Syntheses, structures, and 1H, 13C{1H} and 119Sn{1H} NMR chemical shifts of a family of trimethyltin alkoxide, amide, halide and cyclopentadienyl compounds

Article abstract of DOI:10.1039/c5dt01980j

The synthesis and full characterization, including Nuclear Magnetic Resonance (NMR) data (¹H, ¹³C{¹H} and ¹¹⁹Sn{¹H}), for a series of Me₃SnX (X = O-2,6-^tBu₂C₆H₃ (1), (Me₃Sn)N(2,6-ⁱPr₂C₆H₃) (3), NH-2,4,6-^tBu₃C₆H₂ (4), N(SiMe₃)₂ (5), NEt₂, C₅Me₅ (6), Cl, Br, I, and SnMe₃) compounds in benzene-d₆, toluene-d₈, dichloromethane-d₂, chloroform-d₁, acetonitrile-d₃, and tetrahydrofuran-d₈ are reported. The X-ray crystal structures of Me₃Sn(O-2,6-^tBu₂C₆H₃) (1), Me₃Sn(O-2,6-ⁱPr₂C₆H₃) (2), and (Me₃Sn)(NH-2,4,6-^tBu₃C₆H₂) (4) are also presented. These compiled data complement existing literature data and ease the characterization of these compounds by routine NMR experiments.

Full text of DOI:10.1039/c5dt01980j

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Syntheses, structures, and 1H, 13C{1H} and
119Sn{1H} NMR chemical shifts of a family of
trimethyltin alkoxide, amide, halide and
cyclopentadienyl compounds†
Cite this: DOI: 10.1039/c5dt01980j
Alejandro G. Lichtscheidl,a Michael T. Janicke,a Brian L. Scott,a Andrew T. Nelson*b
and Jaqueline L. Kiplinger*a
The synthesis and full characterization, including Nuclear Magnetic Resonance (NMR) data (1H, 13C{1H}
and 119Sn{1H}), for
a series of Me3SnX (X =
O-2,6-tBu2C6H3 (1), (Me3Sn)N(2,6-iPr2C6H3) (3),
NH-2,4,6-tBu3C6H2 (4), N(SiMe3)2 (5), NEt2, C5Me5 (6), Cl, Br, I, and SnMe3) compounds in benzene-d6,
toluene-d8, dichloromethane-d2, chloroform-d1, acetonitrile-d3, and tetrahydrofuran-d8 are reported.
The X-ray crystal structures of Me3Sn(O-2,6-tBu2C6H3) (1), Me3Sn(O-2,6-iPr2C6H3) (2), and (Me3Sn)-
(NH-2,4,6-tBu3C6H2) (4) are also presented. These compiled data complement existing literature data and
ease the characterization of these compounds by routine NMR experiments.
Received 26th May 2015,
Accepted 6th August 2015
DOI: 10.1039/c5dt01980j
www.rsc.org/dalton
common deuterated solvents (benzene-d6, toluene-d8, dichloro-
methane-d2, chloroform-d1, acetonitrile-d3, and tetrahydro-
Introduction
Among main-group organometallics, organotin amide, alkox- furan-d8). In addition, 119Sn{1H} NMR data is also presented
ide, and halide compounds show a diverse array of appli- (in benzene-d6 or chloroform-d1) for all compounds. We antici-
cations ranging from all sorts of biological activity,1 pate that these collocated data will serve as a resource for che-
ionophores in sensors,2 precursors for hybrid organic– mists working with trimethyltin compounds.
inorganic nano and non-linear optical materials,3 and catalysts
for a variety of widely-used organic carbon–carbon coupling
processes.4 Although their use as marine antifoulants is being
Results and discussion
phased out, new organotin derivatives with N, O and S donat-
Synthesis and solid-state structural characterization
ing groups are showing promise as antimicrobial, antifungal,
and anticancer agents.5 Despite their broad utility and long-
Scheme 1 presents the synthetic methods used and the yields
obtained in the preparation of trimethyltin compounds 1–6.
All of these compounds were prepared by transmetallation.
For example, treatment of a tetrahydrofuran (THF) solution
of Me3SnCl with one equivalent of either K(O-2,6-tBu2C6H3)
or K(O-2,6-iPr2C6H3) at room temperature afforded the
corresponding trimethyltin aryloxide compounds Me3Sn-
(O-2,6-tBu2C6H3) (1) and Me3Sn(O-2,6-iPr2C6H3) (2), in 81%
and 86% isolated yields respectively. Following workup by fil-
tration through Celite and recrystallization, both complexes
were isolated as white and off-white solids, respectively. The
X-ray crystal structures of complexes 1 and 2 are presented in
Fig. 1 and 2, respectively. Both compounds represent rare
examples of structurally characterized trimethyltin aryloxides;
they are monomeric in the solid state with similar bond
lengths and angles. The tin(IV) atom in both complexes is four-
coordinate and possesses a distorted tetrahedral geometry.
The Sn–O bond distances, Sn–O–Cipso bond angles, and
Sn–C bond distances for complexes 1 (Sn–O = 2.0270(11) Å,
standing history in organometallic and inorganic chemistry, it
is surprising that very little solution and solid-state structural
information has been reported for even the simple organotin
compounds Me3SnX (where X = NR2, OR, halide, C5Me5, and
SnMe3).6 Herein, we report the synthesis and characterization
of a family of trimethyltin amide, alkoxide, and cyclopenta-
dienyl compounds. We show that transmetallation from a potass-
ium amide, alkoxide or cyclopentadienyl reagent and Me3SnCl
provides an improved route for accessing the corresponding
trimethyltin derivatives and offers an alternative to existing lit-
erature procedures. For completeness, we have compiled 1H
and 13C{1H} NMR data of eleven Me3SnX compounds in six
aLos Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA
bLos Alamos National Laboratory, Mail Stop E-549, Los Alamos, NM 87545, USA.
E-mail: Kiplinger@lanl.gov; Fax: +1 505-667-9905; Tel: +1 505-665-9553
†CCDC 1062520–1062522 for 1, 2 and 4. For crystallographic data in CIF or
other electronic format see DOI: 10.1039/c5dt01980j
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Fig. 2 Molecular structure of Me3Sn(O-2,6-iPr2C6H3) (2) with thermal
ellipsoids projected at the 50% probability level. Hydrogen atoms have
been omitted for clarity. Selected bond distances (Å) and angles (°):
Sn(1)–O(1), 2.032(3); Sn(1)–C(1), 2.124(4); Sn(1)–C(2), 2.118(3); Sn(1)–
C(3), 2.130(4); C(4)–O(1), 1.364(4); Sn(1)–O(1)–C(4), 121.19(18); C(1)–Sn(1)–
C(2), 118.98(16); C(1)–Sn(1)–C(3), 113.71(13); C(1)–Sn(1)–O(1), 101.74(13).
Sn–O–Cipso = 133.64(9)°, Sn–C = 2.1251(17)–2.1279(13) Å) and 2
(Sn–O = 2.032(3) Å, Sn–O–Cipso = 121.19(18)°, Sn–C = 2.118(3)–
2.130(4) Å) are comparable to those reported for the handful of
known four-coordinate trialkyltin aryloxide complexes: [1,4-
(Et3SnO)2C6Cl4] (Sn–O = 2.08 Å, Sn–O–Cipso = 127°, Sn–C =
2.15–2.21 Å),7 (PhMe2CCH2)3Sn(OC6H4-4-NO2) (Sn–O = 2.0454(13)
Å, Sn–O–Cipso = 127.98(12)°, Sn–C = 2.1415(13)–2.1584(18) Å),8
Scheme 1 Synthetic routes to trimethyltin alkoxide (1–2), amide (3–5)
and cyclopentadienyl (6) compounds.
(CH3)3Sn(O-2,6-tBu2C6H4-4-Me) (Sn–O
=
2.0082(15) Å,
Sn–O–Cipso = 133.77(14)°, Sn–C = 2.127(2)–2.139(3) Å),9
(CH3)3Sn[OC6H4-4-CMe2-C6H4-4-OH] (Sn–O = 2.094(2) Å, Sn–O–
Cipso
= 127.60(10)°, Sn–C =
2.115(3)–2.120(2) Å),10 and
(PhMe2CCH2)3Sn(OC6H4-2-OMe-4-CHO) (Sn–O = 2.038(3) Å,
Sn–O–Cipso = 127.1(2)°, Sn–C = 2.142(4)–2.148(4) Å).11 The only
marked difference between the two trimethyltin aryloxide com-
plexes are in the Sn(1)–O(1)–C(3)/C(4) angle which is larger for
1 (133.64(9)°) than for 2 (121.19(18)°) and is attributed to the
greater steric interactions between the Me3Sn group and the
ortho tBu versus iPr substituents on the aromatic ring.
Similarly, reaction of a THF solution of Me3SnCl with one
equivalent of K(NH-2,6-iPr2C6H3)·12THF at room temperature
for 1 h afforded the redistribution products (Me3Sn)2N-
(2,6-iPr2C6H3) (3) and H2N-2,6-iPr2C6H3. Cooling a saturated
1 : 5 toluene–acetonitrile solution of this mixture to −30 °C
furnished 3 as a white crystalline solid in 37% isolated yield.
Although 3 has been previously reported, the synthesis takes
Fig. 1 Molecular structure of Me3Sn(O-2,6-tBu2C6H3) (1) with thermal 2–4 days to complete and involved isolation of (Me3Sn)-
(NH-2,6-iPr2C6H3).6f The authors noted that the monostannyl-
ellipsoids projected at the 50% probability level. Hydrogen atoms have
been omitted for clarity. Selected bond distances (Å) and angles (°):
Sn(1)–O(1), 2.0270(11); Sn(1)–C(1), 2.1279(13); Sn(1)–C(1A), 2.1279(13);
Sn(1)–C(2), 2.1251(17); C(3)–O(1), 1.3531(19); Sn(1)–O(1)–C(3), 133.64(9);
C(1)–Sn(1)–C(1A), 107.32(8); C(1)–Sn(1)–C(2), 119.82(4); C(1)–Sn(1)–O(1),
102.86(4).
amine (Me3Sn)(NH-2,6-iPr2C6H3) is not thermodynamically
stable; two equivalents of (Me3Sn)(NH-2,6-iPr2C6H3) similarly
yielded a mixture of 3 and H2N-2,6-iPr2C6H3. The synthesis
of Me3Sn(NH-2,4,6-tBu3C6H2) (4) has also been previously
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C5Me5 (6), Cl, Br, I, and SnMe3) compounds are given in
1
Tables 1, 2, and 3, respectively. The H NMR chemical shifts
are reported at two concentrations (4–10 mM and 0.3–1.0 M)
while the 13C{1H} chemical shifts are only reported at the
higher concentration in benzene-d6, toluene-d8, dichloro-
methane-d2, chloroform-d1, acetonitrile-d3, and tetrahydro-
furan-d8. The 119Sn{1H} chemical shifts are reported at 0.3–1.0
M concentrations in benzene-d6 and chloroform-d6. Table 1
shows the 119Sn{1H} NMR data in benzene-d6 for all complexes,
except 1, where chloroform-d1 was used. The 119Sn{1H} reso-
nances in benzene for Me3SnX (X = halides, NEt2, N(SiMe3)2 and
SnMe3)6d,e,g have been reported before and are shown here for
completion. Thorough reviews discussing trends in 119Sn{1H}
NMR have been previously reported and it is sufficient to say
that resonance shifts are dependent on the electron density of
the element attached to tin, the concentration of the sample,
and the solvents used.6e
Fig. 3 Molecular structure of Me3Sn(NH-2,4,6-tBu3C6H2) (4) with
thermal ellipsoids projected at the 50% probability level. Hydrogen
atoms have been omitted for clarity. Selected bond distances (Å) and
angles (°): Sn(1)–N(1), 2.050(2); Sn(1)–C(19), 2.144(3); Sn(1)–C(20), 2.1375(19);
Sn(1)–C(21), 2.131(2); C(1)–N(1), 1.424(2); Sn(1)–N(1)–C(1), 126.50(14);
C(19)–Sn(1)–C(20), 106.23(14); C(19)–Sn(1)–C(21), 112.84(11); C(19)–
Sn(1)–N(1), 108.13(17).
1
Table 2 shows the H NMR data. Me3SnNEt2 was unstable
in acetonitrile-d3; hence no data could be obtained in that
solvent. The observed J1H–119 constant for the Me3Sn group of
Sn
all complexes is measured to be between 49–61 Hz, which is
typical of this type of coupling.6e In polar solvents the peaks
are generally shifted downfield relative to nonpolar solvents,
except for those of 3 and 6 where the resonances stay relatively
in the same region regardless of solvent used. The difference
can be ascribed to the higher steric demands of these com-
plexes, which may prevent direct binding of polar solvent
molecules to the tin center. The 1H NMR trimethyltin reso-
nances of all tin complexes are dependent on concentration of
analyte. Dilute samples (4–10 mM) generally shift downfield
relative to the higher concentration samples (0.3–1.0 M), but
there are notable exceptions. For instance, 2 and Me3SnX (X =
halides) shift upfield when dilute in benzene-d6 and toluene-
d8. Similarly, an upfield shift of the Me3Sn proton signal is
observed for dilute solutions of 1, 2 and 4 in chloroform-d1. In
tetrahydrofuran-d8 the Me3Sn resonance of 2 is the only one
that shifts at different concentrations. In benzene-d6 and
reported.12 The authors reported that compound 4 is obtained
by transmetallation from Me3SnCl and Li(NH-2,4,6-tBu3C6H2)
in diethyl ether at room temperature. However, in our hands,
this reaction consistently yielded a mixture of the redistribu-
tion products, H2N-2,4,6-tBu3C6H2 and (Me3Sn)2N(2,4,6-tBu3C6H2).
We found that reaction of K(NH-2,4,6-tBu3C6H2) with Me3SnCl
in tetrahydrofuran at −30 °C, gave 4 in 81% yield following
workup. Single crystals suitable for X-ray diffraction were
grown from a saturated acetonitrile solution of 4 at −30 °C.
The molecular structure of 4 is shown in Fig. 3. Similar to the
aryloxide complexes discussed above, the tin(IV) atom in 4 is
four-coordinate and possesses a distorted tetrahedral geome-
try. The most relevant aspects of the structure are the Sn–N
bond distance, Sn–N–Cipso bond angle, and the Sn–C bond dis-
tances (Sn–N = 2.050(2) Å, Sn–N–Cipso = 126.50(14)°, Sn–C =
2.131(2)–2.144(3) Å), which compare favorably with those
reported for the few structurally characterized four-coordinate
trialkyltin arylamide complexes: (Me3Sn)2(NC6H5) (Sn–N =
2.053(3), 2.058(3) Å, Sn–N–Cipso = 119.8(2), 118.7(2)°, Sn–C =
2.133(4)–2.142(4) Å),6c (Me3Sn)2(N-2,6-iPr2C6H3) (Sn–N = 2.044(3)
Å, Sn–N–Cipso = 117.5(2)°, Sn–C = 2.118(6)–2.122(8) Å),6f
[1,3-{(Me3Sn)(-2,6-iPr2C6H3)NCH2}2C6H4] (Sn–N = 2.0454(13) Å,
Sn–N–Cipso = 127.98(12)°, Sn–C = 2.1318(23)–2.1584(18) Å).13
Finally, preparation of the known compounds Me3SnN(SiMe3)2
(5) and Me3Sn(C5Me5) (6) is straightforward by reaction of
Me3SnCl with K[N(SiMe3)2] or K(C5Me5), respectively, yielding
the products in 66% and 90% isolated yields.
Table 1 119Sn{1H} NMR data of organometallic tin(IV) compounds
Compound
δ
Me3Sn(O-2,6-tBu2C6H3) (1)
Me3Sn(O-2,6-iPr2C6H3) (2)
(Me3Sn)2(N-2,6-iPr2C6H3) (3)
Me3Sn(NH-2,4,6-tBu3C6H2) (4)
Me3SnN(SiMe3)2 (5)
Me3SnNEt2
Me3Sn(C5Me5) (6)
Me3SnCl
Me3SnBr
129.9b
138.2
64.2
63.3
46.7a
60.0a
48.2
164.2a
128.0a
38.6a
Me3SnI
Me3Sn–SnMe3
−109.0a
NMR studies
All NMR resonances are reported in ppm and externally referenced to
20% Me3SnBr in C6D6, unless otherwise noted. Sample concentration
The 119Sn{1H}, 1H and 13C{1H} NMR spectral data for the
range
=
0.3–1.0 M. a Resonances were previously reported.6e,g
Me3SnX (X = O-2,6-tBu2C6H3 (1), O-2,6-iPr2C6H3 (2), (Me3Sn)N-
b Resonance was measured in CDCl3 with 20% Me3SnBr as the
(2,6-iPr2C6H3) (3), NH-2,4,6-tBu3C6H2 (4), N(SiMe3)2 (5), NEt2, standard.6g
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Table 2 1H NMR data of organometallic tin(IV) compounds
Compound
Proton
Mult J1H–1H J1H–119
C6D6
Tol-d8
CD2Cl2
CDCl3
CD3CN
THF-d8
Sn
Me3Sn(O-2,6-tBu2C6H3) (1) SnCH3
s
s
t
d
s
d
m
t
d
s
d
m
t
d
s
s
s
s
s
s
s
s
t
54.3
(0.32)
(1.49)
(6.90)
(7.35)
(0.33)
(1.45)
(6.81)
(7.26)
0.62 (0.60)
1.41 (1.39)
6.66 (6.65)
7.16 (7.14)
0.52 (0.54)
1.23 (1.26)
3.27 (3.31)
6.82 (6.86)
7.04 (7.08)
0.15 (0.22)
1.11 (1.19)
3.68 (3.76)
6.87 (6.95)
6.98 (7.06)
0.29 (0.39)
1.28 (1.40)
1.47 (1.59)
2.73 (2.84)
7.21 (7.45)
0.11 (0.21)
0.33 (0.42)
0.24 (0.29)
1.05 (1.10)
2.97 (3.02)
−0.04
0.62 (0.60)
1.43 (1.41)
6.73 (6.71)
7.21 (7.19)
0.51 (0.48)
1.22 (1.19)
3.27 (3.24)
6.86 (6.83)
7.05 (7.02)
(0.57)
(1.38)
(6.60)
(7.12)
0.44 (0.49)
1.15 (1.20)
3.24 (3.31)
6.72 (6.78)
6.97 (7.02)
0.58 (0.56)
1.39 (1.37)
6.52 (6.51)
7.06 (7.04)
0.44 (0.49)
1.15 (1.20)
3.25 (3.31)
6.63 (6.68)
6.90 (6.95)
0.15 (0.15)
1.11 (1.12)
3.71 (3.72)
6.80 (6.82)
6.95 (6.96)
0.24 (0.24)
1.26 (1.27)
1.46 (1.47)
2.76 (2.77)
7.19 (7.29)
0.11 (0.12)
0.34 (0.34)
0.17 (0.17)
0.98 (0.99)
2.91 (2.93)
−0.07
tBu-CH3
p-ArH
7.84
7.77
m-ArH
Me3Sn(O-2,6-iPr2C6H3) (2)
SnCH3
iPr-CH3
iPr-CH
p-ArH
55.7
0.25 (0.20)
1.27 (1.30)
3.38 (3.41)
6.93 (7.00)
7.12 (7.36)
0.14 (0.15)
1.19 (1.20)
3.77 (3.78)
7.01 (7.01)
7.07 (7.09)
0.17 (0.17)
1.38 (1.38)
1.56 (1.56)
2.68 (2.68)
7.48 (7.48)
0.21 (0.22)
0.25 (0.25)
0.14 (0.14)
1.06 (1.06)
3.00 (2.99)
−0.06
0.20 (0.20)
1.24 (1.26)
3.32 (3.35)
6.88 (6.91)
7.06 (7.08)
0.12 (0.13)
1.16 (1.17)
3.74 (3.75)
6.94 (6.94)
7.02 (7.01)
0.16 (0.16)
1.34 (1.35)
1.52 (1.53)
2.62 (2.63)
7.39 (7.41)
0.17 (0.19)
0.24 (0.24)
0.12 (0.13)
1.02 (1.04)
2.95 (2.97)
−0.08
7.98
6.72
7.45
8.07
m-ArH
SnCH3
iPr-CH3
iPr-CH
p-ArH
(Me3Sn)2(N-2,6-iPr2C6H3)
(3)
55.7
51.7
0.13a (0.24) (0.12)
1.10a (1.22) (1.09)
3.65a (3.77) (3.70)
6.88a (7.01) (6.84)
6.98a (7.10) (6.98)
7.56
6.99
7.84
7.37
m-ArH
Me3Sn(NH-2,4,6-tBu3C6H2) (4) SnCH3
0.30 (0.19)
1.29 (1.21)
1.49 (1.40)
2.76 (2.65)
7.24 (7.04)
0.10 (0.22)
0.32 (0.43)
0.47 (0.59)
1.08 (1.21)
2.62 (2.74)
−0.02
(0.26)
(1.26)
(1.46)
(2.75)
p-tBu-CH3
o-tBu-CH3
N–H
m-ArH
SiCH3
(7.22)
Me3SnN(SiMe3)2 (5)
0.10 (0.08)
0.33 (0.31)
IC
SnCH3
SnCH3
NCH2CH3
NCH2
54.7
54.1
Me3SnNEt2
7.02
7.05
q
s
Me3Sn(C5Me5) (6)
SnCH3
49.6
−0.08
(−0.04)
(−0.05)
(−0.07)
(−0.00)
(−0.02)
(−0.07)
C5(CH3)5
SnCH3
SnCH3
SnCH3
SnCH3
s
s
s
s
s
19.7
59.5
56.4
61.5
47.8
1.79 (1.83)
0.29 (0.22)
0.40 (0.32)
0.48 (0.46)
0.25 (0.25)
1.77 (1.78)
0.28 (0.23)
0.35 (0.33)
0.50 (0.48)
0.23 (0.24)
1.80 (1.85)
0.65 (0.70)
0.75 (0.83)
0.88 (0.93)
0.22 (0.20)
1.85 (1.89)
0.64 (0.74)
0.75 (0.83)
0.87 (0.96)
0.21 (0.20)
1.76 (1.80)
0.60 (0.65)
0.72 (0.77)
0.87 (0.91)
0.19 (0.18)
1.76 (1.77)
0.58 (0.59)
0.70 (0.70)
0.88 (0.87)
0.21 (0.21)
Me3SnCl
Me3SnBr
Me3SnI
Me3Sn–SnMe3
All NMR resonances are reported in ppm. Sample concentration range = 0.3–1.0 M. Values in parenthesis for sample concentration range =
4–10 mM. J1H–1H and J1H–119Sn coupling constants are reported in Hz. Multiplicity listed as singlet (s), doublet (d), triplet (t), quartet (q), or multiplet (m).
All resonances are referenced to solvent impurities.14 IC = incompatible solvent. a Resonances previously reported.6f
toluene-d8 the Me3Sn proton resonances of 4, 5, and plexes 1–6, along with Me3SnX (X = NEt2, Cl, Br, I, SnMe3) in
Me3SnNEt2 remain unchanged regardless of concentration.
six common deuterated organic solvents were presented in
Table 3 shows 13C NMR data for all complexes. Compound 1 tabulated form, which we hope will better aid the future
is sparingly soluble in benzene-d6, toluene-d8, and acetonitrile- researchers to identify tin(IV) compounds present in reactions
d3; 13C{1H} NMR data could not be obtained in those solvents. involving trimethyltin.
Compound 3 is sparingly soluble in acetonitrile-d3, thus suit-
able 13C{1H} NMR data could not be obtained in this solvent. As
observed in Table 2, the Me3Sn resonance in the 13C{1H} NMR
Experimental
shifts farther downfield with solvent polarity. However, there is
General synthetic considerations
a difference between the Me3Sn resonances in dichloro-
Unless otherwise noted, all reactions and manipulations were
performed at 20 °C in a recirculating Vacuum Atmospheres
NEXUS 2 model inert atmosphere (N2) drybox equipped with a
40CFM Dual Purifier NI-Train. Glassware was dried overnight
at 150 °C before use. All NMR spectra were obtained using a
Bruker Avance 400 MHz spectrometer at room temperature.
Chemical shifts for 1H and 13C{1H} NMR spectra were refer-
enced to solvent impurities.14 119Sn{1H} NMR spectra were
methane-d2 or chloroform-d1 and those found in acetonitrile-d3
or tetrahydrofuran-d8, with the latter two having the most
upfield resonances. The J
coupling constants for the
13C–119Sn
Me3Sn resonance reside mostly in the 300–400 Hz range.
Conclusions
The synthesis and X-ray characterization of complexes 1, 2 and referenced to a 20% Me3SnBr solution in the corresponding
4 have been presented and discussed. These data add to the deuterated NMR solvent.6g Melting points were determined
rather small number of trimethyl tin compounds characterized with a Mel-Temp II capillary melting point apparatus equipped
crystallographically in the literature. A modified synthetic with a Fluke 50S K/J thermocouple using capillary tubes flame-
route was also presented for complexes 3–6 that simplifies sealed under N2; values are uncorrected. Elemental Analyses
purification. The 1H, 13C{1H}, and 119Sn{1H} NMR data of com- were performed by ALS Environmental (Tucson, AZ).
Dalton Trans.
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Table 3 13C{1H} NMR data of organometallic tin(IV) compounds
Compound
Carbon
J
C6D6
Tol-d8
CD2Cl2
CDCl3
CD3CN
THF-d8
13C–119Sn
Me3Sn(O-2,6-tBu2C6H3) (1)
SnCH3
tBu-CH3
tBu-C
Ar–C
Ar–C
392
391
368
1.02
31.45
35.51
118.24
125.70
141.38
160.52
−2.76
23.75
1.07
31.34
35.34
118.00
125.46
141.08
160.17
−2.77
23.67
1.02
31.60
35.58
117.81
125.48
140.95
161.14
−2.73
23.64
27.55
118.73
122.94
139.06
157.21
−4.42
24.69
27.65
122.30
123.13
147.23
150.99
−3.34
31.91
32.54
34.77
36.52
122.33
140.79
142.92
148.52
−0.82
5.63
SS
SS
SS
Ar–C
Ar–CO
SnCH3
iPr-CH3
iPr-CH
Ar–C
Ar–C
Ar–C
Ar–CO
SnCH3
iPr-CH3
iPr-CH
Ar–C
Ar–C
Ar–C
Me3Sn(O-2,6-iPr2C6H3) (2)
(Me3Sn)2(N-2,6-iPr2C6H3) (3)
Me3Sn(NH-2,4,6-tBu3C6H2) (4)
−3.23
23.76
27.49
119.87
123.35
139.09
156.25
−4.24
24.78
−3.48
23.72
27.50
120.07
123.33
139.04
156.05
−4.30
24.74
−2.13
23.79
27.58
119.64
123.68
139.94
157.14
−4.18
24.75
27.74
122.33
123.43
147.97
SS
−2.79
31.98
32.51
34.99
36.99
122.99
141.08
143.03
149.10
−0.73
5.63
27.33
26.94
119.69
123.30
139.55
155.93
−4.18
24.70
119.58
123.04
139.24
155.18
−4.34a
24.42a
26.95a
121.27a
122.46a
146.78a
150.30a
−2.79
31.81
32.29
34.51
36.11
122.26
140.43
141.79
147.95
−0.70
5.50
−7.06
15.49
44.05
−9.19
11.72
118.22
−0.76
−0.86
−1.24
−9.99
27.43
27.44
27.42
9.8
9.1
13.3
122.54
123.17
146.92
150.41
−3.21
31.99
32.51
34.64
36.30
122.43
141.05
142.69
148.05
−0.89b
5.66b
−6.65
17.51
46.70
122.60
123.13
146.88
150.34
−3.30
31.96
32.52
34.63
36.30
122.35
140.99
142.69
147.96
−0.92
5.64
−6.67
17.56
46.73
121.81
122.93
147.40
151.00
−2.88
31.82
32.31
34.66
36.28
122.49
140.67
142.22
148.32
−0.68
5.57
−6.53
17.13
46.70
Ar–CN
SnCH3
tBu-CH3
tBu-CH3
tBu-C
376
tBu-C
Ar–C
Ar–C
Ar–C
Ar–CN
SnCH3
SiCH3
SnCH3
NCH2CH3
NCH2
SnCH3
C5(CH3)5
C5(CH3)5
SnCH3
SnCH3
SnCH3
SnCH3
Me3SnN(SiMe3)2 (5)
379
373
Me3SnNEt2
IC
−6.89
17.47
46.81
−9.71
11.68
118.58
0.07
0.47
0.83
−10.32
Me3Sn(C5Me5) (6)
303
−9.38
11.92
−9.46
11.84
−9.23
11.88
−9.38
11.85
118.88
0.68
1.10
1.28
118.39
−1.48
−1.37
−2.09
−10.08
118.38
−1.69
−1.81
−2.25
−10.09
118.50
−0.79
−0.81
−1.22
−9.94
Me3SnCl
Me3SnBr
Me3SnI
Me3Sn–SnMe3
369
357
342
238
−10.13
All NMR resonances are reported in ppm. Sample concentration range = 0.3–1.0 M. J
coupling constants are reported in Hz. All resonances
13C–119Sn
are referenced to solvent impurities.14 IC = incompatible solvent. SS = sparingly soluble in solvent. a Resonances previously reported.6f
b Resonances previously reported.6d
Materials
passed through a column of activated alumina and stored over
fresh 3 Å molecular sieves for one day prior to use. Me3SnCl
Unless otherwise noted, reagents were purchased from com- (Acros), Me3SnBr (Aldrich) and Me3SnI (Gelest) were pur-
mercial suppliers and used without further purification. Celite chased and used without further purification. K(C5Me5),15
(Aldrich), alumina (Brockman I, Aldrich), and 3 Å molecular K(O-2,6-iPr2C6H3),15 K(O-2,6-tBu2C6H3),15 and Me3SnNEt2,6i were
sieves (Aldrich) were dried under dynamic vacuum at 250 °C prepared according to literature procedures.
for 48 h prior to use. All solvents (Aldrich) were purchased
Synthesis of K(NH-2,6-iPr2C6H3)·21THF. This is a modifi-
anhydrous, dried over KH for 48 h, passed through a column cation of a literature procedure.16 A 20 mL scintillation vial
of activated alumina, and stored over activated 3 Å molecular equipped with a stir bar was charged with H2N-2,6-iPr2C6H3
sieves prior to use. Benzene-d6, toluene-d8, and tetrahydro- (0.990 g, 5.58 mmol) and THF (5 mL). K[N(SiMe3)2] (1.14 g,
furan-d8 (all Cambridge Isotopes) were dried over KH for 48 h, 5.58 mmol) was added as a solid to the resulting solution and
passed through a column of activated alumina, and stored the reaction mixture was stirred at room temperature for 2 h.
over activated 3 Å molecular sieves prior to use. Chloroform-d1, The volatiles were then removed under reduced pressure to
dichloromethane-d2, and acetonitrile-d3 (all Cambridge Iso- give K(NH-2,6-iPr2C6H3)·21THF as
topes) were dried over activated 3 Å molecular sieves for 48 h, 5.56 mmol, 99%). 1H NMR (THF-d8): δ 6.58 (2H, d, JH,H
a white solid (1.40 g,
=
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7.3 Hz, m-H), 5.84 (1H, t, JH,H = 7.3 Hz, p-H), 3.62 (4H, THF), residue was dissolved in a 1 : 5 toluene : acetonitrile solution
3.49 (1H, s, NH), 3.13 (2H, hept, JH,H = 6.8 Hz, CHMe2), 1.77 and stored at −30 °C overnight to give (Me3Sn)2(N-2,6-iPr2C6H3
(4H, THF), 1.16 (12H, d, JH,H = 6.8 Hz, CH(CH3)2).
Synthesis of K(NH-2,4,6-tBu3C6H2). This is a modification of and dried under reduced pressure (0.184 g, 0.366 mmol, 37%).
a literature procedure.17 A 50 mL round bottom flask equipped Synthesis of Me3Sn(NH-2,4,6-tBu3C6H2) (4). This is a modifi-
(3) as a white crystalline solid, which was collected by filtration
with a stir bar was charged with H2N-2,4,6-tBu3C6H2 (4.07 g, cation of a literature procedure.12 A 20 mL scintillation vial
15.5 mmol) and THF (20 mL). While stirring, KN(SiMe3)2 was charged with K(NH-2,4,6-tBu3C6H2) (0.100 g, 0.332 mmol)
(3.10 g, 15.5 mmol) was added as a solid. The solution became and THF (15 mL) and cooled to −30 °C. A 50 mL round
increasingly cloudy, and the white suspension was stirred for bottom flask was charged with a stir bar, Me3SnCl (0.069 g,
18 h at room temperature. The reaction mixture was filtered 0.332 mmol), and THF (5 mL), and cooled down to −30 °C.
through a medium-porosity fritted filter to collect a white The cooled K(NH-2,4,6-tBu3C6H2)/THF solution was added
powder, which was washed with hexane (3 × 10 mL) and dried dropwise with stirring over the course of 10 min to the cooled
under reduced pressure to give K(NH-2,4,6-tBu3C6H2) as a Me3SnCl/THF solution. The reaction mixture was warmed to
white powder (4.33 g, 14.4 mmol, 93%). 1H NMR (THF-d8): room temperature and stirred 1 h, after which the volatiles
δ 6.73 (2H, s, m-H), 3.38 (1H, s, NH), 1.45 (18H, s, o-C(CH3)3), were removed under reduced pressure. The resulting solid was
1.17 (9H, s, p-C(CH3)3).
redissolved in toluene (10 mL) and filtered through a Celite-
Synthesis of Me3Sn(O-2,6-tBu2C6H3) (1). A 20 mL scintil- padded coarse-porosity fritted filter. The filtrate was collected
lation vial was charged with a stir bar, K(O-2,6-tBu2C6H3) and the volatiles were removed under reduced pressure to yield
(0.300 g, 1.23 mmol), Me3SnCl (0.245 g, 1.23 mmol), and THF a white solid powder containing Me3Sn(NH-2,4,6-tBu3C6H2) (4)
(5 mL). The reaction mixture was stirred at room temperature (0.114 g, 0.269 mmol, 81%). Crystals of 4 suitable for X-ray
for 1 h, after which the volatiles were removed under reduced diffraction were grown by dissolving this white solid in aceto-
pressure. The resulting solid was redissolved in toluene nitrile and storing at −30 °C for two days.
(20 mL) and filtered through a Celite-padded coarse-porosity
Synthesis of Me3SnN(SiMe3)2 (5). This is a modification of a
fritted filter. The colorless filtrate was collected and the vola- literature procedure.18 A 20 mL scintillation vial was charged
tiles were removed under reduced pressure to give Me3Sn- with a stir bar, KN(SiMe3)2 (0.300 g, 1.50 mmol), Me3SnCl
(O-2,6-iPr2C6H3) (1) as a white solid (0.370 g, 1.00 mmol, 81%). (0.300 g, 1.50 mmol), and THF (5 mL). The reaction mixture
Crystals suitable for X-ray diffraction were obtained by dissol- was stirred at room temperature for 1 h, after which the vola-
ving compound 1 in hot toluene (100 °C) and then cooling the tiles were removed under reduced pressure. The resulting solid
concentrated solution to room temperature. M.p. 197–199 °C. was redissolved in toluene (5 mL) and filtered through a
Anal. Calcd for C17H30OSn (mol. wt 369.13 g mol−1): C, 55.31; Celite-padded coarse-porosity fritted filter. The colorless fil-
H, 8.19. Found: C, 55.56; H, 8.66.
trate was collected and the volatiles were removed under
Synthesis of Me3Sn(O-2,6-iPr2C6H3) (2). A 20 mL scintil- reduced pressure to yield Me3SnN(SiMe3)2 (5) as an oil
lation vial was charged with a stir bar, K(O-2,6-iPr2C6H3) (0.323 g, 0.995 mmol, 66%). Note: it is important not to leave
(0.300 g, 1.39 mmol), Me3SnCl (0.276 g, 1.39 mmol), and THF this product under vacuum for prolonged periods of time
(5 mL). The solution was stirred at room temperature for 1 h, (after solvent removal) because the product is slightly volatile.
after which the volatiles were removed under reduced pressure.
Synthesis of Me3Sn(C5Me5) (6). This is a modification of a
The resulting solid was redissolved in toluene (5 mL) and fil- literature procedure.6h A 20 mL scintillation vial was charged
tered through a Celite-padded coarse-porosity fritted filter. The with a stir bar, K(C5Me5) (0.100 g, 0.574 mmol), Me3SnCl
colorless filtrate was collected and the volatiles were removed (0.114 g, 0.574 mmol), and THF (5 mL). The reaction mixture
under reduced pressure to give Me3Sn(O-2,6-iPr2C6H3) (2) as an was stirred at room temperature for 1 h, after which time the
off-white pink solid (0.407 g, 1.19 mmol, 86%). Crystals suit- volatiles were removed under reduced pressure. The resulting
able for X-ray diffraction were obtained by dissolving com- solid was redissolved in toluene (5 mL) and filtered through a
pound 2 in hot toluene (100 °C), cooling the concentrated Celite-padded coarse-porosity fritted filter. The colorless fil-
solution to room temperature, and then storing it at −30 °C trate was collected and the volatiles were removed under
for 2 d. m.p. 86–88 °C. Anal. Calcd for C15H26OSn (mol. wt reduced pressure to yield Me3Sn(C5Me5) (6) as an oil (0.154 g,
341.08 g mol−1): C, 52.82; H, 7.68. Found: C, 52.20; H, 8.24.
0.515 mmol, 90%). Note: it is important not to leave this
Synthesis of (Me3Sn)2(NH-2,6-iPr2C6H3) (3). This is a modifi- product under vacuum for prolonged periods of time (after
cation of a literature procedure.6f A 20 mL scintillation vial was solvent removal) because the product is slightly volatile.
charged with a stir bar, K(NH-2,6-iPr2C6H3)·21THF (0.500 g,
X-ray crystallography
1.99 mmol), Me3SnCl (0.396 g, 1.99 mmol), and THF (5 mL).
The solution was stirred at room temperature for 1 h, after Crystals of 1–4 were mounted in nylon cryoloops from Para-
which the volatiles were removed under reduced pressure. The tone-N oil. The data were collected on a Bruker D8 diffracto-
resulting solid was redissolved in toluene (60 mL) and filtered meter, with APEX II charge-coupled-device (CCD) detector,
through a Celite-padded coarse-porosity fritted filter. The and Bruker Kryoflex liquid N2 low temperature device (140 K).
colorless filtrate was collected and the volatiles removed to The instrument was equipped with graphite monochromatized
yield an oily residue (mixture of 3 and H2N-2,6-iPr2C6H3). The MoKα X-ray source (λ = 0.71073 Å) and a 0.5 mm mono-
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capillary. A hemisphere of data was collected using ω scans,
with 10-second frame exposures and 0.5° frame widths. Data
collection and initial indexing and cell refinement were
handled using APEX II software.19 Frame integration, includ-
ing Lorentz-polarization corrections, and final cell parameter
calculations were carried out using SAINT+ software.20 The
data were corrected for absorption using redundant reflections
and the SADABS program.21 Decay of reflection intensity was
not observed, as monitored by analysis of redundant frames.
The structures were solved using direct methods and differ-
ence Fourier techniques. Unless otherwise noted, non-hydro-
gen atoms were refined anisotropically and hydrogen atoms
were treated as idealized contributions. For compound 4, the
tin atom and two methyl groups (C(19) and C(20)) reside on a
mirror plane, with the third methyl group, C(21), and the aryl
amine group disordered across the mirror plane. The amine
nitrogen atom, N(1) and methyl group, C(21), were each
refined at one half-occupancy, with coordinates and tempera-
ture factors constrained to be identical. Hydrogen atom posi-
tions were not included in the model due to the disorder.
Structure solution, refinement, graphics, and creation of publi-
cation materials were performed using SHELXTL.22
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Acknowledgements
For financial support of this work, we acknowledge the U.S.
Department of Energy through the LANL LDRD Program and
the LANL G. T. Seaborg Institute for Transactinium Science
(PD Fellowship to A.G.L.), the Advanced Fuels Campaign Fuel
Cycle Research & Development Program (A.G.L., A.T.N.), and
the Office of Basic Energy Sciences, Heavy Element Chemistry
program (J.L.K., B.L.S., materials & supplies). Los Alamos
National Laboratory is operated by Los Alamos National Secur-
ity, LLC, for the National Nuclear Security Administration of
U.S. Department of Energy (contract DE-AC52-06NA25396).
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