz), 7.16–7.50m (15H, ꢀC6H4ꢀ,
H3–5
,
SnꢀC6H5-meta+para, PꢀC6H5-meta+para),
3 3
7.65d (4H, SnꢀC6H5-ortho, JHH 6.5, JSnH 65.4 Hz),
3
3
7.70dd (4H, PꢀC6H5-ortho, JHH 7.3, JPH 13.7 Hz),
8.59d (1H, ꢀC6H4ꢀ, H6, JHH 6.9, JSnH 70.3 Hz); 13C-
NMR: l 45.65s (NꢀCH3), 64.63s (ꢀCH2ꢀ), 127.27s
(3JSnC 62.6 Hz), 128.02s (C3,5), 127.61d (PꢀC6H5-meta,
3JPC 13.1 Hz), 128.38s (SnꢀC6H5-meta), 128.99s
(SnꢀC6H5-para), 129.72s (PꢀC6H5-para, C4), 130.72d
3
3
3.2. Preparation of
C,N-[2-(dimethylaminomethyl)phenyl]diphenyltin(IV)
chloride, [2-(Me2NCH2)C6H4]SnPh2Cl (1)
2
A solution of BuLi in hexane (23 ml, 1.63 M, 10%
excess) was added dropwise to a stirred solution of
N,N-dimethylbenzylamine (4.58 g, 0.034 mol) in 100 ml
anhydrous diethyl ether, at room temperature, under
argon, using Schlenk techniques. After 24 h a white
precipitate deposited which was washed with 3×30 ml
of hexane. The solid product was suspended in toluene
and added dropwise under stirring to a cooled (−
78°C) solution of Ph2SnCl2 (11.64 g, 0.034 mol) in 200
ml toluene. After the organotin dichloride solution was
added, the reaction mixture was stirred for 1 h at
−78°C, then stirred over night to reach the room
temperature. The reaction mixture was filtered in open
atmosphere and the solvent removed under vacuum.
The white solid residue was recrystallized from toluene
to give 8.76 g (58,4%) of the title compound as colorless
crystals. M.p. 204–206°C. Anal. Found: C, 56.72; H,
5.00; N, 3.25. Calc. for C21H22ClNSn: C, 56.99; H, 5.01;
(PꢀC6H5-ortho, JPC 11.3 Hz), 136.29s (SnꢀC6H5-ortho,
2JSnC 43.5 Hz), 138.82d (PꢀC6H5-ipso, JPC 90.2 Hz),
1
2
140.16s (C6, JSnC 41.8 Hz), 141.12s, 143.21s (C1,
SnꢀC6H5-ipso); 31P-NMR: l 57.9s (2JSnP 21.2 Hz).
3.4. Preparation of C,N-[2-(dimethylaminomethyl)-
phenyl]diphenyltin(IV)diphenylmonothiophosphinate,
[2-(Me2NCH2)C6H4]SnPh2[O(S)PPh2].0.5CH2Cl2 (3)
A
mixture of 1 (0.276 g, 0.62 mmol) and
NH4[OSPPh2] (0.16 g, 0.62 mmol) in 50 ml anhydrous
toluene was stirred at room temperature for 3 h. The
reaction mixture was filtered to remove NH4Cl and the
clear filtrate was evaporated in vacuo to give the title
compound as a white solid. Recrystallization from
CH2Cl2/n-hexane affords colorless crystals. Yield: 0.36
g (84%), M.p. 149–151°C. Anal. Found: C, 59.02; H,
5.17; N, 1.93. Calc. for C33H32NOPSSn.0.5CH2Cl2: C,
58.93; H, 4.84; N, 2.05%. IR (cm−1): 1017vs [w(PꢀO)],
1
3
N, 3.16%. H-NMR: l 1.87s (6H, NꢀCH3, JSnH 38.7
1
3
645s [w(PꢁS)]. H-NMR: l 1.53s (6H, NꢀCH3), 3.15s
Hz), 3.55s (2H, ꢀCH2ꢀ, JSnH 38.9 Hz), 7.19d (1H,
3
(2H, ꢀCH2ꢀ), 6.95–7.50m (15H, ꢀC6H4ꢀ, H3–5
,
ꢀC6H4ꢀ, H3, JHH 7.3 Hz), 7.44m (8H, ꢀC6H4ꢀ, H4,5
,
SnꢀC6H5-meta+para, PꢀC6H5-meta+para), 7.60d
SnꢀC6H5-meta+para), 7.72d (4H, SnꢀC6H5-ortho,
3
3
3
3JHH 5.7, JSnH 65.5 Hz), 8.50d (1H, ꢀC6H4ꢀ, H6,
(4H, SnꢀC6H5-ortho, JHH 6.8, JSnH 60.0 Hz), 7.70dd
3
3
3JHH=7.1, JSnH 71.4 Hz); 13C-NMR:
l
45.84s
3
(4H, PꢀC6H5-ortho, JHH 8.2, JPH 13.0 Hz), 8.79d (1H,
3
3
ꢀC6H4ꢀ, H6, JHH 7.5, JSnH 66.6 Hz); 31P-NMR: l
64.7s (2JSnP 122.3, 117.6 Hz); 119Sn-NMR: l −209.1d
(2JSnP 122.9 Hz).
(NꢀCH3), 64.87s (ꢀCH2ꢀ, JSnC 28.2 Hz), 127.26s (3JSnC
2
63.8 Hz), 128.34s (3JSnC 71.5 Hz) (C3,5), 128.96s
3
(SnꢀC6H5-meta, JSnC 68.6 Hz), 129.52s (SnꢀC6H5-
2
para), 130.17s (C4), 135.64s (SnꢀC6H5-ortho, JSnC 45.5
Hz), 138.83s (C6, JSnC 44.9 Hz), 141.51s (1JSnC 50.4
2
3.5. X-ray structure determination
Hz), 142.79s (1JSnC 42.1 Hz) (C1, SnꢀC6H5-ipso); 119Sn-
NMR: l −176.9s.
Intensity data for the colorless crystals of 1–3 were
collected on a Nonius KappaCCD diffractometer with
graphite-monochromated MoKa radiation at 291 K.
The data collection covered almost the whole sphere of
reciprocal space with 360 frames via ꢀ-rotation (D/ꢀ=
1°) at two times 5s (2) 10s (1), and 30s (3) per frame.
The crystal-to-detector distance was 2.8 for 1 and 2,
and 3.0 cm with a detector-q-offset of 5° for 2 and 3,
respectively. Crystal decay was monitored by repeating
the initial frames at the end of data collection. Analyz-
ing the duplicate reflections there was no indication for
any decay. The structure was solved by direct methods
SHELXS-97 [29] and successive difference Fourier syn-
theses. Refinement applied full-matrix least-squares
methods SHELXL-97 [30].
3.3. Preparation of C,N-[2-(dimethylaminomethyl)-
phenyl]diphenyltin(IV)diphenyldithiophosphinate,
[2-(Me2NCH2)C6H4]SnPh2[S(S)PPh2] (2)
A mixture of 1 (0.271 g, 0.6 mmol) and NH4[S2PPh2]
(0.164 g, 0.6 mmol) in 50 ml anhydrous CH2Cl2 was
stirred at room temperature for 3 h. The reaction
mixture was filtered to remove NH4Cl and the clear
filtrate was evaporated in vacuo to give the title com-
pound as a white solid. Recrystallization from CH2H2/
n-hexane affords colorless crystals. Yield: 0.37 g (92%),
M.p. 196–198°C. Anal. Found: C, 60.11; H, 4.78; N,

166
R.A. Varga et al. / Journal of Organometallic Chemistry 623 (2001) 161–167
Table 2
X-ray crystal data and structure refinement for 1–3
Compound
1
2
3
Empirical formula
Formula weight
Temperature (K)
C21H22ClNSn
442.54
291(1)
C
656.38
291(1)
33H32NPS2Sn
C33H32NOPSSn·0.5CH2Cl2
682.78
291(1)
,
Wavelength (A)
0.71069
Monoclinic
P21/n
0.71069
Monoclinic
P21/n
0.71069
Monoclinic
P21/c
Crystal system
Space group
Unit cell dimensions
,
a (A)
8.490(1)
15.330(1)
15.296(1)
92.622(1)
1988.7(3)
4
1.478
1.421
9.133(1)
8.855(1)
37.885(1)
93.134(1)
3059.3(5)
4
1.425
1.046
10.120(1)
20.614(1)
15.770(1)
107.381(1)
3139.6(4)
4
1.444
1.043
,
b (A)
,
c (A)
i (°)
V (A )
3
,
Z
Dcalc (g cm−3
)
Absorption coefficient (mm−1
F(000)
)
888
1336
1388
Crystal size (mm)
q range for data collections (°)
Reflections collected
0.18×0.15×0.15
4.20–27.48
26230
0.30×0.20×0.20
4.11–25.41
30958
0.35×0.22×0.20
2.91–27.48
40441
Complete collected qmax
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indicies [I\2|(I)]
R indicies (all data)
98.2
92.3
99.8
4473 [Rint=0.040]
4473/0/220
0.950
R1=0.0282, wR2=0.0637
R1=0.0541, wR2=0.0684
0.477 and −0.298
5199 [Rint=0.063]
5199/0/346
0.897
R1=0.0341, wR2=0.0767
R1=0.0716, wR2=0.0839
0.541 and −0.469
7177 [Rint=0.028]
7177/0/365
0.944
R1=0.0316, wR2=0.0773
R1=0.0584, wR2=0.0812
0.826 and −0.713
−3
,
Largest difference peak and hole (e A
)
The H atoms were placed in geometrically calculated
positions using a riding model and refined with com-
mon isotropic temperature factors (CꢀHaryl 0.93,
Acknowledgements
This work was supported by the Romanian National
Council for High Education Scientific Research (CNC-
SIS) through research project No. 32575-76-280/1999.
,
CꢀHprim 0.96, CꢀHsec 0.97 A, Uiso 0.086(2) (1), 0.095(3)
(2), 0.081(2) (3)) and for the methylene dichloride
molecule in 3 with isotropic temperature factors con-
strained to be 1.5 times to those of the carrier atom.
The C atom of the disordered solvent molecule methyl-
ene dichloride was refined with an occupancy of 0.5.
Atomic scattering factors for neutral atoms and real
and imaginary dispersion terms were taken from Inter-
national Tables for X-ray Crystallography [31]. The
figures were created by SHELXTL [32]. Crystallographic
data are given in Table 2.
References
[1] G. van Koten, J.G. Noltes, A.L. Spek, J. Organomet. Chem. 118
(1976) 183.
[2] G. van Koten, J.T.B.H. Jastrzebski, J.G. Noltes, W.M.G.F.
Pontenagel, J. Kroon, A.L. Spek, J. Am. Chem. Soc. 100 (1978)
5021.
[3] J.T.B.H. Jastrzebski, J. Boersma, G. van Koten, J. Organomet.
Chem. 413 (1991) 43.
[4] G. van Koten, J.T.B.H. Jastrzebski, J.G. Noltes, A.L. Spek, J.C.
Schoone, J. Organomet. Chem. 148 (1978) 233.
[5] J.T.B.H. Jastrzebski, P.A. van der Schaaf, J. Boersma, G. van
Koten, M.C. Zoutberg, D. Heijdenrijk, Organometallics 8 (1989)
1373.
[6] J.T.B.H. Jastrzebski, P.A. van der Schaaf, G. van Koten, M. de
Wit, Y. Wang, D. Heijdenrijk, C.H. Stam, J. Organomet. Chem.
407 (1991) 301.
[7] P. Steenwinkel, J.T.B.H. Jastrzebski, B.-J. Deelman, D.M.
Grove, H. Kooijman, N. Veldman, W.J.J. Smeets, A.L. Spek, G.
van Koten, Organometallics 16 (1997) 5486.
[8] V.K. Jain, Coord. Chem. Rev. 135/136 (1994) 809 and references
therein.
4. Supplementary material
Crystallographic data for the structural analysis of
compounds 1–3 have been deposited with the Cam-
bridge Crystallographic Data Centre, CCDC no.
148292 (1), 148291 (2), 148293 (3)). Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (Fax: +44-1223-336033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk).
[9] I. Haiduc, D.B. Sowerby, S.-F. Lu, Polyhedron 14 (1995) 3389.
[10] I. Haiduc, D.B. Sowerby, Polyhedron 15 (1996) 2469.

R.A. Varga et al. / Journal of Organometallic Chemistry 623 (2001) 161–167
167
[22] K.C. Molloy, M.B. Hossain, D. van der Helm, J.J. Zuckerman,
I. Haiduc, Inorg. Chem. 18 (1979) 3507.
[23] K.C. Molloy, M. Mahon, I. Haiduc, C. Silvestru, Polyhedron 14
(1995) 1169.
[24] B. Krebs, G. Henkel, Z. Anorg. Allg. Chem. 475 (1981) 143.
[25] A. Meller, H. Hoppe, W. Meringgele, A. Haase, M. Noltemeyer,
Organometallics. 17 (1998) 123.
[26] C. Silvestru, A. Silvestru, I. Haiduc, R.Gavino Ramirez, R.
Cea-Olivares, Heteroatom Chem. 5 (1994) 327.
[27] W.A. Higgins, R.W. Vogel, W.G. Craig, J. Am. Chem. Soc. 77
(1955) 1864.
[28] C. Silvestru, I. Haiduc, K.H. Ebert, H.J. Breunig, D.B. Sowerby,
J. Organomet. Chem. 468 (1994) 113.
[29] G.M. Sheldrick, Acta Crystallogr. Sect. A 46 (1990) 467.
[30] G.M. Sheldrick, SHELXTL-97, University of Go¨ttingen, Germany,
1997.
[11] A. Silvestru, C. Silvestru, I. Haiduc, J.E. Drake, J. Yang, F.
Caruso, Polyhedron 16 (1997) 949 and references therein.
[12] A. Silvestru, J.E. Drake, J. Yang, Polyhedron 16 (1997) 4113.
[13] E. Lindner, H.M. Ebinger, Chem. Ber. 107 (1974) 135.
[14] A.-F. Shihada, I.A.-A. Jasmin, F. Weller, J. Organomet. Chem.
268 (1984) 125.
[15] J. Lorberth, J. Organomet. Chem. 16 (1969) 235.
[16] J.C. Tebby (Ed.), CRC Handbook of Phosphorus-31 Nuclear
magnetic Resonance Data, CRC Press, Boca Raton, 1991, pp.
364.
[17] B. Wrackmeyer, Ann. Rep. NMR Spectrosc. 16 (1985) 73.
[18] J.S. Tse, F.L. Lee, E.J. Gabe, Acta Crystallogr. Sect. C 42 (1986)
1876.
[19] C. Silvestru, I. Haiduc, S. Klima, U. Thewalt, M. Gielen, J.J.
Zuckerman, J. Organomet. Chem. 327 (1987) 182.
[20] C. Silvestru, F. Ilies, I. Haiduc, M. Gielen, J.J. Zuckerman, J.
Organomet. Chem. 330 (1987) 315.
[31] International Tables for Crystallography, Vol. C. Dordrecht:
Kluwer Academic Publishers, 1992.
21] C. Silvestru, I. Haiduc, J. Organomet. Chem. 365 (1989)
83.
[32] G.M. Sheldrick, SHELXTL-97. Release 5.1 Software Reference
Manual, Bruker AXS, Inc., Madison, Wisconsin, USA, 1997.
.