Organotin-substituted [13]-crown-4 ethers: Ditopic receptors for lithium and cesium halides

5456 Organometallics 2010, 29, 5456–5471

DOI: 10.1021/om100409v

Organotin-Substituted [13]-Crown-4 Ethers: Ditopic Receptors for

Lithium and Cesium Halides^†

€

Alain C. Tagne Kuate, Ljuba Iovkova, Wolf Hiller, Markus Schurmann, and

Klaus Jurkschat*

€

Lehrstuhl fu€r Anorganische Chemie II, Technische Universitat Dortmund, D-44221 Dortmund, Germany.

Received May 2, 2010

The synthesis of the organotin- and the bis(organostannyl)methane-substituted crown ethers

Ph_(3-n)X_nSnCH₂-[13]-crown-4 (1, n = 0; 2, n = 1, X = I; 3, n = 1, X = Cl; 4, n = 1, X = F; 5, n = 2,

X = I; 6, n = 3, X = I; 8, n = 3, X = Cl; 9, n = 2, X = Cl) and Ph_(3-n)X_nSnCH₂Sn(X)_n-

Ph_(2-n)CH₂-[13]-crown-4 (10, n = 0; 11, n = 1, X = I; 12, n = 2, X = I; 13, n = 1, X = F; 14, n=2,

X = Cl) as well as of the ditopic complexes 8 LiCl H₂O and Ph₂(SCN)SnCH₂-[13]-crown-4 LiSCN

3

(15 LiSCN) are reported. These compounds were characterized by elemental analyses, by ¹H, ¹³C,

3

¹⁹F, and ¹¹⁹Sn NMR spectroscopy, electrospray mass spectrometry, and in the case of 2 and 4 also by

¹¹⁹Sn MAS NMR spectroscopy. Single-crystal X-ray diffraction analyses reveal distorted tetrahedral

configurations for the tin atoms in compounds 1, 11 (Sn2), and 12 (Sn2), whereas intramolecular

OfSn interactions (Sn-O = 2.416(2) (6) to 2.471(3) (11, Sn1) A) characterize the molecular

structures of compounds 2, 6, 9, and 11 (Sn1), in which the tin atoms display distorted trigonal-

˚

bipyramidal configurations. The spatial arrangement of the Sn(1) atom in compound 12 is distorted

˚

octahedral (Sn-O = 2.497(3) and 2.649(3) A), while the tin atom in compound 8 LiCl H₂O is also

3

trigonal bipyramidal. In the latter compound there are both intra- and intermolecular O-H Cl

3 3 3

hydrogen bridges. Moreover, the ditopic complexation of cesium fluoride, CsF, lithium iodide, LiI,

and lithium chloride, LiCl, by compounds 4 and 6, respectively, as well as of LiCl by compounds 3

and 14, is unambiguously proved by NMR spectroscopy and electrospray mass spectrometry.

Introduction

considerable attention in the field of supramolecular host-

guest chemistry.^1-18The so-called ditopic receptors are

multifunctional ligands that complex both an anion and a

cation as a contact ion pair or solvent- or spatially-separated

ion pair. The growing interest in such compounds is stimu-

lated by the shortcomings of ion-pairing effects involved in

the recognition processes of simple anion or cation receptors.

Indeed, recent reports showed the strong dependence of the

countercation on the complexation affinities of anion recep-

tors.^19-22Furthermore, ditopic receptors are of potential

Compounds that incorporate in their framework indivi-

dual anion- and cation-binding sites continue to attract

^†Part of the Dietmar Seyferth Festschrift. Dedicated in great admiration

and gratitude to Prof. Dr. h. c. mult. Dietmar Seyferth for his outstanding and

sustainable service he has made to the worldwide community of organome-

tallic chemists and beyond.

*To whom correspondence should be addressed. E-mail: klaus.

jurkschat@uni-dortmund.de.

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r

pubs.acs.org/Organometallics

Published on Web 08/02/2010

2010 American Chemical Society

Article

Organometallics, Vol. 29, No. 21, 2010 5457

interest because they can easily solubilize hydrophilic salts in

non-polar solvents and, notably, extract salts from an aqu-

eous phase and transport them through an organic mem-

brane, whereas the extraction and transport abilities of

simple anion or cation receptors are drastically affected by

the counterion.^23-26

Chart 1

In spite of these applications, only a limited number of

hosts has been reported that incorporate neutral Lewis acidic

organometallic/organoelement moieties,^8,17,27,28while seve-

ral ditopic receptors involving H-bond-donating groups or

the electrostatic attraction of metal cations as anion-binding

sites are known.^{1-6,13,15,29,30}For instance, Sessler recently

designed ditopic compounds based on a crown ether and

calixpyrole that are able to bind cesium fluoride as a solvent-

separated ion pair.³¹On the other hand, Smith reported

ditopic receptors containing amide moieties capable of bind-

ing and extracting lithium chloride as a water-separated ion

pair.³²For ditopic hosts using Lewis acidic metal cations, we

are aware of only two closely related examples of CsF and

LiCl receptors. Thus, an uranyl-salophen complex contain-

ing aromatic pendants^33,34binds CsF as a contact ion pair,

whereas an organoaluminum-substituted crown ether³⁵

complexes LiCl as a separated ion pair in the solid state.

However, the radioactivity of uranyl-containing compounds

and the instability of the latter system under non-inert

conditions limit potential applications.

Recently, we reported easy-to-synthesize and robust orga-

notin- and bis(organostannyl)methane-substituted crown-5

and crown-6 compounds of types A, B, C, and D (Chart 1)

and demonstrated by means of multinuclear NMR spectros-

copy, electrospray mass sprectrometry, and X-ray diffrac-

tion analysis as well as extraction and transport experi-

ments their ability to ditopically complex sodium and

potassium halides as solvent-separated or spatially separated

ion pairs.^36-40

In continuation of this work, we have prepared and struc-

turally characterized the corresponding organotin- and bis-

(organostannyl)methane-substituted [13]-crown-4 compounds

of types E and F (Chart 1).

We show here that the fluoridotriorganotin-substituted

[13]-crown-4 ether (type E) forms a 1:1 ditopic complex with

CsF in CD₃CN/CDCl₃(2:1). Moreover, the bis(dichloridodiorg-

anostannyl)methane-, the chloridodiphenyltin-, and the tri-

chloridoorganotin-substituted [13]-crown-4 ethers (types

F and E), respectively, are capable of ditopically complexing

LiCl in CD₃CN. The latter complex has been isolated in the

solid state and shows the LiCl salt being complexed as a

water-separated ion pair.

Results and Discussion

Synthetic Aspects and Molecular Structures in the Solid

State. The synthesis of the organotin-substituted [13]-crown-

4 derivatives was carried out according to the procedure

reported for the synthesis of the analogous organotin-sub-

stituted [16]-crown-5³⁶and [19]-crown-6 ethers.³⁹Thus, the

reaction of 13-methylene-1,4,7,10-tetraoxacyclotridecane⁴¹

with triphenyltin hydride provided the tetraorganotin-sub-

stituted crown ether 1 in good yield (eq 1).

(23) Wintergerst, M. P.; Levitskaia, T. G.; Moyer, B. A.; Sessler, J. L.;

Delmau, L. H. J. Am. Chem. Soc. 2008, 130, 4129.

~

(24) Costero, A. M.; Rodrıguez-Munit, G. M.; Gil, S.; Peransi, S.;

~

Gavina, P. Tetrahedron 2008, 64, 110.

(25) Aydogan, A.; Coady, D. J.; Kim, S. K.; Akar, A.; Bielwaski,

C. W.; Marquez, M.; Sessler, J. L. Angew. Chem., Int. Ed. 2008, 47, 9648.

(26) Mahoney, J. M.; Nawaratna, G. U.; Beatty, A. M.; Duggan,

P. J.; Smith, B. D. Inorg. Chem. 2004, 43, 5902.

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hedron 2005, 61, 8095.

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Ed. Engl. 1991, 30, 1474.

Treatment of the tetraorganotin compound 1 with one

molar equivalent of iodine provided the iodidotriorganotin-

substituted crown ether 2 in almost quantitative yield.

Compound 2 was reacted with an excess of silver chloride,

AgCl, in acetonitrile over a period of 14 days in the dark

to give quantitatively the chloridotriorganotin-substituted

crown ether 3. Compound 2 was also converted to its

fluorido-substituted derivative 4 by reaction with an excess of

sodium fluoride, NaF, in the biphasic mixture CH₂Cl₂/H₂O for

two days at room temperature (Scheme 1).

The reaction of the tetraorganotin- and the iodidotri-

organotin-substituted crown ethers 1 and 2, respectively,

with two molar equivalents of iodine afforded the diiodi-

dodiorganotin- and the triiodidomonoorganotin-substi-

tuted crown ethers 5 and 6 in almost quantitative yield

(Scheme 1).

(29) Beer, P. D.; Dent, S. W. Chem. Commun. 1998, 825.

(30) Rudkevich, D. M.; Mercer-Chalmers, J. D.; Verboom, W.;

Ungaro, R.; De Jong, F.; Reinhoudt, D. N. J. Am. Chem. Soc. 1995,

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Lynch, V. M. J. Am. Chem. Soc. 2008, 130, 13162.

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43, 7617.

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L. Inorg. Chem. 2006, 45, 6099.

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K. J. Am. Chem. Soc. 2005, 127, 3831.

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nometallics 2007, 26, 4170.

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Chem.;Eur. J. 2007, 13, 10239.

€

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3398.

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(40) Tagne Kuate, A. C. Ph.D. Thesis, Technische Universitat

Dortmund, 2009.

€

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1984, 49, 4805.

5458 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

Scheme 1

Figure 2. Molecular structure of 2 showing 30% probability

displacement ellipsoids and the crystallographic numbering

scheme.

Figure 1. Molecular structure of 1 showing 30% probability

displacement ellipsoids and the crystallographic numbering

scheme.

derivative 5. Its molecular structure is given in the Support-

ing Information, but the geometric parameters are given in

Tables 1 and 2 as well.

The treatment of 1 with gaseous HCl in CH₂Cl₂at

room temperature for six hours provided a mixture of the

partially hydrolyzed dichloridohydoxymonorganotin-, the

trichloridomonoorganotin-, and the dichloridodiorganotin-

substituted crown ethers 7⁴²(47%), 8 (48%), and 9 (5%).

The compounds 8 and 9 were removed from the mixture by

recrystallization from ethanol and diethyl ether (Scheme 1).

The compounds 1-6, 8, and 9 were isolated as colorless

(1-4, 8, 9) or yellow (5, 6) crystalline solids that are soluble

in dichloromethane, chloroform, acetone, THF, acetonitrile,

and, for 2-4, methanol.

In compound 1 the Sn(1) atom adopts a monocapped

tetrahedral configuration. The O(1) atom approaches the

Sn(1) atom via the tetrahedral face defined by C(1), C(13),

˚

and C(21). The Sn-O distance of 2.976(16) A is shorter than

the sum of the van der Waals radii⁴³of tin (2.20 A) and

˚

oxygen (1.50 A). The distance is similar to the corresponding

distance found in Ph₃SnCH₂-[19]-crown-6 (2.9820(13) and

39

˚

2.9963(14) A), but significantly shorter than the Sn-O

distance in Ph₃SnCH₂-[16]-crown-5 (3.206(1) A). The

36

˚

Sn(1) atom lies 0.5310(1) A out of the trigonal plane defined

The molecular structures of the tetraorganotin compound

1 and the iodidoorganotin-substituted crown ethers 2, 5, and

6 are shown in Figures 1-4. Selected bond distances and

bond angles are listed in Tables 1 and 2. The dichlorido-

substituted crown ether 9 is isostructural with the diodido

by C(1), C(13), and C(21) in the direction of C(7). The crown

ether oxygen atoms O(1) and O(2) are above while O(3) and

O(4) are below the equatorial plane formed by these atoms.

The tin atom in compound 2 is pentacoordinated and

exhibits a distorted trigonal-bipyramidal configuration (geo-

metrical goodness⁴⁴

P

Δ

(θ) 62.07°) with C(1), C(7), and

(42) Compound 7 is a hydroxido-bridged dimer that shows a ¹¹⁹Sn

chemical shift of -450 ppm. It will be presented together with other

dihalogenido(di-μ-hydroxy)organostannoxanes in a forthcoming paper.

(43) Bondi, A. J. Phys. Chem. 1964, 68, 441.

Article

Organometallics, Vol. 29, No. 21, 2010 5459

comparison with the corresponding bond in tetracoordi-

nated triorganotin iodides^45,46and exceeds the sum of the

47

˚

covalent radii of Sn (1.40 A) and I (1.33 A).

˚

The tin atoms in compounds 5, 6, and 9 are pentacoordi-

nated, and each exhibits a distorted trigonal-bipyrami-

P

dal configuration (geometrical goodness⁴⁴Δ (θ) 61.3° (5),

54.4° (6), 65.0° (9)) with C(1), C(21), and I(1) (5), C(21), I(2),

and I(3) (6), and C(1), C(21), and Cl(2) (9) occupying the

equatorial and O(1) and I(2) (5), O(1) and I(1) (6), and O(1)

and Cl(1) (9) occupying the axial positions.

The tin atoms are displaced by 0.308(3) (5), 0.3764(2) (6),

˚

and 0.2551(1) A (9) from the corresponding trigonal plane in

the direction of I(2), I(1), and Cl(1), respectively. Although

they have the same substituent pattern around the tin atom,

the configuration adopted by the tin atom in compounds 5, 6,

and 9 contrasts well with that observed for the correspond-

ing dichloridodiorganotin- and triiodidomonoorganotin-

substituted crown ethers PhCl₂SnCH₂-[16]-crown-5³⁶and

I₃SnCH₂-[16]-crown-5.⁴⁸Indeed, the tin atoms in the two

latters are intramolecularly coordinated by two oxygen atoms

of the crown ether ring, and each adopts a distorted octa-

hedral configuration. The coordination of only one oxygen

atom from the crown ether ring to the tin atom in 5, 6,

and 9 reflects the high rigidity of the [13]crown-4 moiety.

The intramolecular Sn(1)-O(1) distances of 2.465(3) (5),

Figure 3. Molecular structure of 5 showing 30% probability

displacement ellipsoids and the crystallographic numbering

scheme.

˚

2.416(2) (6), and 2.4177(13) A (9) are almost equal. They are

shorter than the corresponding Sn-O distances found in 1

(see above), PhCl₂SnCH₂-[16]-crown-5 (2.522(1), 2.4793(9) A),

36

˚

PhX₂SnCH₂-[19]-crown-6 (2.525(3), 2.554(3) A; X = I;

2.516(3), 2.506(3) A, X = Br),⁴⁰andclosetothoseinI₃SnCH₂-

˚

48

˚

[16]-cronw-5 (2.432(3), 2.470(3) A).

The reaction of the iodidotriorganotin-substituted crown

ether 2 with triphenylstannylmethylmagnesium bromide,

Ph₃SnCH₂MgBr, in tetrahydrofuran, at reflux, provided

the bis(triorganostannyl)methane-substituted crown ether

10 in good yield as a colorless oil that is soluble in most

organic solvents. Its treatment with two and four molar

equivalents of iodine in CH₂Cl₂at 0 °C gave quantitatively

the bis(iodidodiorganostannyl)- and bis(diiodidoorgano-

stannyl)methane-substituted crown ethers 11 and 12, respec-

tively (Scheme 2).

The reaction of compound 11 with an excess of potassium

fluoride, KF, in CH₂Cl₂/H₂O at room temperature gave

the bis(fluoridotriorganostannyl)methane-substituted crown

ether 13 in good yield, while the reaction of 12 with an

excess of silver chloride, AgCl, in CH₃CN for 14 days at

room temperature and in the dark afforded the bis(dichlo-

rido-organostannyl)methane-substituted crown ether 14 in

moderate yield (Scheme 2).

Compounds 11-14 are colorless (13, 14) to yellow (11)

and red (12) crystalline solids that are soluble in CH₂Cl₂,

CHCl₃, and CH₃CN and partially (11, 14) in methanol but

insoluble in diethyl ether. The molecular structures of com-

pounds 11 and 12 are shown in Figures 5 and 6; selected bond

distances and bond angles are listed in Tables 3 and 4.

In both compounds 11 and 12 the Sn(2) atom exhibits a

distorted tetrahedral configuration. The tetrahedral angles

Figure 4. Molecular structure of 6 showing 30% probability

displacement ellipsoids and the crystallographic numbering

scheme.

C(21) occupying the equatorial and O(1) and I(1) occupying

the axial positions. The distortion is manifested by the

O(1)-Sn(1)-I(1) angle of 171.68(5)°, which deviates by

8.32° from the ideal 180°. The Sn(1) atom is displaced by

˚

0.282(1) A from the trigonal plane in the direction of I(1).

˚

The Sn(1)-O(1) distance in compound 2 of 2.467(2) A is the

shortest as compared with the intramolecularly coordinated

iodidotriorganotin-substituted crown ethers Ph₂ISnCH₂-

36

[16]-crown-5 (2.554(2) A) and Ph₂ISnCH₂-[19]-crown-6

˚

39

(2.610(2) A). This difference shows that the OfSn inter-

˚

action becomes stronger when the cavity of the crown ether

ring decreases and is very likely the result of the small ring

being more rigid than the bigger ones. Moreover, and as

observed for the analogous Ph₂ISnCH₂-[16]-crown-5³⁶and

Ph₂ISnCH₂-[19]-crown-6,³⁹the OfSn interaction influences

(45) Kayser, F.; Biesemans, F.; Delmotte, A.; Verbruggen, I.; Gielen,

M.; Willem, R.; Tiekink, E. R. T. Organometallics 1994, 13, 4026.

(46) Hartson, P.; Howie, A.; McQuillan, G. P.; Wardell, J. L.;

Zanetti, E. Polyhedron 1991, 10, 1085.

˚

the Sn(1)-I(1) (2.8249(12) A) bond, which is lengthened in

(47) Holleman, A. F.; Wiberg, E., Inorganic Chemistry; , Wiberg N.,

Ed.; Academic Press: London, 2001.

(48) Arens, V. Diploma Thesis, Technische Universitat Dortmund, 2008.

€

(44) Kolb, U.; Drager, M.; Jousseaume, B. Organometallics 1991, 10,

2737.

€

5460 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

Scheme 2

˚

Table 1. Selected Bond Distances (A) for Compounds 1, 2, 5, 6, and 9

1

2

5

6

9

X(1) = I(1)

X(1) = Cl(1)

X(2) = I(2)

X(3) = I(3)

X(1) = C(13)

X(1) = I(1)

X(2) = I(2)

2.137(4)

X(2) = Cl(2)

2.119(2)

Sn(1)-C(1)

Sn(1)-C(7)

Sn(1)-C(21)

Sn(1)-O(1)

Sn(1)-X(1)

Sn(1)-X(2)

Sn(1)-X(3)

2.136(2)

2.150(2)

2.1560(2)

2.976(2)

2.128(2)

2.151(3)

2.134(3)

2.145(3)

2.466(2)

2.8248(3)

2.136(5)

2.465(3)

2.7067(5)

2.7854(5)

2.139(3)

2.416(2)

2.7717(3)

2.6953(3)

2.6930(3)

2.123(2)

2.418(1)

2.4190(5)

2.3636(5)

Table 2. Selected Bond Angles (deg) for Compounds 1, 2, 5, 6, and 9

1

2

5

6

9

X(1) = C(13)

X(1) = I(1)

X(1) = Cl(1)

X(2) = I(2)

X(3) = I(3)

X(2) = Cl(2)

C(1)-Sn(1)-C(7)

C(1)-Sn(1)-C(21)

C(1)-Sn(1)-O(1)

C(1)-Sn(1)-X(1)

C(1)-Sn(1)-X(2)

C(7)-Sn(1)-C(21)

C(7)-Sn(1)-O(1)

C(7)-Sn(1)-X(1)

C(21)-Sn(1)-O(1)

C(21)-Sn(1)-X(1)

C(21)-Sn(1)-X(2)

C(21)-Sn(1)-X(3)

X(1)-Sn(1)-O(1)

X(1)-Sn(1)-X(2)

X(1)-Sn(1)-X(3)

X(2)-Sn(1)-O(1)

X(2)-Sn(1)-X(3)

X(3)-Sn(1)-O(1)

C(23)-O(1)-Sn(1)

C(24)-O(1)-Sn(1)

C(22)-C(21)-Sn(1)

105.87(8)

119.71(8)

111.9(1)

113.9(1)

86.97(8)

97.95(6)

132.3(2)

86.9(2)

111.6(1)

100.6(1)

136.41(7)

88.34(6)

98.68(5)

109.19(5)

108.59(8)

102.17(8)

167.134(99)

105.27(8)

129.0(1)

85.81(9)

98.46(7)

75.48(9)

96.34(7)

75.0(2)

110.5(1)

96.0(1)

75.3(1)

98.25(8)

127.65(8)

117.71(8)

172.17(5)

98.30(1)

100.05(1)

82.58(5)

107.61(1)

87.03(5)

108.8(2)

128.6(2)

113.8(2)

76.20(6)

96.75(6)

109.74(5)

113.73(8)

171.68(5)

85.5(1)

96.52(2)

172.49(4)

94.95(2)

170.82(7)

85.17(3)

105.6(2)

124.7(2)

115.1(2)

105.2(3)

125.6(3)

114.7(3)

106.7(1)

126.1(1)

113.8(1)

120.5(1)

are ranging between 102.29(13)° (C(47)-Sn(2)-I(2)) and

120.25(17)° (C(7)-Sn(2)-C(47)) (11) and between 102.26(10)°

(C(7)-Sn(2)-I(4)) and 128.63(15)° (C(7)-Sn(2)-C(41)) (12).

The distortion of the tetrahedral configuration is brought

about by the I(1) atom intramolecularly approaching the Sn(2)

˚

atom at distances of 4.2614(4) (11) and 3.8914(4) A (12),

respectively, which are respectively shorter than the sum of

˚

the van der Waals radii of tin (2.2 A) and iodine (2.1 A). The

Article

Organometallics, Vol. 29, No. 21, 2010 5461

˚

Table 3. Selected Bond Distances (A) for Compounds 11 and 12

11

12

Sn(1)-C(21)

Sn(1)-C(7)

Sn(1)-C(1)

Sn(1)-I(1)

Sn(1)-I(2)

Sn(1)-O(1)

Sn(1)-O(4)

Sn(2)-C(7)

Sn(2)-C(41)

Sn(2)-C(47)

Sn(2)-I(2)

Sn(2)-I(3)

Sn(2)-I(4)

2.144(5)

2.152(5)

2.172(2)

2.8006(4)

2.137(4)

2.115(4)

2.7878(4)

2.7546(4)

2.497(3)

2.649(3)

2.109(4)

2.128(4)

2.471(3)

2.118(4)

2.137(5)

2.149(5)

2.7396(4)

2.6951(4)

2.7185(4)

Table 4. Selected Bond Angles (deg) for compounds 11 and 12

11

12

C(21)-Sn(1)-C(7)

C(21)-Sn(1)-C(1)

C(21)-Sn(1)-I(1)

C(21)-Sn(1)-I(2)

C(21)-Sn(1)-O(1)

C(21)-Sn(1)-O(4)

C(7)-Sn(1)-C(1)

C(7)-Sn(1)-I(1)

C(7)-Sn(1)-I(2)

C(7)-Sn(1)-O(1)

C(7)-Sn(1)-O(4)

C(1)-Sn(1)-I(1)

C(1)-Sn(1)-O(1)

I(1)-Sn(1)-I(2)

125.9(2)

118.4(2)

96.4(1)

145.67(15)

Figure 5. Molecular structure of 11 showing 30% probability dis-

placement ellipsoids and the crystallographic numbering scheme.

99.9(1)

102.0(1)

72.13(13)

69.71(13)

74.3(2)

110.9(2)

94.1(1)

102.2(1)

99.8(1)

80.8(1)

82.3(1)

85.0(2)

101.74(8)

90.2(1)

99.90(1)

166.69(6)

95.29(7)

I(1)-Sn(1)-O(1)

I(1)-Sn(1)-O(4)

I(2)-Sn(1)-O(1)

I(2)-Sn(1)-O(4)

O(1)-Sn(1)-O(4)

C(41)-Sn(2)-C(7)

C(41)-Sn(2)-C(47)

C(41)-Sn(2)-I(2)

C(41)-Sn(2)-I(3)

C(41)-Sn(2)-I(4)

C(7)-Sn(2)-C(47)

C(7)-Sn(2)-I(2)

C(7)-Sn(2)-I(3)

C(7)-Sn(2)-I(4)

C(47)-Sn(2)-I(2)

I(3)-Sn(2)-I(4)

167.47(8)

92.30(7)

163.82(6)

72.09(9)

128.63(15)

116.4(2)

105.3(2)

108.4(1)

107.9(1)

102.8(1)

120.3(2)

102.8(1)

109.0(1)

102.3(1)

116.0(2)

103.08(1)

120.8(2)

Sn(1)-C(7)-Sn(2)

Figure 6. Molecular structure of 12 showing 30% probability dis-

placement ellipsoids and the crystallographic numbering scheme.

The distorted octahedral configuration at the Sn(1) atom

in compound 12 contrasts well with that exhibited by the tin

atom in the diiodidodiorganotin-, triiodidomonoorganotin-,

and dichloridodiorganotin-substituted crown ethers 5, 6,

and 9 (see above). In compound 12, both oxygen atoms

intramolecularly coordinate to the tin atom at distances of

˚

Sn(2)-I(2) distance of 2.7396(4) A (11) is slightly longer than

the Sn(2)-I(3) and Sn(2)-I(4) distances of 2.6951(4) and

2.7185(4) A (12), respectively. They all fall in the range of the

˚

Sn-I distances in tetracoordinated organotin iodides.^45,46

The Sn(1) atom in compound 11 shows a distorted tri-

gonal-bipyramidal configuration (geometrical goodness⁴⁴

˚

2.497(3) (Sn1-O1) and 2.649(3) A (Sn1-O4). The former is

P

Δ θ 62.96°) with O(1) and I(1) occupying the axial and

C(1), C(7), and C(21) occupying the equatorial positions.

˚

The Sn(1) atom is displaced by 0.2729(3) A from the trigonal

similar to the corresponding one measured for compound 11

but longer than the Sn-O bonds in compounds 2, 5, 6, and 9,

whereas the latter distance lies considerably above the Sn-O

bond lengths measured for 2, 6, 9, 11, PhX₂SnCH₂-[16]-

plane in the direction of I(1). In compound 12 the Sn(1) atom

is hexacoordinated by C(7), C(21), I(1), I(2), O(1), and O(4)

and exhibits a configuration that represents a real structure

along the path trigonal bipyramid f octahedron. The O(4)

atom approaches the Sn(1) atom via the C(7), C(21) edge

with the result that the C(7)-Sn(1)-C(21) angle increases to

145.7(2)°. In fact, this O(4)fSn(1) coordination illustrates

the enhanced Lewis acidity of the Sn(1) atom in compound

12 as compared with that of compound 11.

˚

crown-5 (2.522(1) and 2.4793(9) A, X = Cl; 2.482(2), X=

I),³⁶I₃SnCH₂-[16]-crown-5 (2.432(3) and 2.470(3) A),⁴⁸and

˚

PhX₂SnCH₂-[19]-crown-6 (2.525(3) and 2.554(3) A, X=I;

40

˚

2.516(3) and 2.506(3) A, X = Br).

Due to the trans influence of the crown ether oxy-

gen atoms, the Sn(1)-I(1) distances of 2.8006(4) (11) and

˚

2.7878(4) A (12) as well as the Sn(1)-I(2) distance of

2.7546(4) A (12) exceed the sum of the covalent radii of

47

˚

5462 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

The ¹¹⁹Sn NMR spectrum in CDCl₃at room temperature

˚

Sn (1.40 A) and I (1.33 A) by 0.071, 0.058, and 0.025 A,

respectively.

of compound 13 showed a broad resonance at δ -27 (ν_1/2

=

Structures in Solution. The ¹¹⁹Sn NMR spectra in CH₂Cl₂/

D₂O or CDCl₃of compounds 1, 10, and 11 (Sn2) show

resonances at δ -107 (1), -53 (10; Sn1), -77 (10; Sn2), and

-50 (11, Sn2) (according to the numbering scheme shown in

Scheme 6), which are comparable to those measured for the

analogous Ph₃SnCH₂-[16]-crown-5 (δ -110),³⁶Ph₃SnCH₂-

[19]-crown-6 (δ -105),³⁹Ph₃SnCH₂SnCH₂-[16]-crown-5

(δ -56 and -77),³⁷Ph₃SnCH₂SnCH₂-[16]-crown-5 (δ -55

and -76),³⁹Ph₂ISnCH₂Sn(I)PhCH₂-[16]-crown-5 (δ -56,

Ph₂ISnCH₂),³⁷and Ph₂ISnCH₂Sn(I)PhCH₂-[19]-crown-6

(δ -55, Ph₂ISnCH₂).³⁹These chemical shifts are close to δ

-90, -60, and -68 reported for Ph₃SnMe,⁴⁹Ph₂SnMe₂,⁵⁰

and Ph₂MeSnI,⁵¹respectively, and correspond to tetracoor-

dinated tin atoms.

Moreover, and as observed for the derivatives Ph₂XSn-

CH₂-[16]-crown-5 and Ph₂XSnCH₂-[19]-crown-6 (X = I,

Cl, F),^36,39the tin atoms in the halogenidotriorganotin-

substituted crown ethers 2-4 as well as the Sn(1) tin atom

in compound 11 are pentacoordinated, with the intramole-

cular OfSn interaction found in the solid state for 2 and 11

being retained in solution. This statement is supported by the

¹¹⁹Sn chemical shifts (CDCl₃) of δ -126 (2), - 87 (3), -111

[d, ¹J(¹¹⁹Sn-¹⁹F) 2208 Hz] (4), and -87 (Sn1, 11) being high-

field shifted as compared with the ¹¹⁹Sn chemical shifts

of nonsubstituted halogenidotriorganotin compounds (see

ref 36 for more details). Furthermore, the ¹¹⁹Sn MAS spec-

trum of 2 shows a chemical shift at δ -121, which is close to

the chemical shift (δ -126) found in solution.

1217 Hz), indicating exchange in solution that is rapid on the

¹¹⁹Sn NMR time scale. No measurements at low temperature

were carried out. The electrospray ionization mass spectrum,

hereafter referred to as ESI-MS, of compound 13 in CH₃CN

showed in the positive mode a mass cluster centered at m/z

703.1 that is assigned to {Ph₂FSnCH₂SnPhCH₂-[13]-crown-

4}^þ. In the negative mode, a mass cluster centered at m/z

743.0 was observed that is assigned to {Ph₂FSnCH₂Sn(F)-

PhCH₂-[13]-crown-4 F}^-.

3

The ESI-MS spectra in the positive mode of compounds

2-4 are characterized by the observation of a mass cluster

centered at 477.1 that is assigned to {Ph₂SnCH₂-[13]-crown-

4}^þ. In addition, for 2 there are mass clusters centered at m/z

627.1 and 668.1 that are assigned to {Ph₂ISnCH₂-[13]-crown-

4 Na}^þand {Ph₂SnCH₂-[13]-crown-4 Na CH₃CN}^þ, re-

3

spectively, while the ESI-MS spectrum (negative mode) of

3 showed a major mass cluster centered at m/z 547.0 that is

assigned to {Ph₂ClSnCH₂-[13]-crown-4 Cl}^-. The ESI-MS

3

(positive mode) spectrum of compound 5 showed mass clus-

ters centered at m/z 417.0, 527.0, 853.2, 1245, and 1267.4 that

are assigned to the species {PhISnCH₂-[13]-crown-4}^þ,

{Ph(OH)SnCH₂-[13]-crown-4}^þ,{(Ph(μ-O)SnCH₂-[13]-crown-

4)₂Na}^þ, {(Ph(μ-O)SnCH₂-[13]-crown-4)₂(Ph(OH)SnCH₂-

3

[13]-crown-4)}^þ, and{(Ph(μ-O)SnCH₂-[13]-crown-4)₂Na}^þ,

respectively. For compounds 6 and 8, the ESI-MS spectra in

3

the positive mode showed mass clusters centered at m/z 798.9

and 385.0 that are assigned to {I₃SnCH₂[13]-crown-4

3

4H₂O Na}^þand {(CH₃O)₂SnCH₂-[13]-crown-4}^þ, respec-

3

However, the ¹¹⁹Sn MAS spectrum of compound 4 dis-

plays a triplet resonance at δ -145 [¹J(¹¹⁹Sn-¹⁹F) 1400 Hz],

which is different from the doublet resonance (δ -111) found

in solution. This result suggests that the fluoridotriorgano-

tin-substituted crown ether 4 is very likely to exist as a

fluoride-bridged dimer or oligomer in the solid state.

The tin atoms in compounds 5, 6, 8, 9, and 12 and the Sn(1)

atom in 14 are also hypercoordinated, as evidenced by the

¹¹⁹Sn chemical shifts in CDCl₃of δ -275 (5), -820 (6), -237

(8), -117 (9), -220 (Sn2, 12), -272 (Sn1, 12), and -94 (Sn1,

14) being low-frequency shifted with respect to the ¹¹⁹Sn

chemical shifts of non-substituted compounds having similar

substituent patterns about the tin atoms such as (PhI₂Sn-

CH₂)₂(δ -169),⁵²(PhCl₂Sn)₂CH₂(δ þ8),⁵³MeSnX₃[δ -700

(X = I); þ21 (X = Cl)],⁵⁴and Me₂SnX₂[δ -159 (X = I); 99

(X = Cl)].^54,55The unambiguous assignment of the signals for

the tetraiodido-substituted compound 12 was achieved by

tively. The ESI-MS spectrum (positive mode) of compound

11 showed mass clusters centered at m/z 813.0 and 862.9 that

are assigned to {Ph₂SnCH₂Sn(I)PhCH₂-[13]-crown-4}^þand

{Ph₂SnCH₂Sn(I)PhCH₂-[13]-crown-4 CH₃OH H₂O}^þ, re-

3

spectively. The ESI-MS spectra in the positive mode of

compounds 12 and 14 showed mass clusters centered at

m/z 838.5 and 639.0 that are assigned to {Ph(OH)ISn-

CH₂ICH₂-[13]-crown-4 2H₂O}^þand {PhClSnCH₂SnCl₂-

3

CH₂-[13]-crown-4}^þ. In the ESI-MS spectrum (negative

mode) of 14, there is a mass cluster centered at m/z 708.9 that

is assigned to {PhClSnCH₂SnCl₂CH₂-[13]-crown-4 Cl}^-.

3

Complexation Studies. The complexation behavior of

the chloridotriorganotin-substituted crown ether 3 toward

lithium rhodanide is similar to that of the halogenidotri-

organotin-substituted crown ether derivatives Ph₂XSn-

CH₂-[16]-crown-5 and Ph₂XSnCH₂-[19]-crown-6 (X = Cl,

SCN)^36,39toward sodium and potassium rhodanide, respec-

tively. Thus, the reaction in dichloromethane/water of com-

pound 3 with excess LiSCN afforded the ditopic complex

1

a H-¹¹⁹Sn-HMQC spectrum (see Supporting Information,

Figure S2) that shows cross-peaks of the ¹¹⁹Sn signal at δ -220

with the H resonances of the o-phenyl and the SnCH₂Sn

1

[15 LiSCN] (15 is here referred to the in situ formed thio-

3

protons, whereas the ¹¹⁹Sn signal at δ -272 shows cross-peaks

with both the SnCH₂Sn and SnCH₂protons.

cyanatotriorganotin-substituted crown ether Ph₂(SCN)Sn-

CH₂-[13]-crown-4) in 62% yield as a colorless viscous oil

(Scheme 3).

The ¹¹⁹Sn NMR spectrum of [15 LiSCN] in CDCl₃

3

(49) Davies, A. G.; Harrison, P. G.; Kennedy, J. D.; Mitchell, T. N.;

Puddephat, R. J.; McFarlan, W. J. Chem. Soc. 1969, 1136.

(50) Hunter, B. K.; Reeves, L. W. Can. J. Chem. 1968, 46, 1399.

(51) Gielen, M.; Jurkschat, K. J. Organomet. Chem. 1984, 273, 303.

(52) Jurkschat, K.; Hesselbarth, F.; Dargatz, M.; Lehmann, J.;

Kleinpeter, E.; Tzschach, A.; Meunier-Piret, J. J. Organomet. Chem.

1990, 388, 259.

(53) Dakternieks, D.; Jurkschat, K.; Wu, H. Organometallics 1993,

12, 2788.

(54) Kennedy, J. D.; McFarlan, W.; Pyne, G. S.; Clarke, P. L.;

Wardell, J. L. J. Chem. Soc., Perkin Trans. 2 1975, 1234.

(55) Mitchell, T. N.; Amamria, A.; Fabisch, B.; Kuivila, H. G.;

Karol, T. J.; Swami, K. J. Organomet. Chem. 1983, 259, 157.

showed a single resonance at δ -239 that is close to δ

-229 and -240 found for the complexes {Ph₂(SCN)Sn-

CH₂-[16]-crown-5 NaSCN}³⁶and {Ph₂(SCN)SnCH₂-[19]-

3

crown-6 KSCN},³⁹respectively. The ¹³C NMR spectrum

of [15 LiSCN] showed that the resonances for the C_i, C20,

3

and C17/C19 (according to the numbering scheme shown in

Scheme 6) carbon atoms are respectively 0.9, 6.2, and 3.8

ppm high-frequency shifted with respect to the correspond-

ing chemical shifts of the parent compound 3. The ESI-MS

spectrum in the positive mode of [15 LiSCN] showed a mass

3

Article

Organometallics, Vol. 29, No. 21, 2010 5463

Scheme 3

Scheme 4

cluster centered at m/z 542.1 that is assigned to {Ph₂-

(SCN)SnCH₂-[13]-crown-4 Li}^þ.

3

The ¹¹⁹Sn NMR spectra at room temperature of CD₃CN

or CDCl₃solutions of the fluoridotriorganotin-substituted

crown ether 4 and the bis(iodido- and fluoridodiorgano-

stannyl)methane-substituted crown ethers 11 and 13, to

which had been added one molar equivalent of lithium

fluoride, LiF, showed no formation of the corresponding

fluoride complexes. This non-reaction between LiF and com-

pounds 4, 11, or 13 is very likely due to the rather high lattice

energy (1033 kJ/mol)⁵⁶of lithium fluoride, which cannot be

compensated for by complex formation. Moreover, the ¹¹⁹Sn

and ¹⁹F NMR spectra of a CDCl₃solution containing

equimolar amounts of 4 and tetrabutylammonium fluoride,

n-Bu₄NF, showed no change of the resonances. Apparently,

the intramolecular OfSn coordination is rather strong and

cannot be broken by attack of the fluoride anion. In contrast,

the crown-6 derivative Ph₂FSnCH₂-[19]-crown-6 reacts with

fluoride anion to give the triorganodifluoridostannate com-

that measured for a salt-free solution of the fluoridotriorga-

notin-substituted crown ether 4 (δ -185.8, ¹J(¹⁹F-^117/119Sn)

2112/2211 Hz), whereas signal (a) including the ¹J(¹⁹F-^117/

¹¹⁹Sn) coupling of 1892 Hz is close to that obtained for the

related KF complex {Ph₂FSnCH₂-[19]-crown-6 KF} [δ

3

1

-157.7, J(¹⁹F-^117/119Sn) 1912 Hz].³⁹The doublet and

triplet ¹⁹F resonances (c) and (d) indicate terminal (F^t) and

bridging fluorine (F^b) atoms, respectively. The chemical shifts

and the ¹J(¹⁹F-^117/119Sn) and ²J(¹⁹F-¹⁹F) couplings of 1796/

1339 Hz and 75/72 Hz are comparable with those measured

for the related complex [o-C₆H₄(SnF₃Me₂)]^-[Et₄N]^þ[δ

plex {Ph₂FSnCH₂-[19]-crown-6 F}^-.³⁹

3

Cesium fluoride, CsF, has a lower lattice energy (748 kJ/

mol)⁵⁶than lithium fluoride, and sandwich complexes for-

med between [12]crown-4 and Cs^þare known.⁵⁷Moreover,

the fluoride anion is able to coordinate to two Lewis acidic

tin atoms with formation of a Sn-F-Sn bridge.⁵⁸Therefore,

for the reaction of compound 4 with CsF one might expect

formation of a sandwich-type complex as well that, in

addition, should be stabilized by a fluoride bridge.

-126.8, J(¹⁹F-^117/119Sn) 1172 Hz, J(¹⁹F-¹⁹F) 84 Hz, F^b;

1

2

δ -155.4, J(¹⁹F-^117/119Sn) 1912 Hz, J(¹⁹F-¹⁹F) 83 Hz,

1

2

F^t].⁵⁹

The ¹¹⁹Sn NMR spectrum at room temperature of a

solution of 4 in CD₃CN/CDCl₃(2:1) to which had been

added one molar equivalent of CsF showed a broad triplet

resonance at δ -277 [¹J(¹¹⁹Sn-¹⁹F) 1885 Hz]. The ¹⁹F NMR

spectrum at room temperature showed a broad signal at δ

-149.1 (ν_1/2= 550 Hz). At -45 °C, the triplet resonance

observed in the ¹¹⁹Sn NMR spectrum sharpened and shifted

slightly to δ -274 [¹J(¹¹⁹Sn-¹⁹F) 1902 Hz], while the ¹⁹F

NMR spectrum displayed a single resonance with satellites

at δ -151.9 [¹J(¹⁹F-¹¹⁷Sn) 1818 Hz, ¹J(¹⁹F-¹¹⁹Sn) 1897 Hz].

These NMR results prove unambiguously the formation of

The ¹⁹F NMR spectrum at room temperature of a

CD₃CN/CDCl₃(3:1) solution containing compound 4 and

CsF in a molar ratio 2:1 showed two broad resonances at

δ -149.1 (ν_1/2= 1011 Hz; integral 1) and -184.8 (ν_1/2= 776

Hz, integral 2). At -45 °C, two major sharp singlet reso-

nances flanked by satellites were observed at δ -152.6

[¹J(¹⁹F-^117/119Sn) 1816/1900 Hz, signal (a)] and -183.4

[¹J(¹⁹F-^117/119Sn) 2098/2183 Hz, signal (b)] of integral ratio

1:2, respectively, as well as two minor intense (total integral

approximately 8%) doublet and triplet resonances at δ

-164.3 [¹J(¹⁹F-^117/119Sn) 1796 Hz, ²J(¹⁹F-¹⁹F) 75 Hz, sig-

nal (c)] and -136.8 [¹J(¹⁹F-^117/119Sn) 1339 Hz, ²J(¹⁹F-¹⁹F)

72 Hz, signal (d)], respectively. No resonance was observed in

the ¹¹⁹Sn NMR spectrum at room temperature. These results

were interpreted in terms of the formation of both a 1:1 and a

2:1 ditopic complex [4 CsF] and [4₂CsF], respectively

the 1:1 ditopic complex [4 CsF] (see Scheme 4) with the latter

3

being kinetically inert at -45 °C on the corresponding NMR

time scales. Support for the interaction between the crown

ether ring and the cesium cation comes from the ¹³C NMR

spectrum. The resonances for the crown ether carbon atoms

C2-C9 and C11/C13 are more broadly distributed as com-

pared with the parent compound 4 and shifted by 1.1 and

4.4 ppm to low and high frequency, respectively. The high

preference of compound 4 to form with CsF a 1:1 rather than

a 2:1 ditopic complex as expected is very likely the result of a

cooperative binding process between Cs^þand F^-.

3

(Scheme 4). Both compounds are in equilibrium with the

free receptor 4, with the equilibrium being slow on the ¹⁹F

and ¹¹⁹Sn NMR time scales at low temperature.

The ¹⁹F NMR resonances as well as the magnitudes of the

2

¹J(¹⁹F-^117/119Sn) and J(¹⁹F-¹⁹F) coupling constants are

consistent with these interpretations. Indeed, the signal (b)

The ¹¹⁹Sn NMR spectra in CD₃CN at room temperature

of the mono-, di-, and triiodido-substituted compounds 2, 5,

and 6 and of the mono- and trichlorido-substituted com-

pounds 3 and 8 to which had been added three molar

1

including the J(¹⁹F-^117/119Sn) coupling of 2183 is close to

(56) Cubicciotti, D. J. Chem. Phys. 1959, 31, 1646.

(57) Ohtsu, K.; Kawashima, T.; Ozutsumi, K. Anal. Sci. 1996, 12, 37.

(58) Dakternieks, D.; Jurkschat, K.; Zhu, H. J.; Tiekink, E. R. T.

Organometallics 1995, 14, 2512.

€

(59) Altmann, R.; Jurkschat, K.; Schurmann, M.; Dakternieks, D.;

Duthie, A. Organometallics 1998, 17, 5858.

5464 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

Scheme 5

whereas that of the H_C14hydrogen atoms is high-frequency

shifted by 0.67 ppm. The ESI-MS spectrum (positive mode)

of this solution showed a mass cluster centered at m/z 787.3

that is assigned to {I₃SnCH₂-[13]-crown-4 Li CH₃CN

3

H₂O}^þ. In the ¹³C NMR spectrum of a sample of 8 þ

LiCl_excessin CD₃CN, the signals of the C11/C13, C12, and

C13 carbon atoms are, with respect to the ¹³C NMR

chemical shifts of pure 8 in CD₃CN, high frequency dis-

placed by 1.7, 1.8, and 11.2 ppm, respectively, while those of

the C2-C9 crown ether carbon atoms moved by 0.4 ppm to

low frequency. Changes were also observed in the ¹H NMR

spectrum of 8 þ LiCl_excess; the signals of the H_C11/C13and

H_C14hydrogen atoms are low-frequency shifted by 0.37 and

0.07 ppm, respectively, whereas that of the H_C12hydrogen

atom moved by 0.19 ppm to high frequency.

equivalents of lithium iodide, LiI, and lithium chloride, LiCl,

respectively, showed single, partially rather broad reso-

nances at δ -150 (ν_1/2= 125 Hz), -331 (ν_1/2= 323 Hz),

-1132 (ν_1/2= 166 Hz), -202 (ν_1/2= 2048 Hz), and -362

(ν_1/2=208 Hz), which are displaced by 18, 67, 325, 107, and

72 ppm to low frequency with respect to the chemical shifts of

the parent compounds 2 (δ -132), 3 (δ -95), 5 (δ -264), 6

(δ -806), and 8 (δ -286). These results can be interpreted in

terms of the equilibrium shown in Scheme 5. The equilibrium

is fast on the ¹¹⁹Sn NMR time scale, and the chemical shifts

are average ones that are composed of the chemical shifts of

the compounds being involved. For each pair of compounds

the position of the equilibrium is reflected by the difference

between the ¹¹⁹Sn chemical shift actually observed and that

of the noncomplexed compound.

From the reactions shown in Scheme 5, the ditopic com-

plex [8 LiCl], as its aqua-complex [8 LiCl H₂O], was iso-

3

lated as a slightly yellow crystalline solid and characterized

by single-crystal X-ray diffraction analysis. The molecular

structure of [8 LiCl H₂O] is shown in Figure 7, and selected

3

bond distances and bond angles are listed in Table 5.

The molecular structure of [8 LiCl H₂O] shows that the

LiCl salt is complexed as a solvent-separated ion pair with a

water molecule being bridged between the Li^þand Cl^-. The

3

˚

Li(1) Cl(2) distance of 4.504(5) A is almost 2-fold bigger

than the Li Cl distance in crystalline lithium chloride

3 3 3

60

(2.565 A). The lithium cation adopts a distorted square-

˚

For the complexes [3 LiCl], [6 LiI], and [8 LiCl] the

3

equilibrium is shifted to the right as their ¹¹⁹Sn chemical

shifts are close to the chemical shifts measured for the

triorganodichloridostannate complex [Ph₂Cl₂SnCH₂-[16]-

crown-5]^-[(Ph₃P)₂N]^þ(δ -199 in CD₃CN)³⁶and the tetra-

iodido- and tetrachloridoorganostannate complexes [I₄Sn-

CH₂-[19]-crown-6]^-[n-Bu₄N]^þ(δ -1032 in CD₃CN)⁴⁰and

planar pyramidal configuration, with the four crown ether

oxygen atoms forming the base of the pyramid and the

oxygen atom of the water molecule in axial position. The

lithium cation lies slightly out of the crown ether cavity and is

˚

placed 0.695(5) A above the pyramid plane in the direction of

O(1W). The Li-O(crown) distances range between 1.9179(4)

[8 Cl]^-[(Ph₃P)₂N]^þ(δ -402 in CD₃CN), respectively. The

(Li(1)-O(4)) and 2.081(5) (Li(1)-O(3)) A, which are slightly

˚

3

formation of the ditopic complexes [3 LiCl], [6 LiI], and

shorter than the Li-O distances measured for the lithium

chloride aqua complex of {(tert-butyl)(bis(N-phenyl)}ben-

3

[8 LiCl] is further supported by ¹H and ¹³C NMR spectros-

3

copy and ESI-MS spectrometry. The ¹³C NMR spectrum of

a solution of 3 þ LiCl_excessin CD₃CN showed high-fre-

quency shifts for the signals of the C_i, C14, and C11/C13

zamide-substituted diazacrown-6 (average Li-O=2.11 A)

32

˚

and also shorter than the Li-O distances reported for the

lithium thiocyanate aqua complex of monoaza-15-crown-5

carbon atoms by 6.3, 9.9, and 6.8 ppm with ¹J(¹³C_i-^117/119

-

(Li-O = 2.109(6)-2.449(6) A). In the latter complexes,

61

˚

Sn) = 769/735 Hz and J(¹³C₁₄-^117/119Sn) = 656/624 Hz,

which are bigger than the corresponding couplings of 662/

634 Hz and 547/524 Hz measured for pure 3. The resonances

of the C2-C9 crown ether carbon atoms moved by 2 ppm to

high frequency. Notably, the ditopic complexation of LiCl

by compound 3 seems to be favored by cooperative effects of

both ions, as the ¹¹⁹Sn NMR spectrum of a solution of 3 in

CD₃CN, to which had been added one molar equivalent of

bis(triphenylphosphoranylidene)ammonium chloride, (Ph₃P)₂-

NCl, showed a resonance at δ -91 indicating that no com-

plexation takes place. The formation of the ditopic complex

the Li-O(water) distances of 1.90 and 1.921(5) A, respec-

1

˚

tively, are however close to the Li(1)-O(1) distance of

˚

1.907(5) A found in [8 LiCl H₂O]. The latter compound

3

forms by intermolecular O(1W)-H Cl(1A) hydrogen

3 3 3

bonding a one-dimensional polymeric chain structure

(Supporting Information, Figure S3). The O(1W)-Cl(1A)

˚

and O(1W)-Cl(2) distances of 3.162(2) and 3.245(2) A,

respectively, are less than the sum of the van der Waals

radii⁴³of O (1.50 A) and Cl (1.80 A).

˚

The tin atom is pentacoordinated and shows a slightly

distorted trigonal-bipyramidal configuration (geometrical

P

[3 LiCl] is in remarkable contrast to the analogous org-

goodness⁴⁴

atoms occupying the equatorial and Cl(1) and Cl(2) occupy-

ing the axial positions. The Sn(1) atom is displaced by

Δ

(θ) 88.1°) with the C(21), Cl(3), and Cl(4)

3

anotin-substituted [16]crown-5 and [19]crown-6 derivatives

that are not able to ditopically complex NaCl and KCl,

respectively.^36,39

˚

0.0308(2) A from the trigonal plane in the direction of Cl(1).

The ¹³C NMR spectrum of an authentic sample contain-

ing 6 þ LiI_excessin CD₃CN showed, in comparison with the

¹³C NMR chemical shifts of pure 6 in CD₃CN, a consider-

able shift (Δδ 31.0) of the C14 signal to low frequency, while

the signals of the C12 and C2-C9 crown ether carbon atoms

moved by 2.0 and 1.7 ppm to high and low frequency,

respectively. In the ¹H NMR spectrum of a CD₃CN solution

containing 6 þ excess LiI, the signals of the H_C11/C13and

H_C12protons moved by 0.2 and 0.27 ppm to low frequency,

The Sn(1)-Cl(3) and Sn(1)-Cl(4) distances of 2.3508(7)

˚

and 2.3428(6) A are within the range of the Sn(1)-Cl(1) and

Sn(1)-Cl(2) distances measured for the compound Cl₃Sn-

CH₂-[16]-crown-5 (2.3625(5) and 2.3843(5) A,⁴⁸respectively),

˚

(60) Olsher, U.; Izatt, R.; Bradshaw, J. S.; Dalley, N. K. Chem. Rev.

1991, 91, 137.

(61) Habata, Y.; Okazaki, C.; Ogura, K.; Akabori, S.; Zhang, X. X.;

Bradshaw, J. S. Inorg. Chem. 2007, 46, 8264.

Article

Organometallics, Vol. 29, No. 21, 2010 5465

Figure 7. Molecular structure of [8 LiCl H₂O] showing 30% probability displacement ellipsoids and the crystallographic numbering

scheme.

3

˚

Table 5. Selected Bond Distances (A) and Bond Angles (deg) for

[8 LiCl H₂O]^a

Scheme 6

3

Sn(1)-C(21)

Sn(1)-Cl(1)

Sn(1)-Cl(2)

Sn(1)-Cl(3)

Sn(1)-Cl(4)

Li(1)-O(1)

2.129(2)

2.4731(7)

2.5128(7)

2.3508(7)

2.3428(6)

2.067(5)

2.005(4)

2.081(6)

1.979(4)

1.907(5)

3.161(2)

3.245(2)

C(21)-Sn(1)-Cl(1)

C(21)-Sn(1)-Cl(2)

C(21)-Sn(1)-Cl(3)

C(21)-Sn(1)-Cl(4)

Cl(1)-Sn(1)-Cl(2)

Cl(1)-Sn(1)-Cl(3)

Cl(1)-Sn(1)-Cl(4)

Cl(2)-Sn(1)-Cl(3)

Cl(2)-Sn(1)-Cl(4)

Cl(3)-Sn(1)-Cl(4)

O(1)-Li(1)-O(2)

94.54(7)

91.14(7)

117.13(7)

130.61(7)

174.22(2)

88.32(2)

88.97(2)

88.16(2)

88.12(3)

112.20(3)

83.25(17)

156.0(2)

90.6(2)

Li(1)-O(2)

reported for the diorganotrichlorostannate complexes

[PhCl₂SnCH₂-[19]-crown-6 Cl]^-[(Ph₃P)₂N]^þ(δ -257, in

Li(1)-O(3)

Li(1)-O(4)

Li(1)-O(1W)

O(1W)-Cl(1A)

O(1W)-Cl(2)

3

CDCl₃)⁴⁰and [(PhCl₂SnCH₂)₂SnCl₂Cl]^-[(Ph₃P)N]^þ(δ -188;

3

in CD₂Cl₂, inner Sn atom),⁶²respectively. These results are

consistent with the equilibrium shown in Scheme 6 being

quantitatively shifted toward the ditopic complex [14 LiCl],

O(1)-Li(1)-O(3)

O(1)-Li(1)-O(4)

O(1)-Li(1)-O(1W)

O(2)-Li(1)-O(3)

O(2)-Li(1)-O(4)

O(2)-Li(1)-O(1W)

O(3)-Li(1)-O(4)

102.8(2)

82.1(2)

121.7(2)

114.7(2)

81.1(2)

3

in which the chloride anion is very likely chelated by two tin

atoms.

Like in [8 LiCl], the complexation of the lithium cation in

3

[14 LiCl] is confirmed by the change observed in the ¹H and

O(3)-Li(1)-O(1W)

O(4)-Li(1)-O(1W)

Li(1)-O(1W)-Cl(1A)

Li(1)-O(1W)-Cl(2)

Cl(1A)-O(1W)-Cl(2)

Sn(1)-Cl(2)-O(1W)

Sn(1)-Cl(1)-O(1WB)

C(22)-C(21)-Sn(1)

100.6(2)

123.1(2)

102.2(2)

119.6(2)

105.35(6)

99.38(4)

114.23(4)

118.3(2)

3

¹³C NMR spectra with regard to the H and ¹³C NMR

1

chemical shifts of pure 14. The H NMR spectrum of the

sample 14 þ LiCl_excessshowed a closer distribution of the

resonances of the H_C2-C10and H_C13hydrogen atoms,

whereas they are more broadly distributed in the ¹H NMR

spectrum of free 14. Moreover, the signals of the H_C14and

H₁₂protons atoms are high-frequency shifted by 0.19 and

0.23 ppm, while that of the H_C15proton atom moved by 0.07

ppm to high field. The ¹³C NMR spectrum of the same

sample showed the signals of the C14, C15, and C_icarbon

atoms being considerably low -field shifted by 10.4, 32.3, and

12.2 ppm, respectively. Furthermore, the resonances of the

crown ether carbon atoms C2-C9 and C11/C13 moved by

0.5 and 4.6 ppm to high and low field, respectively.

^aA = 1þx, y, z; B = -1þx, y, z.

as the latter is analogous to the parent compound 8. On the

other hand and as a result of their involvement in hydrogen-

bonding interactions, the Sn(1)-Cl(1) and Sn(1)-Cl(2) dis-

˚

tances of 2.4731(7) and 2.5128(7) A are longer as com-

pared with the sum of the covalent radii⁴⁷of Sn (1.40 A)

˚

and Cl (0.99 A).

The ditopic complexation of lithium chloride was also

achieved with the bis(dichlorido-organostannyl)methane-

substituted crown ether 14, in which the presence of two

doubly functionalized tin atoms reflects an improved Lewis

acidity with regard to compound 3. The ¹¹⁹Sn NMR spec-

trum at room temperature of a solution of 14 in CD₃CN to

which had been added three molar equivalents of LiCl

showed two single resonances at δ -207 (ν_1/2= 118 Hz,

Sn1) and -279 (ν_1/2= 126 Hz, Sn2), which are 181 and 173

ppm low-frequency shifted in comparison with the ¹¹⁹Sn

NMR chemical shifts of free 14 in CD₃CN [δ -26 (Sn1)

and -106 (Sn2)], but close to the ¹¹⁹Sn NMR chemical shifts

Conclusion

Novel ditopic hosts based on organotin- and bis(organo-

stannyl)methane-substituted [13]-crown-4 ethers have been

synthesized and completely characterized. Systematic NMR

studies reveal that the receptors 3 and 4 bind LiCl and CsF,

respectively, in a cooperative fashion, as no affinity of 3 for

(Ph₃P)NCl and of 4 for n-Bu₄NF is observed. We also

€

(62) Altmann, R. Ph.D. Thesis, Technische Universitat Dortmund,

1999.

5466 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

demonstrated that increasing the Lewis acidity at the tin

atom is a good way to achieve efficient binding, as evidenced

by the ditopic complexation of LiI by compound 6, whereas 2

is not able to bind this salt. The same concept applies for

compounds 8 and 14, which quantitatively complex LiCl.

The isolation of the ditopic complex [8 LiCl H₂O] in the

Chart 2

3

solid state shows that the cooperative binding is supported

through a water molecule that provides, by a hydrogen

bridge, communication between the lithium cation and the

chloride anion. This resembles the situation observed for

the ditopic complex {Ph₂(I)SnCH₂Sn(Ph)(I)CH₂-[16]-

crown-5} NaF CH₃OH, in which a methanol molecule

Electrospray mass spectra were recorded on a Thermoquest-

Finnigan instrument using CH₃CN as the mobile phase. The

samples were introduced as a solution in CH₃CN via a syringe

pump operating at 0.5 μL/min. The capillary voltage was 4.5 kV,

while the cone skimmer voltage varied between 50 and 250 kV.

Identification of the expected ions was assisted by comparison

of experimental and calculated isotope distribution patterns.

The m/z values reported correspond to those of the most intense

peak in the corresponding isotope pattern.

Crystallography. Intensity data for the colorless (1, 2, 9), light

yellow (11, 8 LiCl H₂O), yellow (5, 6), and dark yellow (12)

crystals were collected on a Nonius KappaCCD (1, 2), Oxford

Diffraction Xcalibur S (5, 6, 9, 12, 8 LiCl H₂O), and Bruker

SMART CCD (11) diffractometers with graphite-monochro-

3

provides such communication between the sodium cation

and the fluoride anion and stabilizes the complex.³⁸

These results inspire us to apply such receptors in extrac-

tion and transport processes and, more challenging, to fine-

tune the affinity of these compounds by modification of the

substituents at the tin atom in order to allow the ditopic

complexation of salts even in pure water.

3

Experimental Section

˚

mated Mo KR (0.71073 A) radiation at 173(1) K. The data

collection covered almost the whole sphere of reciprocal space

General Methods. Solvents were dried and distilled from the

appropriate desiccants prior to use. All manipulations were

performed under an inert atmosphere of nitrogen or argon.

Literature procedures were used to prepare 1,4,7,10-tetra-

oxacyclotridecane⁴¹and triphenyltin hydride.⁶³The atom num-

bering of the crown ether fragment is shown in Chart 2.

with 4 (1), 5 (2, 5, 8 LiCl H₂O), 6 (9), 9 (12), 13 (6), and 4 (11)

3

sets at different κ- (1, 2,5, 6, 9, 12, 8 LiCl H₂O) and j-angles

(11) with 427 (1), 471 (2) 337 (5) 736 (6) 287 (9), 1131 (11), 473

3

(12), and 194 (8 LiCl H₂O) frames via ω-rotation (Δ/ω = 0.5°

3

(11) and 1° (1, 2, 5, 6, 9, 12, 8 LiCl H₂O) at two times 2 s (9),

3

NMR Spectroscopy. The ¹H, ¹³C, ¹⁹F, and ¹¹⁹Sn NMR spec-

tra were recorded on Bruker DRX 500, DRX 400, and DPX 300,

Varian Nova 600, and Varian Mercury 200 spectrometers with

broad band decoupling of ¹¹⁹Sn at 111.92 MHz, ¹⁹F at 282.4

MHz, ¹³C at 100.61 or 125.77 MHz, and ¹H at 400.13 or 500.13

MHz. Chemical shifts δ are given in ppm and referenced to

tetramethylstannane (¹¹⁹Sn), CFCl₃(¹⁹F), and tetramethylsi-

lane (¹H, ¹³C). The solid-state ¹¹⁹Sn NMR spectra of com-

pounds 2 and 4 were recorded on a Bruker AVANCE III 400

spectrometer equipped with a double-bearing CP/MAS probe at

room temperature. CP/MAS (cross-polarization/magic angle

spinning) experiments were used with a repetition delay of 10 s,

and the contact time was set at 2 ms. Two spinning rates (5000

and 7000 Hz) were used to identify the isotropic chemical shift.

The number of scans was set at 1000. The ¹¹⁹Sn chemical shifts

were calibrated using tetracyclohexyltin (δ = -97.35).

2.5 s (8 LiCl H₂O), 3 s (6, 12), 40 s (2), 65 s (5), 100 s (1), and 20 s

(11) per frame. The crystal-to-detector distance was 3.4 cm

(1, 2), 4 cm (11), and 4.5 cm (5, 6, 9, 12, 8 LiCl H₂O). Crystal

3

decay was monitored by repeating the initial frames at the end of

data collection. On analyzing the duplicate reflections, there was

no indication for any decay. The structure was solved by direct

methods with SHELXS97⁶⁴(1, 2, 5, 6, 9, 12, 8 LiCl H₂O)

3

and SIR-97⁶⁵(11) and successive difference Fourier syntheses.

Refinement applied full-matrix least-squares methods with

SHELXL97.⁶⁶

The H atoms were placed in geometrically calculated posi-

tions using a riding model with U_isoconstrained to 1.2 times U_eq

of the carrier atom. Only in 8 LiCl H₂O have the coordinates of

3

the water molecule (O(1W)) been refined.

In 5 three atoms of the crown ether ring are disordered over

two positions with occupancies of 0.5 (O(3), O(3⁰), C(28),

C(28⁰),C(29), C(29⁰)). Atomic scattering factors for neutral

atoms and real and imaginary dispersion terms were taken

from International Tables for X-ray Crystallography.⁶⁷The

figures were created by SHELXTL.⁶⁸Crystallographic data

are given in Table 6; selected bond distances and angles in

Tables 1-5.

The ¹H-¹¹⁹Sn correlation was measured with a 500 MHz

UnityINOVA NMR spectrometer from Varian, Inc., equipped

with a 5 mm gradient triple resonance probe H(C,X). The phase-

sensitive gradient HMQC sequence was used for the ¹H-¹¹⁹Sn

correlation without decoupling. It was optimized for a coupl-

ing constant of 78 Hz. The gradient strength was 10 G/cm

(corresponding to 3.727 G/cm for ¹¹⁹Sn); 10.9 and 46 μs were

CCDC-769242 (1), -769243 (2), -769244 (5), -769245 (6),

-769246 (8 LiCl H₂O), -769247 (9), -769248 (11), and -769249

1

calibrated for the H and ¹¹⁹Sn 90° pulse width, respectively.

3

(12) contain the supplementary crystallographic data for this

paper. These data can be obtained free of charge at www.ccdc.

cam.ac.uk/conts/retrieving.html [or from the Cambridge Crys-

tallographic Data Centre, 12 Union Road, Cambridge CB2

1EZ, UK; fax: (internat.) þ44-1223/336-033; e-mail: deposit@

ccdc.cam.ac.uk].

Two scans per increment and 256 increments were acquired for

a 5.5 kHz proton spectral width (4kb data) and a 21 kHz spectral

width of ¹¹⁹Sn. The Fourier transformation was performed with

4kb ꢀ 1kb data. The proton spectrum was carried out with 16

scans, 64 kb data, and a recycle delay of 6 s by using a 45° pulse.

Inverse gated decoupling was applied for measuring the ¹¹⁹Sn

spectrum; 128 kb data for a 100 kHz window were acquired with

a 20° pulse.

(64) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.

(65) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.;

Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.;

Spagna, R. J. Appl. Crystallogr. 1999, 32, 115–119.

(66) Sheldrick, G. M. SHELXL97; University of Gottingen, Germany,

1997.

Complexation Studies. The samples for NMR analyses were

prepared by dissolving ca. 50 mg of the corresponding organotin

halide and the corresponding amounts of the lithium and cesium

salt, respectively, in deuterated solvents. The metal salts used for

the complexation studies were dried in vacuo (10^-6mbar) at

100 °C for one day and stored under nitrogen.

€

(67) International Tables for Crystallography; Kluwer Academic Pub-

lishers: Dortrecht, 1992; Teil C.

(68) Sheldrick, G. M. SHELXTL, Release 5.1 Software Reference

Manual; Bruker AXS, Inc.: Madison, WI, 1997.

(63) Kuivila, H. G.; Beumel, O. F. J. Am. Chem. Soc. 1961, 83, 1246.

Article

Organometallics, Vol. 29, No. 21, 2010 5467

5468 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

Synthesis of (1,4,7,10-Tetraoxacyclotridec-12-ylmethyl)triphe-

nylstannane, Ph₃SnCH₂-[13]-crown-4 (1). 12-Methylene-1,4,7,10-

tetraoxacyclotridecane (4.93 g, 24.376 mmol) was mixed with

triphenyltinhydride, Ph₃SnH (8.56 g, 24.376mmol). After a small

quantity of AIBN (150 mg) had been added, the mixture was

stirred at 60-80 °C for 15 h, followed by cooling to room

temperature. Addition of CH₂Cl₂(100 mL) followed by filtration

through Celite and removal of the solvent in vacuo afforded a

viscous oil. Purification of the oil by column chromatography

with silica gel/CH₂Cl₂and elution with ethanol gave 9.18 g (68%)

of 1 as a colorless viscous oil, which solidified after it had been

kept a few days at room temperature, mp 65-68 °C. Single

crystals of 1 suitable for X-ray diffraction analysis were obtained

by slow evaporation of a solution of the compound in CH₂Cl₂/

n-hexane.

C11/C13), 128.6 (³J(¹³C-^117/119Sn) = 62 Hz, C_m), 129.4

(⁴J(¹³C-^117/119Sn) = 14 Hz, C_p), 135.7 (²J(¹³C-^117/119Sn) =

1

49 Hz, C_o), 140.9 (¹J(¹³C-¹¹⁷Sn) = 632 Hz, J(¹³C-¹¹⁹Sn) =

663.2 Hz), C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293 K)

δ: -87. Anal. Calcd for C₂₂H₂₉ClO₄Sn (511.63): C 51.6; H 5.7.

Found: C 51.8; H 5.6.

SynthesisofFluorido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-

diiphenylstannane, Ph₂FSnCH₂-[13]-crown-4 (4). A solution of 2

(1.0 g, 1.658 mmol) in CH₂Cl₂(25 mL) was mixed with a solution

of KF (0.96 g, 16.580 mmol) in water (30 mL). The biphasic

mixture was stirred at room temperature for two days. The

organic phase was then separated, dried over MgSO₄, and fil-

tered. Removing the solvent in vacuo afforded a colorless viscous

oil. The oil was dissolved in diethyl ether. Cooling the solution at

-5 °C gave 0.42 g (51%) of pure 4 as a colorless solid, mp 115 °C.

¹HNMR(CDCl₃, 400.13 MHz, 293 K) δ:1.51(d, ³J(¹H-¹H) =

8.0 Hz, ²J(¹H-¹¹⁷Sn) = 72.0 Hz, ²J(¹H-¹¹⁹Sn) = 88.0 Hz, 2H,

Sn-CH₂), 2.66 (m, 1H, CH), 3.33-3.75 (complex pattern, 16H,

CH₂-O-CH₂), 7.37-7.79 (m, 10H, Ph). ¹³C{¹H} NMR (CDCl₃,

100.63 MHz, 293 K) δ: 13.2 (d, ²J(¹³C-¹⁹F) = 12 Hz, ¹J-

¹H NMR (CDCl₃, 400.13 MHz, 293 K) δ: 1.54 (d, ³J(¹H-¹H) =

8.0 Hz, ²J(¹H-¹¹⁷Sn) = 48.0 Hz, ²J(¹H-¹¹⁹Sn) = 64.0 Hz, 2H,

Sn-CH₂), 2.37 (m, 1H, CH), 3.41-3.64 (complex pattern, 16H,

CH₂-O-CH₂), 7.35-7.63 (m, 15H, Ph). ¹³C{¹H} NMR (CDCl₃,

100.63 MHz, 293 K) δ: 10.8 (¹J(¹³C-¹¹⁷Sn) = 388 Hz, ¹J-

(¹³C-¹¹⁹Sn) = 407.6 Hz, C14), 37.0 (²J(¹³C-^117/119Sn) = 20

Hz, C12), 69.0-70.0 (C2-C9), 71.4 (³J(¹³C-^117/119Sn) = 45 Hz,

C11/C13), 128.3 (³J(¹³C-^117/119Sn) = 48 Hz, C_m), 128.6 (⁴J-

(¹³C-^117/119Sn) = 12 Hz, C_p), 136.9 (²J(¹³C-^117/119Sn) = 35

Hz, C_o), 140.0 (¹J(¹³C-¹¹⁷Sn) = 471 Hz, ¹J(¹³C-¹¹⁹Sn) = 495

Hz), C_i). ¹¹⁹Sn{¹H} NMR (CH₂Cl₂/D₂O capillary, 111.93 MHz,

293 K) δ: -107. Anal. Calcd for C₂₈H₃₄O₄Sn (553.28): C 60.8; H

6.2. Found: C 61.1; H 6.4.

1

(¹³C-¹¹⁷Sn) = 523 Hz, J(¹³C-¹¹⁹Sn) = 549 Hz, C14), 35.9

(²J(¹³C-^117/119Sn) = 27 Hz, C12), 69.2-70.1 (C2-C9), 70.9

(³J(¹³C-^117/119Sn) = 36 Hz, C11/C13), 128.5 (³J(¹³C-^117/119Sn) =

64 Hz, C_m), 129.5 (⁴J(¹³C-^117/119Sn) = 13 Hz, C_p), 135.8

2

(²J(¹³C-^117/119Sn) = 47 Hz, C_o), 140.9 (d, J(¹³C-¹⁹F) = 13

1

Hz, J(¹³C-¹¹⁷Sn) = 667 Hz, J(¹³C-¹¹⁹Sn) = 669 Hz), C_i).

¹⁹F{¹H} NMR (CDCl₃, 282.4 MHz, 293 K) δ: -192.1

(¹J(¹⁹F-¹¹⁷Sn) = 2110 Hz, J(¹⁹F-¹¹⁹Sn) = 2208 Hz). ¹¹⁹Sn-

1

{¹H} NMR (CDCl₃, 111.93 MHz, 293 K) δ: -111 (d, ¹J-

Synthesis of Iodido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-

diphenylstannane, Ph₂ISnCH₂-[13]-crown-4 (2). Over a period

of three hours, iodine (4.02 g, 15.851 mmol) was added in small

portions at 0 °C to a stirred solution of 1 (8.77 g, 15.851 mmol) in

CH₂Cl₂(150 mL). Stirring was continued and the reaction

mixture was warmed to room temperature overnight. Dichloro-

methane and iodobenzene were removed in vacuo (10^-3mm Hg)

to give a viscous and slightly yellow oil. The latter was dissolved

in ethanol. Cooling the solution at -5 °C gave 7.18 g (75%) of

pure 2 as a white solid of mp 120 °C. Single crystals of 2 suitable

for X-ray diffraction analysis were obtained by slow evapora-

tion of a solution of the compound in CH₂Cl₂/n-hexane.

¹H NMR (CDCl₃, 400.13 MHz, 293 K) δ: 1.84 (d, ³J(¹H-¹H) =

4.0 Hz, ²J(¹H-¹¹⁷Sn) = 68.0 Hz, ²J(¹H-¹¹⁹Sn) = 76.0 Hz, 2H,

Sn-CH₂), 2.62 (m, 1H, CH), 3.27-3.73 (complex pattern, 16H,

CH₂-O-CH₂), 7.35-7.82 (m, 10H, Ph). ¹³C{¹H} NMR (CDCl₃,

100.63 MHz, 293 K) δ: 20.4 (¹J(¹³C-¹¹⁷Sn) = 478 Hz, ¹J-

(¹³C-¹¹⁹Sn) = 499 Hz, C14), 37.2 (²J(¹³C-^117/119Sn) = 30 Hz,

C12), 69.2-70.0 (C2-C9), 71.2 (³J(¹³C-^117/119Sn) = 38.0 Hz,

C11/C13), 128.5 (³J(¹³C-^117/119Sn) = 63 Hz, C_m), 129.3

(⁴J(¹³C-^117/119Sn)=14 Hz, C_p), 135.9 (²J(¹³C-^117/119Sn) = 47

Hz, C_o), 140.3 (¹J(¹³C-¹¹⁷Sn) = 592 Hz, ¹J(¹³C-¹¹⁹Sn) = 620

Hz), C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293 K) δ:

-126. ¹¹⁹Sn MAS NMR (149.20 MHz) δ: -121. Anal. Calcd for

C₂₂H₂₉IO₄Sn (603.08): C 43.8; H 4.8. Found: C 44.3; H 4.8.

Synthesis of Chlorido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-

diphenylstannane, Ph₂ClSnCH₂-[13]-crown-4 (3). To a solution

of 2 (1.0 g, 1.658 mmol) in CH₃CN (20 mL) was added excess

silver chloride, AgCl (0.71 g, 4.974 mmol). The resulting mixture

was stirred at room temperature and in the dark for 14 days.

After the AgI formed and the nonreacted AgCl had been

removed by filtration the solvent was evaporated in vacuo.

The colorless oil thus obtained was dissolved in ethanol and

cooled at -5 °C to give 0.60 g (71%) of pure 3 as a white solid,

mp 118 °C.

(

¹¹⁹Sn-¹⁹F) = 2208 Hz). ¹¹⁹Sn MAS NMR (149.20 MHz) δ:

-145 (t, J(¹¹⁹Sn-¹⁹F) = 2685 Hz). Anal. Calcd for C₂₂H₂₉-

FO₄Sn (495.18): C 53.4; H 5.9. Found: C 52.9; H 5.4.

1

Synthesis of Diiodido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-

phenylstannane, PhI₂SnCH₂-[13]-crown-4 (5). Over a period of

three hours, iodine (0.42 g, 1.658 mmol) was added in small

portions at 0 °C to a stirred solution of 2 (1.0 g, 1.658 mmol) in

CH₂Cl₂(30 mL). Stirring was continued and the reaction

mixture was warmed to room temperature overnight. Dichlor-

omethane and iodobenzene were removed in vacuo (10^-3Torr)

to afford a yellow solid. Recrystallization from ethanol at -5 °C

gave 0.89 g (82%) of pure 5 as yellow crystals, mp 102 °C.

¹HNMR(CDCl₃, 400.13 MHz, 293 K) δ:2.19(d, ³J(¹H-¹H) =

4.0 Hz, ²J(¹H-¹¹⁷Sn) = 68.0 Hz, ²J(¹H-¹¹⁹Sn) = 76.0 Hz, 2H,

Sn-CH₂), 2.58 (m, 1H, CH), 3.44-3.78 (complex pattern, 16H,

CH₂-O-CH₂), 7.33-7.81 (m, 5H, Ph). ¹³C{¹H} NMR (CDCl₃,

100.63 MHz, 293 K) δ: 28.3 (¹J(¹³C-¹¹⁷Sn) = 512 Hz, ¹J-

(¹³C-¹¹⁹Sn) = 535 Hz, C14), 37.4 (²J(¹³C-^117/119Sn) = 41 Hz,

C12), 69.2-69.8 (C2-C9), 70.8 (³J(¹³C-^117/119Sn) = 51 Hz,

C11/C13), 128.7 (³J(¹³C-^117/119Sn) = 84 Hz, C_m), 130.3

(⁴J(¹³C-^117/119Sn) = 12 Hz, C_p), 134.1 (²J(¹³C-^117/119Sn) =

1

64 Hz, C_o), 139.8 (¹J(¹³C-¹¹⁷Sn) = 686 Hz, J(¹³C-¹¹⁹Sn)=

717 Hz), C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293 K) δ:

-275. Anal. Calcd for C₁₆H₂₄I₂O₄Sn (652.88): C 29.4; H 3.7.

Found: C 29.6; H 3.7.

Synthesis of Triiodido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-

stannane, I₃SnCH₂-[13]-crown-4 (6). Over a period of three

hours, iodine (0.84 g, 3.316 mmol) was added in small portions

at 0 °C to a stirred solution of 2 (1.0 g, 1.658 mmol) in CH₂Cl₂

(30 mL). Stirring was continued, and the reaction mixture was

warmed to room temperature overnight. Dichloromethane and

iodobenzene were removed in vacuo (10^-3Torr) to afford a

yellow solid. Recrystallization from ethanol at -5 °C gave 0.90 g

(77%) of pure 6 as yellow crystals, mp 100 °C.

¹HNMR(CDCl₃, 400.13 MHz, 293 K) δ:1.66(d, ³J(¹H-¹H) =

4.0 Hz, ²J(¹H-¹¹⁷Sn) = 76.0 Hz, ²J(¹H-¹¹⁹Sn) = 84.0 Hz, 2H,

Sn-CH₂), 2.66 (m, 1H, CH), 3.30-3.74 (complex pattern, 16H,

CH₂-O-CH₂), 7.37-7.82 (m, 10H, Ph). ¹³C{¹H} NMR (CDCl₃,

100.63 MHz, 293 K) δ: 17.1 (¹J(¹³C-¹¹⁷Sn) = 511 Hz, ¹J-

(¹³C-¹¹⁹Sn) = 535 Hz, C14), 36.3 (²J(¹³C-^117/119Sn) = 28 Hz,

C12), 69.2-70.1 (C2-C9), 71.0 (³J(¹³C-^117/119Sn) = 37 Hz,

¹HNMR(CDCl₃, 400.13 MHz, 293 K) δ:2.48(d, ³J(¹H-¹H) =

4.0 Hz, ²J(¹H-¹¹⁷Sn) = 60.0 Hz, ²J(¹H-¹¹⁹Sn) = 68.0 Hz, 2H,

Sn-CH₂), 2.40 (m, 1H, CH), 3.61-3.80 (complex pattern, 16H,

CH₂-O-CH₂). ¹³C{¹H} NMR (CDCl₃, 100.63 MHz, 293 K) δ:

33.0 (¹J(¹³C-¹¹⁷Sn) = 562 Hz, ¹J(¹³C-¹¹⁹Sn) = 588 Hz, C14),

38.4 (²J(¹³C-^117/119Sn) = 60 Hz, C12), 68.7-70.2 (C2-

C9), 69.6 (³J(¹³C-^117/119Sn) = 70 Hz, C11/C13). ¹¹⁹Sn{¹H}

Article

Organometallics, Vol. 29, No. 21, 2010 5469

NMR (CDCl₃, 111.93 MHz, 293 K) δ: -820. Anal. Calcd for

C₁₀H₁₉I₃O₄Sn (702.68): C 17.1; H 2.7. Found: C 17.3; H 2.8.

Synthesis of Trichlorido(1,4,7,10-tetraoxacyclotridec-12-yl-

methyl)stannane, Cl₃SnCH₂-[13]-crown-4 (8), and Dichlorido-

(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)phenylstannane, PhCl₂-

SnCH₂-[13]-crown-4 (9). Hydrogen chloride gas, produced by

adding dropwise concentrated sulfuric acid to sodium chloride,

was bubbled through a solution of 1 (0.92 g, 1.663 mmol) in

CH₂Cl₂(70 mL) for 3 h at 0 °C and for 6 h at RT. The solvent,

the benzene, and the remaining HCl were removed in vacuo to

afford a white solid consisting of the dichloridoorganotin

hydroxide 7,⁴²the monoorganotin trichloride 8, and the dio-

rganotin dichloride 9. Compound 8 was separated from the

mixture as colorless crystals by recrystallization from ethanol.

Yield: 48%, mp 160 °C.

¹J(¹³C-¹¹⁷Sn) = 455 Hz, ¹J(¹³C-¹¹⁹Sn) = 475 Hz), SnPh₂,

C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293 K) δ: -53

(²J(¹¹⁹Sn-^117/119Sn) = 238 Hz, SnPh₂), -77 (²J(¹¹⁹Sn-

^117/119Sn) = 241 Hz). Anal. Calcd for C₄₁H₄₆O₄Sn₂(840.23):

C 58.6; H 5.5. Found: C 58.9; H 5.7.

Synthesis of 12-({Iodidophenyl[(iodidodiphenylstannyl)methyl]-

stannyl}methyl)-1,4,7,10-tetraoxacyclononadecane, Ph₂ISnCH₂-

Sn(I)PhCH₂-[13]-crown-4 (11). Iodine (1.87 g, 7.378 mmol)

was added in small portions and under ice-cooling to a stirred

solution of 10 (3.1 g, 3.689 mmol) in CH₂Cl₂(80 mL). The

reaction mixture was stirred while warming to room tempera-

ture overnight. The solvent and the iodobenzene were removed

in vacuo (10^-3mm Hg) to afford a yellow oil. The oil was

dissolved in diethyl ether (20 mL); cooling the solution at -5 °C

gave 2.77 g (80%) of pure 11 as slightly yellow crystals, mp

132 °C.

¹HNMR(CDCl₃, 400.13 MHz, 293 K) δ:1.80(d, ³J(¹H-¹H) =

¹H NMR (CDCl₃, 599.83 MHz, 293 K) δ: 1.24/1.60 (br,

ABX-type resonance, Sn-CH₂), 1.84/2.06 (br, AB-type reso-

nance, ³J(¹H-¹H) = 12.0 Hz, Sn-CH₂-Sn), 2.37 (m, 1H, CH),

3.18-3.59 (complex pattern, 16H, CH₂-O-CH₂), 7.33-7.91 (m,

15H, Ph). ¹³C{¹H} NMR (CDCl₃, 100.63 MHz, 293 K) δ: 4.9

2

4.0 Hz, J(¹H-¹¹⁷Sn) = 92.0 Hz, J(¹H-¹¹⁹Sn) = 108.0 Hz,

2H, Sn-CH₂), 2.59 (m, 1H, CH), 3.61-4.21 (complex pattern,

16H, CH₂-O-CH₂). ¹³C{¹H} NMR (CDCl₃, 100.63 MHz,

293 K) δ: 30.4 (C14), 34.3 (C12), 68.7-69.3 (C2-C9), 72.8

(³J(¹³C-^117/119Sn) = 66 Hz, C11/C13). ¹¹⁹Sn{¹H} NMR

(CDCl₃, 111.93 MHz, 293 K) δ: -237. Anal. Calcd for

C₁₀H₂₀Cl₃O₄Sn (428.33): C 28.0; H 4.5. Found: C 27.9, H 4.4.

Compound 9 was removed from the mixture as colorless

crystals by recrystallization from diethyl ether. Yield: 5%, mp

150 °C.

1

(¹J(¹³C-¹¹⁷Sn) = 291/303 Hz, J(¹³C-¹¹⁹Sn) = 326/341 Hz,

C15), 20.0 (¹J(¹³C-¹¹⁷Sn) = 489 Hz, ¹J(¹³C-¹¹⁹Sn) = 517 Hz,

C14), 37.0 (²J(¹³C-^117/119Sn) = 31 Hz, C12), 69.0-69.9

(C2-C9), 71.2 (C11/C13), 128.5 (³J(¹³C-^117/119Sn) = 62 Hz,

SnIPh, C_m), 128.7 (³J(¹³C-^117/119Sn) = 62 Hz, SnIPh₂, C_m),

129.3 (⁴J(¹³C-^117/119Sn) = 13 Hz, SnIPh, Cp), 129.9 (⁴J-

(¹³C-^117/119Sn)=14 Hz, SnIPh₂, C_p), 134.9 (²J(¹³C-^117/119Sn) =

49 Hz, SnIPh, C_o), 136.6 (br, ²J(¹³C-^117/119Sn) = 50 Hz,

SnIPh₂, C_o), 137.9 (br, SnIPh, C_i), 141.8 (³J(¹³C-^117/119Sn) =

29 Hz, SnIPh₂, C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293

K) δ: -50 (²J(¹¹⁹Sn-^117/119Sn) = 251 Hz, SnIPh), -87(²J-

¹H NMR (CDCl₃, 500.13 MHz, 293 K) δ: 1.86 (d, ³J(¹H-¹H) =

4.0 Hz, ²J(¹H-¹¹⁷Sn) = 80.0 Hz, ²J(¹H-¹¹⁹Sn) = 90.0 Hz, 2H,

Sn-CH₂), 2.70 (m, 1H, CH), 3.52-3.90 (complex pattern, 16H,

CH₂-O-CH₂), 7.46-7.95 (m, 5H, Ph). ¹³C{¹H} NMR (CDCl₃,

125.77 MHz, 293 K) δ: 24.5 (¹J(¹³C-¹¹⁷Sn) = 624 Hz, ¹J-

(¹³C-¹¹⁹Sn) = 654 Hz, C14), 35.6 (²J(¹³C-^117/119Sn) = 40 Hz,

C12), 69.24-69.9 (C2-C9), 71.0 (³J(¹³C-^117/119Sn) = 47 Hz,

C11/C13), 129.0 (³J(¹³C-^117/119Sn) = 89 Hz, C_m), 130.7

(⁴J(¹³C-^117/119Sn)=18 Hz, C_p), 134.9 (²J(¹³C-^117/119Sn) = 65

Hz, C_o), 141.5 (C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293

K) δ: -93. Anal. Calcd for C₁₆H₂₄Cl₂O₄Sn (469.97): C 40.9; H

5.1. Found: C 40.5; H 4.8.

(

¹¹⁹Sn-^117/119Sn) = 251 Hz, SnIPh₂). Anal. Calcd for C₂₉H₃₆-

I₂O₄Sn₂(939.83): C 37.1; H 3.9. Found: C 36.9; H 3.9.

Synthesis of 12-({Diiodido[(diiodidophenylstannyl)methyl]-

stannyl}methyl)-1,4,7,10-tetraoxacyclononadecane, PhI₂Sn-

CH₂SnI₂CH₂-[13]-crown-4 (12). Iodine (0.27 g, 1.064 mmol)

was added in small portions and under ice-cooling to a stirred

solution of 11 (0.5 g, 0.532 mmol) in CH₂Cl₂(20 mL). The

reaction mixture was stirred while warming to room tempera-

ture for three days. The solvent and the iodobenzene were

removed in vacuo (10^-3mm Hg) to afford a dark yellow oil.

The oil was dissolved in ethanol (10 mL); cooling the solution at

-5 °C gave 0.41 g (75%) of pure 12 as dark yellow crystals, mp

145 °C.

Synthesis of 12-({Diphenyl[(triphenylstannyl)methyl]stannyl}-

methyl)-1,4,7,10-tetraoxacyclononadecane, Ph₃SnCH₂Sn(Ph)₂-

CH₂-[13]-crown-4 (10). A solution of (bromomagnesium-

methyl)triphenylstannane, prepared from (bromomethyl)tri-

phenylstannane (2.21 g, 4.974 mmol) and magnesium (0.13 g,

5.223 mmol) in THF (50 mL), was added dropwise to a stirred

solution of 2 (3.0 g, 4.974 mmol) in THF (50 mL) for a period of

2 h. After the addition had been completed, the reaction mixture

was heated at reflux overnight and then cooled to room tem-

perature. Cold water (60 mL) was added and the mixture was

extracted two times with 50 mL of diethyl ether. The combined

organic phases were dried with MgSO₄and filtered, and the

solvents evaporated in vacuo to give the crude product. The

latter was purified by column chromatography (Al₂O₃, CH₂Cl₂,

ethyl acetate) to yield 3.34 g (80%) of pure 10 as a colorless

viscous oil.

¹H NMR (CDCl₃, 400.13 MHz, 293 K) δ: 2.18 (d, ³J(¹H-¹H) =

4.0 Hz, ²J(¹H-¹¹⁷Sn) = 80.0 Hz, ¹J(¹H-¹¹⁹Sn) = 88.0 Hz, 2H,

1

Sn-CH₂), 2.43 (m, 1H, CH), 3.09 (s, J(¹H-^117/119Sn) = 68.0

Hz, Sn-CH₂-Sn), 3.53-3.86 (complex pattern, 16H, CH₂-O-

CH₂), 7.37-7.87 (m, 5H, Ph). ¹³C{¹H} NMR (CDCl₃, 100.63

MHz, 293 K) δ: 20.5 (C15), 30.5 (C14), 37.4 (C12), 68.8-69.8

(C2-C9), 70.3 (³J(¹³C-^117/119Sn) = 48 Hz, C11/C13), 128.8

(SnI₂Ph, C_m), 131.0 (SnI₂Ph, Cp), 135.0 (²J(¹³C-^117/119Sn) = 65

Hz, SnI₂Ph, C_o), 136.4 (SnI₂Ph, C_i). ¹¹⁹Sn{¹H} NMR (CDCl₃,

111.93 MHz, 293 K) δ: -220 (²J(¹¹⁹Sn-^117/119Sn) = 214 Hz,

SnI₂Ph), -272 (²J(¹¹⁹Sn-^117/119Sn) = 218 Hz, SnI₂). Anal.

Calcd for C₁₇H₂₆I₄O₄Sn₂(1039.42): C 19.6; H 2.5. Found: C

19.4; H 2.8.

2

¹H NMR (CDCl₃, 400.13 MHz, 293 K) δ: 0.77 (s, J(¹H-

^117/119Sn) = 64 Hz, 2H, Sn-CH₂-Sn), 1.04 (d, ³J(¹H-¹H) = 8.0

Hz, ²J(¹H-¹¹⁷Sn) = 48.0 Hz, ²J(¹H-¹¹⁹Sn) = 64.0 Hz, 2H, Sn-

CH₂), 1.63 (m, 1H, CH), 3.29-3.57 (complex pattern, 16H,

CH₂-O-CH₂), 7.19-7.43 (m, 25H, Ph). ¹³C{¹H} NMR (CDCl₃,

100.63 MHz, 293 K) δ: -16.0 (¹J(¹³C-¹¹⁷Sn) = 254/268 Hz,

¹J(¹³C-¹¹⁹Sn) = 285/298 Hz, C15), 11.6 (¹J(¹³C-¹¹⁷Sn) = 378

Hz, ¹J(¹³C-¹¹⁹Sn) = 396 Hz, C14), 36.9 (²J(¹³C-^117/119Sn) =

20 Hz, C12), 69.0-70.0 (C2-C9), 71.5 (³J(¹³C-^117/119Sn) = 45

Hz, C11/C13), 128.1 (³J(¹³C-^117/119Sn) = 46 Hz, SnPh₂, C_m),

Synthesis of 12-({Fluoridophenyl[(fluorodiphenylstannyl)-

methyl]stannyl}methyl)-1,4,7,10-tetraoxacyclononadecane, Ph₂FSn-

CH₂Sn(F)PhCH₂-[13]-crown-4 (13). A solution of 11 (0.5 g,

0.532 mmol) in CH₂Cl₂(20 mL) was mixed with a solution of

KF (0.93 g, 16.008 mmol) in water (25 mL). The biphasic

mixture was stirred at room temperature for 10 days. The

organic phase was then separated, dried over MgSO₄, and

filtered. Removing the solvent in vacuo afforded 0.3 g (78%)

of pure 13 as a white solid, mp 110 °C. ¹H NMR (CDCl₃, 599.83

MHz, 293 K) δ: 1.14 (br, Sn-CH₂), 1.28 (br, Sn-CH₂-Sn), 2.52

(br, 1H, CH), 3.31-3.56 (m, br, complex pattern, 16H, CH₂-O-

CH₂), 7.33-7.83 (m, br, 15H, Ph). ¹³C{¹H} NMR (CDCl₃,

3

128.3 (⁴J(¹³C-^117/119Sn)=16 Hz, SnPh₂, C_p), 128.3, J(¹³C-

^117/119Sn) = 50 Hz, SnPh₃, C_m), 128.7 (⁴J(¹³C-^117/119Sn) = 11

Hz, SnPh₃, C_p), 136.5 (²J(¹³C-^117/119Sn) = 35 Hz, SnPh₂, C_o),

136.8 (²J(¹³C-^117/119Sn)=38 Hz, SnPh₃, C_o), 139.6 (³J(¹³C-

1

^117/119Sn)=10 Hz, J(¹³C-¹¹⁷Sn)=485 Hz, J(¹³C-¹¹⁹Sn) =

507 Hz), SnPh₃, C_i), 141.3 (³J(¹³C-^117/119Sn) = 12 Hz,

5470 Organometallics, Vol. 29, No. 21, 2010

Tagne Kuate et al.

100.63 MHz, 293 K) δ: 14.9 (br, C15), 29.6 (br, C12), 35.8 (br,

C14), 69.0-69.8 (br, C2-C9), 71.5 (br, C11/C13), 128.2-129.5

(br, SnFPh and SnFPh₂, C_mþ C_p), 135.3 (br, SnFPh, C_o), 136.1

(br, SnFPh₂, C_o), 137.1 (br, SnFPh, C_i), 142.9 (br, SnFPh₂, C_i).

¹⁹F{¹H} NMR (CDCl₃, 282.4 MHz, 293 K) δ: -139 (ν_1/2= 358

Hz), -175 (s,¹J(¹⁹F-^117/119Sn) = 2107 Hz), -189 (ν_1/2= 110

Hz), -195 (ν_1/2= 960 Hz). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93

MHz, 293 K) δ: -27 (br, ν_1/2= 1217 Hz). ESI-MS (MeCN, m/

z), positive mode: 703.1 (100%), {Ph₂FSnCH₂SnPh-[13]-crown-

4}^þ; negative mode: 743.0 (60%), {Ph₂FSnCH₂Sn(F)Ph-[13]-

crown-4 F}^-. Anal. Calcd for C₂₉H₃₆F₂O₄Sn₂2H₂O (760.05):

pattern, 16H, CH₂-O-CH₂). ¹³C{¹H} NMR (CD₃CN, 100.63

MHz, 293 K) δ: 35.4 (¹J(¹³C-^117/119Sn) = 56 Hz, C12), 42.9

(C14), 68.2-68.8 (C2-C9), 74.4 (³J(¹³C-^117/119Sn) = 149 Hz,

C11/C13). ¹¹⁹Sn{¹H} NMR (CDCl₃, 111.93 MHz, 293 K) δ:

-360. Anal. Calcd for C₁₀H₂₁Cl₄LiO₅Sn (488.72): C 24.6; H 4.3.

Found: C 24.2; H 4.3.

Complexation Studies. In Situ Reaction of 4 with CsF in

CD₃CN/CDCl₃at Different Molar Ratios. (a) CsF (3.8 mg,

0.025 mmol) was added to a solution of 4 (25.0 mg, 0.050 mmol)

in CD₃CN/CDCl₃(3:1) (600 μL), and the mixture was studied

by NMR spectroscopy.

3

¹⁹F{¹H} NMR (282.4 MHz) 293 K: δ: -149.1 (ν_1/2= 1011

Hz, integral 1), -184.8 (ν_1/2776 Hz, integral 2); 248 K: δ -136.8

[¹J(¹⁹F-^117/119Sn) = 1339 Hz, ²J(¹⁹F-¹⁹F) = 72 Hz, signal d],

-152.6 [¹J(¹⁹F-¹¹⁷Sn) = 1816 Hz, ¹J(¹⁹F-¹¹⁹Sn) = 1900 Hz,

signal a], -164.3 [¹J(¹⁹F-^117/119Sn) = 1796 Hz, ²J(¹⁹F-¹⁹F) =

75 Hz, signal c], -183.4 [¹J(¹⁹F-¹¹⁷Sn) = 2098 Hz, ¹J-

(¹⁹F-¹¹⁹Sn) = 2183 Hz, signal b].

C 45.8; H 5.3. Found: C 46.2; H 4.8.

Synthesis of 12-({Dichlorido[(dichloridophenylstannyl)methyl]-

stannyl}methyl)-1,4,7,10-tetraoxacyclononadecane, PhCl₂SnCH₂-

SnCl₂CH₂-[13]-crown-4 (14). To a solution of 12 (0.5 g, 0.481

mmol) in CH₃CN (20 mL) was added an excess of silver

chloride, AgCl (0.83 g, 5.791 mmol). The resulting mixture

was stirred at room temperature and in the dark for 14 days.

After the AgI formed and the nonreacted AgCl had been

removed by filtration, the solvent was evaporated in vacuo.

The slightly yellow oil thus obtained was dissolved in ethanol

and cooled at -5 °C to give 0.11 g (34%) of pure 14 as white

solid, mp 180 °C.

¹¹⁹Sn{¹H} NMR (111.92 MHz, 293 K): No resonance

observed.

(b) CsF (15.3 mg, 0.101 mmol) was added to a solution of 4

(50.0 mg, 0.101 mmol) in CD₃CN/CDCl₃(2:1) (600 μL), and the

mixture was studied by NMR spectroscopy.

¹H NMR (CD₃CN, 400.13 MHz, 293 K) δ: 1.69 (d, ³J-

(¹H-¹H) = 4.0 Hz, ²J(¹H-^117/119Sn) = 100.0 Hz, 2H, Sn-

CH₂), 2.58 (m, 1H, CH), 2.88 (s, ¹J(¹H-¹¹⁷Sn) = 84.0 Hz,

¹J(¹H-¹¹⁹Sn) = 92.0/100.0 Hz, 2H, Sn-CH₂-Sn),, 3.36-3.99

(complex pattern, 16H, CH₂-O-CH₂), 7.49-7.97 (m, 5H, Ph).

¹³C{¹H} NMR (CD₃CN, 100.63 MHz, 293 K) δ: 29.8

(¹J(¹³C-¹¹⁷Sn)=562 Hz, ¹J(¹³C-¹¹⁹Sn) = 582 Hz, C14), 31.3

(¹J(¹³C-¹¹⁷Sn)=499 Hz, ¹J(¹³C-¹¹⁹Sn) = 521 Hz, C14), 34.3

(²J(¹³C-^117/119Sn)=64 Hz, C12), 65.9-69.6 (C2-C9), 72.3 (³J-

(¹³C-^117/119Sn) = 34 Hz, C11/C13), 128.9 (³J(¹³C-^117/119Sn) =

92 Hz, SnCl₂Ph, C_m), 130.7 (⁴J(¹³C-^117/119Sn)=18 Hz, SnCl₂-

Ph, C_p), 135.1 (²J(¹³C-^117/119Sn) = 66 Hz, SnCl₂Ph, C_o), 142.9

(³J(¹³C-^117/119Sn) = 10 Hz, SnCl₂Ph, C_i). ¹¹⁹Sn{¹H} NMR

(CD₃CN, 111.93 MHz, 293 K) δ: -11 (ν_1/2= 237 Hz, SnCl₂),

-94 (ν_1/2= 122 Hz, SnCl₂Ph). Anal. Calcd for C₁₇H₂₆Cl₄O₄Sn₂

(673.60): C 30.3, H 3.9. Found: C 29.9; H 4.0.

¹H NMR (400.13 MHz, 293 K) δ: 1.13 (br, ²J(¹H-^117/119Sn) =

80.0 Hz, 2H, Sn-CH₂), 2.44 (m, 1H, CH), 3.26-3.56 (complex

pattern, 16H, CH₂-O-CH₂), 7.25-7.95 (m, 10H, Ph). ¹³C{¹H}

NMR (100.63 MHz, 293 K) δ: 19.1 (C14), 35.9 (²J(¹³C-

^117/119Sn)=22 Hz, C12), 68.1-68.3 (C2-C9), 74.9 (C11/C13),

127.5 (³J(¹³C-^117/119Sn) = 62 Hz, C_m), 127.8 (C_p), 136.8

(²J(¹³C-^117/119Sn) = 46 Hz, C_o).

¹⁹F{¹H} NMR (282.4 MHz) 293 K: -149.1 (ν_1/2= 550 Hz);

248 K: δ -151.9 (¹J(¹⁹F-¹¹⁷Sn) = 1818 Hz, ¹J(¹⁹F-¹¹⁹Sn) =

1897 Hz). ¹¹⁹Sn{¹H} NMR (111.93 MHz, 293 K): δ -277 (t,

1

¹J(¹¹⁹Sn-¹⁹F)=1885 Hz); 248 K: δ -274 [t, J(¹¹⁹Sn-¹⁹F) =

1902 Hz.

In Situ Reaction of 2 with Three Molar Equivalents of LiI in

CD₃CN. LiI (33.3 mg, 0.249 mmol) was added to a solution of 2

(50.0 mg, 0.083 mmol) in CD₃CN (600 μL), and the mixture was

studied by NMR spectroscopy.

¹¹⁹Sn{¹H} NMR (111.92 MHz, 293 K) δ: -150 (ν_1/2= 125 Hz).

In Situ Reaction of 5 with Three Molar Equivalents of LiI in

CD₃CN. LiI (30.9 mg, 0.231 mmol) was added to a solution of 5

(50.0 mg, 0.077 mmol) in CD₃CN (600 μL), and the mixture was

studied by NMR spectroscopy.

Synthesis of the Ditopic Complex Ph₂(SCN)SnCH₂-[13]-

crown-4 LiSCN ([15 LiSCN]). Lithium thiocyanate (50.7 mg,

3

0.780 mmol) was added to a solution of 3 (100.0 mg, 0.195

mmol) in CH₂Cl₂(10 mL). The mixture was stirred at room

temperature for two days. After the excess insoluble salts had

been filtered the solvent was removed in vacuo to give 0.07 g

¹¹⁹Sn{¹H} NMR (111.92 MHz, 293 K) δ: -331 (ν_1/2= 254 Hz).

In Situ Reaction of 6 with Three Molar Equivalents of LiI in

CD₃CN. LiI (28.5 mg, 0.213 mmol) was added to a solution of 6

(50.0 mg, 0.071 mmol) in CD₃CN (600 μL), and the mixture was

studied by NMR spectroscopy.

(62%) of pure [15 LiSCN] as a colorless viscous oil.

3

¹H NMR (CDCl₃, 400.13 MHz, 293 K) δ: 1.48 (d, ³J(¹H-¹H)

= 4.0 Hz, ²J(¹H-¹¹⁷Sn) = 68.0 Hz, ²J(¹H-¹¹⁹Sn) = 84.0 Hz,

2H, Sn-CH₂), 2.54 (m, 1H, CH), 3.30-3.63 (complex pattern,

16H, CH₂-O-CH₂), 7.30-7.99 (m, 10H, Ph). ¹³C{¹H} NMR

(CDCl₃, 100.63 MHz, 293 K) δ: 20.8 (¹J(¹³C-¹¹⁷Sn) = 616 Hz,

¹J(¹³C-¹¹⁹Sn)=644 Hz, C14), 36.2 (²J(¹³C-^117/119Sn)=24 Hz,

C12), 66.9-67.8 (C2-C9), 77.6 (C11/C13), 128.3 (³J(¹³C-

^117/119Sn)=70 Hz, C_m), 129.1 (⁴J(¹³C-^117/119Sn)=14 Hz, C_p),

136.3 (²J(¹³C-^117/119Sn) = 47 Hz, C_o), 141.8 (¹J(¹³C-¹¹⁷Sn) =

772 Hz, ¹J(¹³C-¹¹⁹Sn) = 806 Hz, C_i). ¹¹⁹Sn {¹H} NMR (CDCl₃,

111.93 MHz, 293 K) δ: -239. Anal. Calcd for C₂₄H₂₉N₂-

¹H NMR (400.13 MHz, 293 K) δ: 2.14 (m, 1H, CH), 3.25 (d,

³J(¹H-¹H) = 8.0 Hz, 2H, Sn-CH₂), 3.68-3.89 (complex pat-

tern, 16H, CH₂-O-CH₂). ¹³C{¹H} NMR (100.63 MHz, 293 K)

δ: 3.5 (C14), 38.4 (²J(¹³C-^117/119Sn) = 38 Hz, C12), 66.9-68.4

(C2-C9), 74.3 (C11/C13). ¹¹⁹Sn{¹H} NMR (111.93 MHz, 293

K) δ: -1132 (ν_1/2= 166 Hz). ESI-MS (MeCN, m/z, positive

mode): 787.3, {I₃SnCH₂-[13]-crown-4 Li CH₃CN H₂O}^þ.

3

In Situ Reaction of 3 with Three Molar Equivalents of LiCl in

CD₃CN. LiCl (12.4 mg, 0.293 mmol) was added to a solution of

3 (50.0 mg, 0.098 mmol) in CD₃CN, and the mixture was studied

by NMR spectroscopy.

LiO₄S₂Sn H₂O (617.30): C 46.7; H 5.1; N 4.7. Found: C 46.9;

3

H 4.8; N 4.3.

Synthesis of the Aqua Complex of the Ditopic Complex Cl₃Sn-

CH₂-[13]-crown-4 LiCl H₂O ([8 LiCl H₂O]). Lithium chlo-

¹H NMR (400.13 MHz, 293 K) δ: 1.59 (d, ³J(¹H-¹H) = 4.0

Hz, 2H, ²J(¹H-¹¹⁷Sn) = 72 Hz, ²J(¹H-¹¹⁹Sn) = 88.0 Hz, Sn-

CH₂), 2.88 (m, 1H, CH), 3.49-3.81 (complex pattern, 16H,

CH₂-O-CH₂), 7.27-7.34 (m, 8H, H_mþp, Ph), 8.02(d, ³J(¹H-¹H) =

8 Hz, ³J(¹H-¹¹⁷Sn) = 56 Hz, ³J(¹H-¹¹⁹Sn) = 72 Hz, 2H, H_o, Ph).

¹³C{¹H} NMR (100.63 MHz, 293 K) δ:26.4(¹J(¹³C-¹¹⁷Sn) = 624

Hz, ¹J(¹³C-¹¹⁹Sn) = 656 Hz, C14), 35.5 (²J(¹³C-^117/119Sn) = 24

Hz, C12), 66.8-67.8 (C2-C9), 77.4 (³J(¹³C-^117/119Sn)=76 Hz,

C11/C13). 127.4 (³J(¹³C-^117/119Sn) = 67 Hz, C_m), 127.9

(⁴J(¹³C-^117/119Sn) = 15 Hz, C_p), 136.6 (²J(¹³C-^117/119Sn) = 49

3

ride (12.5 mg, 0.296 mmol) was added to a solution of 8 (31.7

mg, 0.074 mmol) in CH₃CN (10 mL), and the mixture was

stirred at room temperature for three days. After filtration of

excess salt, slow diffusion of diethyl ether into the clear acet-

onitrile solution provided 25.0 mg (69%) of pure [8 LiCl H₂O]

3

as sligthly yellow crystals, mp 233 °C.

¹H NMR (CD₃CN, 400.13 MHz, 293 K) δ: 1.64 (d, ³J-

(¹H-¹H)=4.0 Hz, J(¹H-¹¹⁷Sn)=116.0 Hz, J(¹H-¹¹⁹Sn)=

2

124.0 Hz, 2H, Sn-CH₂), 2.80 (m, 1H, CH), 3.64-3.81 (complex

Article

Organometallics, Vol. 29, No. 21, 2010 5471

1

Hz, C_o), 147.6 (¹J(¹³C-¹¹⁷Sn) = 735 Hz, J(¹³C-¹¹⁹Sn) = 769

H_o). ¹³C{¹H} NMR (100.63 MHz, 293 K) δ: 35.3 (²J(¹³C-

^117/119Sn) = 148 Hz, C12), 40.19 (¹J(¹³C-¹¹⁷Sn) = 880 Hz,

¹J(¹³C-¹¹⁹Sn) = 922 Hz, C14), 64.0 (¹J(¹³C-¹¹⁷Sn) = 793 Hz,

¹J(¹³C-¹¹⁹Sn) = 827 Hz, C14), 66.8-67.8 (C2-C9), 76.9

(³J(¹³C-^117/119Sn) = 101 Hz, C11/C13), 127.0 (³J(¹³C-¹¹⁷Sn) =

Hz), C_i).

¹¹⁹Sn{¹H} NMR (111.92 MHz, 293 K) δ:-202 (ν_1/2= 2048 Hz).

In Situ Reaction of 8 with One Molar Equivalent of (Ph₃P)₂NCl

in CD₃CN. (Ph₃P)₂NCl (27.0 mg, 0.047 mmom) was added to a

solution of 8 (20.0 mg, 0.047 mmol) in CD₃CN (600 μL), and the

mixture was studied by NMR spectroscopy.

3

111 Hz, J(¹³C-¹¹⁷Sn) = 116 Hz, SnCl₃Ph, C_m), 127.9 (⁴J(¹³C-

^117/119Sn) = 22 Hz, SnCl₃Ph, C_p), 134.9 (²J(¹³C-^117/119Sn) = 71

Hz, SnCl₃Ph, C_o), 155.1 (SnCl₃Ph, C_i). ¹¹⁹Sn{¹H} NMR (111.93

¹¹⁹Sn{¹H} NMR (CD₃CN), 111.92 MHz, 293 K) δ: -402 (ν_1/2

=

MHz, 293 K) δ: -207 (ν_1/2= 118 Hz, SnCH₂CH), -279 (ν_1/2

126 Hz, SnPh).

=

156 Hz).

In Situ Reaction of 14 with Excess LiCl in CD₃CN. Lithium

chloride (3.69 mg, 8.91 ꢀ 10^-5mol) was added to a solution of 14

(20.0 mg, 2.97 ꢀ 10^-5mol) in CD₃CN (600 μL), and the mixture

was studied by NMR spectroscopy.

Acknowledgment. A.C.T.K. is grateful to the German

Academic Exchange Board (DAAD) for a scholarship.

We thank Dr. G. Bradtmoller for recording the ¹¹⁹Sn-

¹H NMR (400.13 MHz, 293 K) δ: 1.76 (d, ³J(¹H-¹H) = 4.0

Hz, ²J(¹H-¹¹⁷Sn) = 108.0 Hz, ²J(¹H-¹¹⁷Sn) = 116 Hz, 2H, Sn-

€

MAS NMR and Mrs. S. Marzian for recording the

electrospray ionization mass spectra.

CH₂), 2.81 (s, J(¹H-^117/119Sn) = 96.0 Hz, 2H, Sn-CH₂-Sn),

1

2.83 (m, 1H, CH), 3.56-3.88 (complex pattern, 16H, CH₂-O-

CH₂), 7.23-7.36 (m, 3H, Ph, H_mþp), 8.07 (d, ³J(¹H-¹H) = 8.0

Hz, ¹J(¹H-¹¹⁷Sn) = 104 Hz, ¹J(¹H-¹¹⁹Sn) = 116 Hz, 2H, Ph,

Supporting Information Available: This material is available

free of charge via the Internet at http://pubs.acs.org.

Article Doi

Organotin-substituted [13]-crown-4 ethers: Ditopic receptors for lithium and cesium halides

DOI: 10.1021/om100409v

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Article abstract of DOI:10.1021/om100409v

Full text of DOI:10.1021/om100409v

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