Cyclo-Stannasiloxanes Containing both Oxygen Atoms and Methylene Moieties within the Ring and Formation of Related Organotin Oxo Clusters

Article abstract of DOI:10.1021/acs.organomet.5b00768

The syntheses of the 8-membered stannasiloxanes cyclo-[RR′SnOSi(Me₂)CH₂]₂ (5, R = R′ = Ph; 6, R = R′ = t-Bu; 7, R = Me₂N(CH₂)₃, R′ = Ph) is reported. These react with organoelement oxides, providing the novel metallasiloxanes cyclo-[Me₂SiCH₂(RR′)SnOMO] (8, R = R′ = Ph, M = t-Bu₂Sn; 9, R = R′ = t-Bu, M = t-Bu₂Sn; 10, R = Me₂N(CH₂)₃, R′ = Ph, M = t-Bu₂Sn; 11, R = Me₂N(CH₂)₃, R′ = Ph, M = Ph₂Ge). Among these, compound 11 is the first example of such species being composed of four different group 14 elements in the 6-membered-ring skeleton. On contact with moist air compound 8 surprisingly undergoes Sn-Ph bond cleavage, giving the diorganotinoxo cluster [PhSn(CH₂Me₂SiO)Sn(≈₃-O)(≈-OH)t-Bu₂]₂ (12), which shows a ladder-type structure. The latter reacts with 2 molar equiv of t-Bu₂SnO, affording the Sn₆-diorganotin oxo cluster [t-Bu₂(≈-OH)Sn(≈₃-O)SnPh(CH₂Me₂SiO)Sn-t-Bu₂(≈₃-O)]₂ (13). The compounds have been characterized by NMR spectroscopy, electrospray mass spectrometry, and in the case of compounds 5-7, 12, and 13 also by single-crystal X-ray diffraction analysis.

Full text of DOI:10.1021/acs.organomet.5b00768

Article
pubs.acs.org/Organometallics
cyclo-Stannasiloxanes Containing both Oxygen Atoms and
Methylene Moieties within the Ring and Formation of Related
Organotin Oxo Clusters
Samer Baba Haj, Christina Dietz, Michael Lutter, and Klaus Jurkschat*
̈
̈
Lehrstuhl fur Anorganische Chemie II, Technische Universitat Dortmund, 44221 Dortmund, Germany
*
S Supporting Information
ABSTRACT: The syntheses of the 8-membered stannasiloxanes cyclo-
RR′SnOSi(Me )CH ] (5, R = R′ = Ph; 6, R = R′ = t-Bu; 7, R =
[
2
2 2
Me N(CH ) , R′ = Ph) is reported. These react with organoelement oxides,
2
2 3
providing the novel metallasiloxanes cyclo-[Me SiCH (RR′)SnOMO] (8, R =
2
2
R′ = Ph, M = t-Bu Sn; 9, R = R′ = t-Bu, M = t-Bu Sn; 10, R = Me N(CH ) ,
2
2
2
2 3
R′ = Ph, M = t-Bu Sn; 11, R = Me N(CH ) , R′ = Ph, M = Ph Ge). Among
2
2
2 3
2
these, compound 11 is the first example of such species being composed of
four different group 14 elements in the 6-membered-ring skeleton. On contact with moist air compound 8 surprisingly undergoes
Sn−Ph bond cleavage, giving the diorganotinoxo cluster [PhSn(CH Me SiO)Sn(μ -O)(μ-OH)t-Bu ] (12), which shows a
2
2
3
2 2
ladder-type structure. The latter reacts with 2 molar equiv of t-Bu SnO, affording the Sn -diorganotin oxo cluster [t-Bu (μ-
2
6
2
OH)Sn(μ -O)SnPh(CH Me SiO)Sn-t-Bu (μ -O)] (13). The compounds have been characterized by NMR spectroscopy,
3
2
2
2
3
2
electrospray mass spectrometry, and in the case of compounds 5−7, 12, and 13 also by single-crystal X-ray diffraction analysis.
INTRODUCTION
goes ROP upon crystallization, in absence of any initiator,
■
giving the first well-defined polymetallasiloxanes
Polysiloxanes are the most important inorganic polymers. They
show a variety of molecular structures and demonstrate an
intimate relationship between structure and properties not
easily achievable by other classes of polymers. Consequently, a
wide diversity of applications is known. The ring-opening
polymerization (ROP) procedure of the cyclo-siloxanes has
been applied to the production of high-molecular-weight
2
a,6
(
R SnOPh SiOPh SiO) .
However, the polymers are not
2
2
2
n
6
stable and they depolymerize upon dissolving in solvent. The
release of the ring strain is foreseen to be the thermodynamic
driving force for the ROP process.
The ability of cyclo-stannasiloxanes to undergo ring-opening
polymerization strongly depends on the identity of the
exocyclic substituents at the tin and silicon atoms, as the
1
polysiloxanes. This initiated activities regarding the synthesis,
2
ferrocenyl-substituted 6-membered stannasiloxane cyclo-Fc Sn-
2
characterization, and reactivity of cyclo-metallasiloxanes. Such
(
OPh Si) O (Fc = CpFeC H ) dimerizes under crystallization,
2 2 5 4
compounds hold potential as single-source precursors for new
2a,3
affording the corresponding 12-membered stannasiloxane cyclo-
inorganic polymers.
A rich structural diversity of cyclo-
2a
[(Fc Sn(OPh SiOPh SiO) SnFc ]. In contrast, the 6-mem-
2 2 2 2 2
metallasiloxanes incorporating various heteroatoms, such as B,
Al, Ge, Sn, Pb, P, Sb, Bi, Ti, Zr, Hf, Cr, Mo, and W, exists
among the cyclo-metallasiloxanes.
bered stannasiloxane cyclo-[Me N(CH ) ] Sn(OPh Si) O con-
2
2 3 2
2
2
2
b,3a,4
taining a built-in ligand does not polymerize or dimerize upon
The first tin-containing
7
crystallization. Furthermore, the connectivity of the atoms
cyclo-metallasiloxane, cyclo-t-Bu Si(OMe SnO) Si-t-Bu , was
2
2
2
2
4
c
within the ring plays a major role. Thus, the 5-membered
prepared in 1986 by Klingebiel et al. In 1997, we reported
the syntheses and molecular structures of the cyclo-stannasilox-
anes cyclo-t-Bu Sn[O(t-Bu )Si] O and cyclo-t-Bu Si[O(t-Bu )-
stannasiloxane cyclo-(Ph SiO) Sn-t-Bu containing a Si−Si
2
2
2
bond does not polymerize upon crystallization. It reversibly
2
2
2
2
2
dimerizes, providing the 10-membered stannasiloxane cyclo-t-
SnO] Si-t-Bu , obtained by the reaction of (t-Bu SnO) with t-
2
2
2
3
2a
5
Bu Sn(OPh SiPh SiO) Sn-t-Bu .
2
2
2
2
2
Bu SiCl . These were followed by the syntheses and reactivity
2
2
The reactions of cyclo-stannasiloxanes with organoelement
oxides allowed the isolation of new interesting cyclo-metal-
lasiloxanes of different ring sizes thanks to the kinetically labile
Sn−OSi bond. Thus, the reaction of the 8-membered
stannasiloxanes cyclo-R Sn(OPh SiO) SnR (R = Me N-
studies of a series of cyclo-stannasiloxanes of different ring sizes
and variable substituents at both the silicon and tin atoms.
2a
The studies showed that the reactivity of the cyclo-
stannasiloxanes differs drastically from that of the parent
cyclo-siloxanes as a result of the higher kinetic lability of the
Sn−O bond in comparison to the Si−O bond. Consequently,
reactions involving Sn−O bonds usually proceed rapidly at
2
2
2
2
2
(
CH ) ) with (t-Bu SnO) , t-Bu Ge(OH) . and PhB(OH)
2 3 2 3 2 2 2
gave the 6-membered metallasiloxanes cyclo-
(R SnOPh SiOMO) (M = t-Bu Sn, t-Bu Ge, PhB), and the
8
2
a
2
2
2
2
room temperature on the laboratory time scale. While the
ROP of cyclo-(Ph SiO) occurs at temperatures between 150
2
3
and 190 °C in the presence of initiators, the cyclo-
Received: September 8, 2015
stannasiloxane cyclo-R Sn(OPh Si) O (R = t-Bu, i-Pr) under-
2
2
2
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
reaction of LPhSn(OPh SiO) SnLPh (L = C H -2,6-
(O(1)−Sn(1)−C(11) in 6) and 118.33(9)° (C(1A)−Sn(1)−
C(21) in 5). The Sn(1)−O(1)−Si(1) angle in 5 (137.52(8)°)
is much smaller than the corresponding angles in 6
2
2
6
3
(
CH NMe ) ) with Ph Si(OH) afforded the 6-membered
2 2 2 2 2
2b
stannasiloxane cyclo-LPhSn(OPh Si) O.
2
2
1
0
Furthermore, the reactions of the 5-membered stannasilox-
(152.29(9)°) and Ph SiOSnPh3 (144.2(6)°), while the
3
ane cyclo-t-Bu Sn(OPh Si) and the 6-membered stannasilox-
Sn(1)−C(1A)−Si(1A) angle (113.86(11)°) is close to that in
6 (117.89(9)°). As result of an intramolecular N→Sn
interaction, the Sn(1) atom in compound 7 is pentacoordinated
and shows a distorted-trigonal-bipyramidal environment (geo-
2
2
2
ane cyclo-t-Bu Sn(OPh Si) O with (t-Bu SnO) result in ring
2
2
2
2
3
enlargement, giving the corresponding 7- and 8-membered
2
a
stannasiloxanes cyclo-O(t-Bu SnOPh Si)
and cyclo-O(t-
2
2
2
4
r,6
11
Bu SnOPh Si) O, respectively.
2
2
2
metrical goodness Δ∑(θ) = 59.1°) with C(1A), C(11), and
C(21) occupying the equatorial positions and O(1) and N(14)
occupying the axial positions. The distortion from ideal
geometry is expressed by the O(1)−Sn(1)−N(14) angle of
To the best of our knowledge, cyclo-stannasiloxanes in which
the oxygen atoms are partially replaced by CH moieties have
2
been almost unexplored. As systematic studies showed that
even very similar compounds can have drastically different
chemical reactivities, this raises interest in synthesizing this type
of cyclo-stannasiloxanes and study their behavior against
organoelement oxides.
1
66.94(17)° being smaller than the ideal value of 180°. The
Sn(1)−N(14) interatomic distance of 2.766(6) Å is rather long
and indicates only weak interaction between these atoms.
Nevertheless, as a consequence of this interaction, the Sn(1)−
O(1) distance of 2.020(4) Å is greater than the corresponding
distances in compounds 5 (1.9815(14) Å) and 6 (1.9687(13)
Å), which in turn are close to those reported for 2,2,6,6-tetra-
tert-butyl-4,8-dimethyl-1,5,9-trioxa-4,8-disila-2,6-
RESULTS AND DISCUSSION
Syntheses and Structures of the 8-Membered
■
Stannasiloxanes cyclo-[RR′SnOSi(Me )CH ] (5, R = R′ =
2
2 2
1
2
Ph; 6, R = R′ = t-Bu; 7, R = Me N(CH ) , R′ = Ph). The
distannabicyclo[3.3.1]nonane.
2
2 3
The 1 Sn NMR spectra of solutions of compounds 5 and 6
19
hydrolyses under basic conditions of the Me (i-PrO)SiCH -
2
2
substituted triorganotin halides [Me (i-PrO)SiCH ]RR′SnX (2,
in CDCl3 showed singlet resonances at δ −31 and 34,
2
2
29
R = R′ = Ph, X = I; 3/3′, R = R′ = t-Bu, X = Cl/OH) provided
respectively. The corresponding Si NMR spectra showed
singlet resonances with unresolved 1
17/119
Sn coupling satellites
the corresponding 8-membered stannasiloxanes cyclo-
[
RR′SnOSi(Me )CH ] (5, R = R′ = Ph; 6, R = R′ = t-Bu).
from two magnetically different tin atoms at δ 8.6 (5,
2
2 2
2
29
117/119
2
29
117/119
29
The subsequent reaction of the tetraorganotin derivative
Me (i-PrO)SiCH }{Me N(CH ) }SnPh (4) with (i) ele-
J( Si−
Sn) = 33 Hz, J( Si−
Sn) = 54 Hz) and δ
{
2
29
117/119
2
117/119
2
2
2
2 3
2
1.8 (6, J( Si−
Sn) = 46 Hz, J( Si−
Sn) = 56 Hz),
mental iodine (I ) and (ii) aqueous sodium hydroxide (NaOH)
2
respectively. On the other hand, compound 7 adopts chirality at
gave the cyclo-stannasiloxane 7 (Scheme 1). Compounds 5−7
were obtained as colorless solid materials in very good yields.
119
the tin atom. A Sn NMR spectrum of a solution of the bulk
material in CDCl showed two resonances at δ −53 (integral
3
2
9
4
5) and −55 (integral 55). Furthermore, a Si NMR spectrum
2 29 117/119
Scheme 1. Syntheses of the Eight-Membered
showed two resonances at δ 1.4 ( J( Si−
Sn) = 38 Hz,
a
Stannasiloxanes 5−7
2
29
117/119
2
29
117/119
J( Si−
Sn) = 47 Hz) and at δ 1.0 ( J( Si−
Sn) =
2
29
117/119
119
4
2 Hz, J( Si−
Sn) = 49 Hz) (Table 2). A Sn NMR
spectrum of a solution of single crystals of 7 in C D at ambient
7
8
temperature displayed two resonances of almost equal intensity
at δ −62.8 and −62.6, respectively. At T = 333 K, these signals
shifted to δ −54.4 and −54.2, respectively. The data indicate
the presence of two diastereomers in solution, with the phenyl
groups being either cis or trans. Apparently, epimerization takes
place in solution. It is fast on the laboratory time scale but slow
119
on the
Sn NMR time scale. The mechanism of this
a
For reactions involving 2 and 3/3′: NaOH, H O, −NaX, −i-PrOH.
epimerization was not investigated in more detail.
2
For the reaction involving 4: (i) I , −PhI; (ii) NaOH, H O, −NaI, −i-
PrOH.
ESI MS spectra of compounds 5−7 in the positive mode
2
2
+
showed major mass clusters centered at m/z 723.1 ([5 + H] ),
+
+
6
43.2 ([6 + H] ), and 741.2 ([7 + H] ), respectively. In
addition, mass clusters for the species [Me (OH)SiCH RR′Sn
They show good solubility in common organic solvents such
as CH Cl , CHCl , toluene, and THF.
2
2
+
+
n H O + m MeCN] , (n, m = natural numbers between 0 and
2
2
2
3
4
) were also observed.
Compounds 5−7 each crystallized in the triclinic space group
Syntheses of the 6-Membered Metallasiloxanes cyclo-
P1 with one molecule in the unit cell. The molecular structures
̅
[
=
=
Me SiCH (RR′)SnOMO] (8, R = R′ = Ph, M = t-Bu Sn; 9, R
are shown in Figures 1−3, respectively, and selected
interatomic distances and bond angles are summarized in
Table 1.
2
2
2
R′ = t-Bu, M = t-Bu Sn; 10, R = Me N(CH ) , R′ = Ph, M
2
2
2 3
t-Bu Sn; 11, R = Me N(CH ) , R′ = Ph, M = Ph Ge). The
2
2
2 3
2
The 8-membered rings are centrosymmetric, with half of
each molecule comprising the crystallographic asymmetric unit
and the other half being generated by an inversion center.
reactions of the 8-membered stannasiloxanes cyclo-[RR′SnOSi-
(Me
Me N(CH
oxide (t-Bu GeO) in
CH Cl at room temperature or in CHCl at reflux gave the
2 3
)CH
]
(5, R = R′ = Ph; 6, R = R′ = t-Bu; 7, R =
) , R′ = Ph) with 2 molar equiv of di-tert-butyltin
2 3
2
2
2
2
According to a classification scheme introduced by Puff, Ko
al., the 8-membered rings in compounds 5 and 6 are of D
type and that in 7 is of J type (Figure 4).
̈
k, et
2
SnO) or diphenylgermanium oxide (Ph
2
4
r,9
2
corresponding 6-membered metallasiloxanes cyclo-
[Me SiCH (RR′)SnOMO] (8, R = R′ = Ph, M = t-Bu Sn; 9,
In compounds 5 and 6, the Sn(1) atoms show a distorted-
tetrahedral geometry with angles ranging between 100.41(6)
2
2
2
R = R′ = t-Bu, M = t-Bu Sn; 10, R = Me N(CH ) , R′ = Ph, M
2
2
2 3
B
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Figure 1. General view (SHELXTL) of a molecule of 5 showing 30% probability displacement ellipsoids and the crystallographic numbering scheme.
Hydrogen atoms are omitted for clarity.
Figure 2. General view (SHELXTL) of a molecule of 6 showing 30% probability displacement ellipsoids and the crystallographic numbering scheme.
Hydrogen atoms are omitted for clarity.
=
t-Bu Sn; 11, R = Me N(CH ) , R′ = Ph, M = Ph Ge) in
constant of 317/335 Hz for each resonance (Figure S36 in the
Supporting Information). Similarly, the 1 Sn NMR spectra of
2
2
2 3
2
19
excellent yields (Scheme 2).
Compounds 8−11 show good solubility in common organic
solvents such as CH Cl , CHCl , and toluene.
solutions of compounds 9 and 10 in CDCl (Figures S40 and
3
2
2
3
S44 in the Supporting Information) showed two resonances (9,
Compounds 8−10 contain two differently substituted tin
atoms linked to one silicon atom by oxygen or carbon bridges.
The first cyclo-stannasiloxane with two differently substituted
tin atoms, cyclo-[Ph SiO(R )SnO(t-Bu )SnO] (R = Me N-
δ
49 [O(t-Bu )SnCH ], −98 [O(t-Bu )SnO],
2
2
2
2
J(119Sn−117/119
Sn) = 351/367 Hz; 10, δ −23 [O{Me N-
2
2
119
117/119
(
2
CH ) Ph}SnCH ], −89 (O(t-Bu )SnO), J( Sn−
Sn) =
2
3
2
2
2
2
2
2
119
93 Hz). A Sn NMR spectrum of a solution of compound 11
(
(
CH ) ), was obtained by the reaction of cyclo-
2 3
8
in CDCl (Figure S47 in the Supporting Information) showed
one resonance at δ −59 (Table 3).
3
Ph SiOR SnO) with di-tert-butyltin oxide. On the other
2
2
2
hand, the compound cyclo-[Me SiCH (t-Bu )SnOPh GeO]
2
2
2
2
29
The Si NMR spectra of compounds 8−11 each showed a
(
11) is the first 6-membered cyclo-metallasiloxane to be
single resonance at δ 5.9, 5.2, 6.5, and 10.7, respectively, with
composed of four different group 14 elements in the ring
skeleton.
2
29
117/119
J( Si−
Sn) coupling satellites ranging between 40 and 49
Hz (Table 3).
The two chemically and magnetically different tin atoms in
1
19
The ESI MS spectra of compounds 10 and 11 in the positive
compounds 8−10 result in two Sn NMR singlet resonances,
1
17/119
119
mode showed major mass clusters that are assigned to the
protonated compounds centered at m/z 620.1 ([10 + H] ) and
614.1 ([11 + H] ). The ESI MS spectrum of compound 8
showed a mass cluster of 12% relative abundance centered at
each with
Sn coupling satellites. The
Sn NMR
+
spectrum of compound 8 in CDCl showed two resonances
3
+
at δ −13 assigned to OPh SnCH and at δ −93 that
2
2
2
119
117/119
corresponds to O-t-Bu SnO with a J( Sn−
Sn) coupling
2
C
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Figure 3. General view (SHELXTL) of a molecule of 7 showing 30% probability displacement ellipsoids and the crystallographic numbering scheme.
Hydrogen atoms are omitted for clarity.
Table 1. Selected Interatomic Distances (Å) and Bond
Angles (deg) in the Stannasiloxanes cyclo-
Table 2. Selected NMR Data of the Stannasiloxanes cyclo-
[RR′SnOSi(Me )CH ] (5, R = R′ = Ph; 6, R = R′ = t-Bu; 7,
2
2 2
[
RR′SnOSi(Me )CH ] (5, R = R′ = Ph; 6, R = R′ = t-Bu; 7,
R = Me N(CH ) , R′ = Ph)
2
2 2
2
2 3
R = Me N(CH ) , R′ = Ph)
2
2 3
29
δ(119Sn) (ppm)
2J(29Si−117/119Sn) (Hz)
δ( Si) (ppm)
5
6
7
5
6
7
8.6
−31
34
33, 54
Sn(1)−O(1)
Sn(1)−C(1A)
Si(1)−O(1)
Sn(1)−C(11)
Sn(1)−C(21)
Sn(1)−N(14)
1.9815(14)
2.125(2)
1.9687(13)
2.1361(17)
1.6072(13)
2.1739(18)
2.1746(19)
2.020(4)
2.135(6)
1.610(4)
2.141(6)
2.136(6)
2.766(6)
101.8(2)
93.2(2)
1.8
46, 56
1.0; 1.4
−53; −55
42, 49; 38, 47
1.6264(15)
2.137(2)
Scheme 2. Syntheses of the 6-Membered Metallasiloxanes
8−11
2.137(2)
O(1)−Sn(1)−C(1A)
O(1)−Sn(1)−C(11)
O(1)−Sn(1)−C(21)
C(1A)−Sn(1)−C(11)
C(1A)−Sn(1)−C(21)
C(11)−Sn(1)−C(21)
Sn(1)−O(1)−Si(1)
Sn(1)−C(1A)−Si(1A)
N(14)−Sn(1)−O(1)
N(14)−Sn(1)−C(1A)
N(14)−Sn(1)−C(11)
N(14)−Sn(1)−C(21)
103.71(8)
106.62(7)
102.84(7)
118.33(9)
113.91(8)
109.76(8)
137.52(8)
113.86(11)
105.84(7)
100.41(6)
108.76(7)
110.10(7)
113.53(7)
116.81(7)
152.29(9)
117.89(9)
99.8(2)
119.0(3)
116.8(2)
118.1(3)
140.7(2)
116.1(3)
166.94(17)
88.7(2)
Table 3. Selected NMR Data of Compounds 8−11
29
2
J( Si−117/119Sn)
29
δ(119Sn)
(ppm)
2J(119Sn−117/119Sn)
74.7(2)
δ( Si)
ppm)
(
(Hz)
(Hz)
82.1(2)
8
9
1
1
5.9
5.2
43, 49
40, 44
40
−13, −93
49, −98
−23, −89
−59
317/335
351/367
292
0
1
6.5
10.7
42
Bu (μ-OH)Sn(μ -O)SnPh(CH Me SiO)Sn-t-Bu (μ -O)]
2
2
3
2
2
2
3
(
[
13). Recrystallization of the stannasiloxane cyclo-
Me SiCH Ph SnO(t-Bu )SnO] (8) by slow evaporation of a
2
2
2
2
solution of the compound in CH Cl /hexane in aerobic
2
2
Figure 4. Reduced ball-and-stick molecular structures of compounds
conditions gave, as the mixture was dried, a few single crystals
suitable for X-ray diffraction analysis of the ladder-type dimeric
tetraorganodistannoxane [PhSn(CH Me SiO)Sn(μ -O)(μ-
5−7. All exocyclic substituents are omitted for clarity.
2
2
3
+
m/z 611.1 for [8 + H] . An ESI MS spectrum of compound 9
OH)t-Bu ] (12). This is a result of Sn−C bond cleavage
2
2
Ph
in the negative mode showed a major mass cluster centered at
in the presence of moist air (Scheme 3). Chandrasekhar et al.
−
m/z 587.1 which fits exactly with [9 + OH] .
reported before on Sn−C bond cleavage, as the reaction of
Ph
Formation of the Ladderlike Diorganotinoxo Clusters
the diorganotin dichloride Ph SnCl with cycPO H (1,1,2,3,3-
2
2
2
[
PhSn(CH Me SiO)Sn(μ -O)(μ-OH)t-Bu ] (12) and [t-
pentamethyltrimethylenephosphinic acid) gave the monoorga-
2
2
3
2 2
D
DOI: 10.1021/acs.organomet.5b00768
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Organometallics
Article
Scheme 3. Hydrolysis of Compound 8 in Moist Air Giving the Ladder-Type Diorganotinoxo Cluster [PhSn(CH Me SiO)Sn(μ -
2
2
3
O)(μ-OH)t-Bu ] (12)
2
2
Figure 5. General view (SHELXTL) of a molecule of 12 showing 30% probability displacement ellipsoids and the crystallographic numbering
scheme. Carbon-bound hydrogen atoms are omitted for clarity.
1
4
notin oxo cluster [(PhSn) (μ -O)(μ-cycPO ) (μ-OH) ]-
diorganotinoxo clusters.
The signal at δ −219
119 117/119
3
3
2
3
3
1
3
2
119
29
2
[
cycPO2].
Compound 12 is a high-melting solid material that shows
good solubility in CH Cl and CHCl .
( J( Sn − Si) = 41 Hz, J( Snendo
−
Sn ) = 228/
exo
endo
2
119
117
2
42 Hz, J( Snendo− Snendo) = 82 Hz) is assigned to the
2
2
3
endocyclic tin atom (Sn1, Figure 5) in compound 12, while the
In an attempt to synthesize compound 12, a solution of 8 in
2
1 1 9
2 9
signal at δ −260 ( J( Sne x o
−
Si) = 71 Hz,
CH Cl to which a few droplets of water had been added was
2
119
117/119
4
119
117
2
2
J( Sn −
Snendo) = 228/242 Hz, J( Sn − Sn )
84 Hz) belongs to the exocyclic tin (Sn2, Figure 5) (Figure
S50 in the Supporting Information). In addition, resonances at
δ −31 (compound 5, 25%), −38 (11%), and −54 (6%) were
observed. The last two signals are likely related to the
exo
exo
exo
stirred for a few days at room temperature. Surprisingly, no
reaction took place. After the solution was evaporated to
=
29
dryness and the residue kept for a few weeks in moist air, Si
and 1 Sn NMR spectra of the residue in CDCl solution were
19
3
2
9
recorded. A Si NMR spectrum showed two signals, at δ 8.6
for the 8-membered cyclo-stannasiloxane 5 and at δ −2.4 with
J( Si−
hydrolysis products that contain the t-Bu Sn moiety, as they
2
9
do not have corresponding signals in the 2 Si NMR spectrum.
We suppose that the cleavage of the Sn−CPh bond in 8 by
water is facilitated by activation of this bond as a result of an
O→Sn donor−acceptor interaction in the solid state, realized
by dimerization. The O→Sn interaction vanishes upon dilution
2
29
117/119
Sn) coupling constants of 40 and 69 Hz assigned
to 12 (Figure S51 in the Supporting Information). The
corresponding 1 Sn NMR spectrum showed major equally
intense resonances at δ −219 and −260 that are characteristic
for pentacoordinated tin atoms found in ladder-type
19
E
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
in solution), explaining why stirring a solution of compound 8
Article
(
and O(3) for Sn(1) in 12, C(1), O(2), O(3A), and O(3) for
Sn(1) in 13, and C(35), O(2), O(3), and O(4) for Sn(3) in
13). The axial positions are occupied by one carbon atom
(C(11) for Sn(1) in 12 and 13; and C(31) for Sn(3) in 13)
(geometrical parameter τ = 0.32 for Sn(1) in 12; τ = 0.37 and
0.12 for Sn(1) and Sn(3), respectively, in 13). The exocyclic tin
atoms Sn(2) exhibit distorted-trigonal-bipyramidal geometry
with the equatorial positions being occupied by the C(21),
C(25), and O(2) atoms and the axial positions by one silicon-
bound oxygen atom (O(1A) in 12 and O(1) in 13) and one μ2
oxygen atom (O(3) in 12 and O(4) in 13) (geometrical
in presence of water does not afford compound 12.
The rearrangement of 6-membered cyclic stannasiloxanes
upon recrystallization to give the corresponding 12-membered
rings was also described for cyclo-[R Sn(OPh Si) O] (R =
15
2
2
2
n
2
a
CpFeC H ).
5
4
Interestingly, when CDCl was allowed to evaporate slowly
3
from a solution containing 8 (93%), 5 (4%), and t-Bu SnO
2
(
3%), in a not completely closed NMR tube, one single crystal
of the ladderlike hydrolysis product [t-Bu (μ-OH)Sn(μ -
2
3
O)SnPh(CH Me SiO)S-nt-Bu (μ -O)] (13) suitable for X-
2
2
2
3
2
11
ray diffraction analysis was isolated. Compound 13 is formed by
goodness Δ∑(θ) = 72.4° for 12 and 75.9° for 13).
The Sn−O interatomic distances range between 2.0253(18)
and 2.301(2) Å for 12 and between 2.035(2) and 2.273(3) for
insertion of two t-Bu SnO moieties into the Sn−OH bonds in
2
12 (Scheme 4).
1
3. The Snendo−μ -O−Sn bridges are not symmetric (12,
2
exo
Scheme 4. Reaction of Compound 12 with Di-tert-butyltin
Oxide Providing the Hexanuclear Diorganotinoxo Cluster 13
Sn(1)−O(3) 2.0936(18) Å, Sn(2)−O(3) 2.301(2) Å; 13,
Sn(3)−O(4) 2.149(3) Å, Sn(2)−O(4) 2.273(3) Å). With
respect to the central Sn O ring being almost (12) or perfectly
2
2
(
13) planar, the phenyl substituents are cis for 12 but trans for
13.
On the basis of the different Sn−O interatomic distances,
compound 12 can formally and with caution be viewed as a 12-
membered ring showing intramolecular O(2)→Sn(1A)
(
2.1266(16) Å) and O(3)→Sn(2) (2.301(2) Å) interactions.
The alternative view of two head-to-tail linked 6-membered
rings giving a centrosymmetric dimer is less favored, as the
Sn(1)−O(2) distance of 2.0344(17) Å) is much shorter.
Regardless of this, the formal replacement of a tin-bound
phenyl substituent in 8 by a hydroxyl group in 12 enhances the
Lewis acidity at the tin atom in the latter, affording a stronger
O→Sn interaction. Consequently, a ladderlike structure results.
The latter consists of three 4-membered and two 6-membered
rings (Figure 7).
Molecular Structures of the Ladderlike Diorganoti-
noxo Clusters 12 and 13. The compounds 12 and 13
crystallized in the monoclinic space groups P2/n and P2 /n,
1
respectively, with two molecules in the unit cell. The molecular
structures of compounds 12 and 13 are shown in Figures 5 and
, respectively, and selected interatomic distances and bond
angles are summarized in Tables 4 and 5, respectively.
6
Compound 13, on the other hand, comprises the structural
motif [Me SiCH (Ph)Sn(μ -O)O(t-Bu )Sn(μ-OH)Sn(t-Bu )]
2
2
3
2
2
that resembles [cyclo-R Si(OSnt-Bu ) O·t-Bu Sn(OH) ] (R =
2
2 2
18
2
2
16
17
Ph, Me ) and related compounds, by replacing one oxygen
atom with a methylene moiety and one oxygen-bound proton
and one tert-butyl substituent with a tin and oxygen atom,
respectively, belonging to the second half of 13 (Chart 1).
A search in the Cambridge Structural Data Base (CCSD)
revealed 12 entries for hexanuclear tin oxo clusters that are
ladderlike, as for compound 13, but show different con-
1
9
nectivities. Eight of them represent open-drum structures,
20
two contain both di- and triorganotin moieties, 1and two show
2
the presence of Sn−O as well as Sn−N bonds.
In conclusion, a series of novel metallasiloxanes cyclo-
[
7
RR′SnOSi(Me )CH ] (5, R = R′ = Ph; 6, R = R′ = t-Bu;
2
2 2
Figure 6. General view (SHELXTL) of a molecule of 13 showing 30%
probability displacement ellipsoids and the crystallographic numbering
scheme. The methyl carbon atoms of the tert-butyl substituents are
omitted for clarity. Only the Cipso carbon atoms (C11, C11A) of the
phenyl substituents are shown. Carbon-bound hydrogen atoms are
omitted for clarity.
, R = Me N(CH ) , R′ = Ph) and cyclo-[Me SiCH (RR′)-
2
2 3
2
2
SnOMO] (8, R = R′ = Ph, M = t-Bu Sn; 9, R = R′ = t-Bu, M =
2
t-Bu Sn; 10, R = Me N(CH ) , R′ = Ph, M = t-Bu Sn; 11, R =
2
2
2 3
2
Me N(CH ) , R′ = Ph, M = Ph Ge) were synthesized and
2
2 3
2
characterized. On contact with air moisture, compound 8
surprisingly undergoes Sn−C bond cleavage to give the
Ph
ladderlike diorganotin oxo cluster [PhSn(CH Me SiO)(μ -
Both 12 and 13 exist as ladder-type compounds that contain
pentacoordinated tin atoms. They can be viewed as symmetric
dimers, as one half of the molecules comprises the crystallo-
graphic asymmetric unit and the other half is generated by a C2
proper axis (in compound 12) or inversion center (in
compound 13). The endocyclic tin atoms have square-
pyramidal environments with one carbon atom and three
oxygen atoms in the equatorial positions (C(1), O(2), O(2A),
2
2
3
O)Sn(μ-OH)t-Bu
equiv of t-Bu SnO, affording the hexanuclear diorganotinoxo
cluster [(t-Bu )(μ-OH)Sn(μ -O)Sn(Ph)(CH Me SiO)Sn(t-
Bu )(μ -O)]
] (12). The latter reacts with 2 molar
2 2
2
2
3
2
2
(13). The cyclic metallasiloxanes 5−11 hold
2
3
2
potential as single-source precursors for new inorganic
polymers and structurally modified polysiloxanes by the so-
2a
called ring-opening polymerization.
F
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Table 4. Selected Interatomic Distances (Å) and Bond Angles (deg) in 12
Sn(1)−O(2)
Sn(1)−O(2A)
Sn(1)−O(3)
Sn(1)−C(1)
2.0344(17)
2.1266(16)
2.0936(18)
2.119(3)
Sn(2)−O(2)
Sn(2)−O(3)
Sn(2)−O(1A)
Sn(2)−C(21)
Sn(2)−C(25)
2.0329(16)
2.301(2)
2.0253(18)
2.167(3)
Sn(1)−C(11)
2.123(3)
2.165(3)
Si(1)−O(1)
1.5993(19)
146.87(7)
73.54(7)
O(3)−Sn(1)−O(2A)
O(3)−Sn(1)−O(2)
O(3)−Sn(1)−C(1)
O(3)−Sn(1)−C(11)
O(2A)−Sn(1)−O(2)
O(2A)−Sn(1)−C(1)
O(2A)−Sn(1)−C(11)
O(2)−Sn(1)−C(1)
O(2)−Sn(1)−C(11)
C(1)−Sn(1)−C(11)
Sn(1)−C(1)−Si(1)
O(3)−Sn(2)−O(1A)
O(3)−Sn(2)−O(2)
O(3)−Sn(2)−C(21)
O(3)−Sn(2)−C(25)
O(1A)−Sn(2)−O(2)
O(1A)−Sn(2)−C(21)
O(1A)−Sn(2)−C(25)
O(2)−Sn(2)−C(21)
O(2)−Sn(2)−C(25)
C(21)−Sn(2)−C(25)
Sn(2A)−O(1)−Si(1)
155.92(7)
69.22(7)
99.68(9)
94.60(10)
90.60(10)
87.32(7)
99.25(10)
74.30(7)
93.59(8)
99.80(10)
98.04(9)
98.78(9)
127.54(9)
109.68(9)
122.67(11)
114.29(13)
113.29(9)
122.73(10)
121.58(11)
143.13(11)
Table 5. Selected Interatomic Distances (Å) and Bond Angles (deg) in 13
Sn(1)−O(2)
Sn(1)−O(3A)
2.128(2)
2.141(2)
Sn(2)−C(21)
Sn(2)−C(25)
2.191(4)
2.200(5)
Sn(1)−O(3)
2.040(3)
Sn(3)−O(4)
2.149(3)
Sn(1)−C(1)
2.119(4)
Sn(3)−O(3)
2.161(2)
Sn(1)−C(11)
2.121(5)
Sn(3)−O(2)
2.049(3)
Sn(2)−O(1)
2.060(3)
Sn(3)−C(31)
2.195(5)
Sn(2)−O(4)
2.273(3)
Sn(3)−C(35)
2.186(5)
Sn(2)−O(2)
2.035(2)
Si(1)−O(1)
1.612(3)
O(2)−Sn(1)−O(3A)
O(2)−Sn(1)−O(3)
O(2)−Sn(1)−C(1)
O(2)−Sn(1)−C(11)
O(3A)−Sn(1)−O(3)
O(1)−Sn(2)−O(4)
O(1)−Sn(2)−O(2)
O(1)−Sn(2)−C(21)
O(1)−Sn(2)−C(25)
O(4)−Sn(2)−O(2)
O(4)−Sn(3)−O(3)
O(4)−Sn(3)−O(2)
O(4)−Sn(3)−C(31)
O(4)−Sn(3)−C(35)
O(3)−Sn(3)−O(2)
Sn(1)−O(2)−Sn(2)
Sn(1)−O(3)−Sn(3)
Sn(2)−O(4)−Sn(3)
Sn(3)−O(3)−Sn(1A)
Si(1)−C(1)−Sn(1)
151.44(10)
74.62(10)
93.09(13)
98.53(13)
78.07(11)
156.15(10)
86.92(10)
97.42(15)
98.14(15)
69.24(11)
141.87(11)
71.54(11)
100.78(14)
93.83(14)
73.74(9)
O(3A)−Sn(1)−C(1)
O(3A)−Sn(1)−C(11)
O(3)−Sn(1)−C(1)
O(3)−Sn(1)−C(11)
C(1)−Sn(1)−C(11)
O(4)−Sn(2)−C(21)
O(4)−Sn(2)−C(25)
O(2)−Sn(2)−C(21)
O(2)−Sn(2)−C(25)
C(21)−Sn(2)−C(25)
O(3)−Sn(3)−C(31)
O(3)−Sn(3)−C(35)
O(2)−Sn(3)−C(31)
O(2)−Sn(3)−C(35)
C(31)−Sn(3)−C(35)
Sn(1)−O(2)−Sn(3)
Sn(1)−O(3)−Sn(1A)
Sn(2)−O(2)−Sn(3)
Si(1)−O(1)−Sn(2)
97.64(12)
98.63(13)
129.00(15)
110.36(13)
120.45(16)
93.28(15)
94.14(16)
118.06(14)
118.41(14)
121.88(17)
105.52(14)
99.52(13)
110.09(15)
134.66(15)
114.81(19)
105.66(10)
101.93(11)
116.05(13)
138.74(17)
137.16(13)
104.75(10)
103.10(13)
153.32(14)
113.8(2)
were performed for compounds that are oils. The electrospray mass
spectra were recorded with a Thermoquest-Finnigan instrument, using
CH CN or CH Cl as the mobile phase.
EXPERIMENTAL SECTION
■
General Considerations. The solvents used for the Grignard-type
reactions were purified by distillation under argon from the
3
2
2
2
2
23
Crystallography. Intensity data for all crystals were collected on a
XcaliburS CCD diffractometer (Oxford Diffraction) using Mo Kα
radiation at 173 K. The structures were solved with direct methods
appropriate drying agents. Me (i-PrO)SiCH Cl, Me N(CH ) Cl,
2
2
2
2 3
24
and (t-Bu SnO)3 were synthesized according to literature methods.
2
Ph GeO was synthesized by a procedure modified from that described
2
26
2
25
using SHELXS-2014/7, and refinements were carried out against F
in the literature. Triphenyltin chloride and diphenylgermanium
dichloride were commercially available, and they were used without
further purification. Bruker DPX-300, DRX-400, and AVIII-600
2
6
by using SHELXL-2014/7. The C−H hydrogen atoms were
positioned with idealized geometry and refined using a riding model.
All non-hydrogen atoms were refined using anisotropic displacement
parameters. The studied crystal of compound 7 was a nonmerohedral
twin. Refinement of the fractional contributions of the two twin
components yielded a ratio of 0.55969:0.44031. The twin operation is
a 180° rotation about the c axis. Both of the compounds exist in the
1
13
29
119
spectrometers were used to obtain H, C, Si, and Sn NMR
spectra at ambient temperature. Solution H, C, Si-INEPT, and
1
13
29
1
19
Sn NMR chemical shifts are given in ppm and were referenced to
1
13
29
119
Me Si ( H, C, Si), and Me Sn ( Sn). Elemental analyses were
4
4
performed on a LECO-CHNS-932 analyzer. No elemental analyses
G
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Figure 7. Reduced ball and stick molecular structures of compounds 12 (left) and 13 (right). The organic substituents are omitted for clarity. For
simplification, the Sn−O interatomic distances (Å) are given without standard deviations.
3
13
117/119
Hz, J( C−
Sn) = 12 Hz, Me Si), 26.3 (Me CH), 65.51 (CHO),
Chart 1. Schematic Presentation of the Structural Similarity
2
2
2
13
117/119
1
29.0 (C ), 129.4 (C ), 137.8 ( J( C−
Sn) = 38 Hz, C ), 140.5
between [cyclo-R Si(OSnt-Bu ) O·t-Bu Sn(OH) ] (Left; R =
m
p
o
2
2 2
2
2
1
13
117/119
29
1
16
17
( J( C−
Sn) = 488/512 Hz, C ). Si{ H} NMR (59.63 MHz,
i
Ph, Me ) and Compound 13 (Right)
2
29
117/119
2
29
13
C D ): δ 14.2 ( J( Si−
Sn) = 25 Hz, J( Si− C) = 57 Hz).
6
19
6
1
1
1 119 13
Sn{ H} NMR (111.92 MHz, C D ): δ −89 ( J( Sn− CCH2) =
6
6
71 Hz, 1J( Sn− C ) = 513 Hz). Electrospray MS: m/z (%),
119
13
2
Ph
+
+
positive mode, calcd for [1 − Ph] (C H OSiSn ) 405.0699, found
18
25
4
05.1.
Synthesis of {Me (i-PrO)SiCH }SnPh I (2). Elemental iodine
2
2
2
(
2.64 g, 10.4 mmol) was added in small portions at 0 °C to a solution
of 1 (5.00 g, 10.4 mmol) in CH Cl (50 mL), and the mixture was
2
2
warmed to reach room temperature and stirred overnight. Removal of
the solvent and iodobenzene in vacuo gave 5.07 g (92%) of compound
2
as a colorless oil.
trans conformation. In compound 13 one tert-butyl group is affected
by disorder and was refined by a split model over two positions. Their
occupancies were allowed to refine freely until a constant number
1
H NMR (400.13 MHz, CDCl ): δ 0.25 (s, 6H, Me Si), 1.06 (d, 6H,
3
2
3
1
1
2
1
117/119
J( H− H) = 6.0 Hz, Me CH), 1.15 (s, 2H, J( H−
Sn) = 87.4/
2
3
1
1
(
0.74627/0.25373) was obtained.
CCDC-1409967 (5), CCDC-1409968 (6), CCDC-1409969 (7),
91.4 Hz, SiCH
7.88 (m, 10H, Ar H). C{ H} NMR (100.63 MHz, CDCl
2
Sn), 4.01 (m, 1H, J( H− H) = 6.1 Hz, CHO), 7.43−
1
3
1
): δ 1.2
Si), 4.6
Sn) = 251/262 Hz, J( C− Si) = 57 Hz, SiCH Sn),
Sn) = 61 Hz, C ),
Sn) = 50
3
1
13
29
3
13
117/119
CCDC-1409970 (12), and CCDC-1409971 (13) contain supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
( J( C− Si) = 58 Hz, J( C−
Sn) = 15 Hz, Me
2
1
13
117/119
1
13
29
( J( C−
25.5 (Me
2
3
13
117/119
CH), 65.5 (CHO), 128.5 ( J( C−
2
m
4
13
117/119
2
13
117/119
129.6 ( J( C−
Sn) = 14 Hz, C ), 136.0 ( J( C−
p
29
1
13
117/119
1
For decimal rounding of numerical parameters and su values the
Hz, C
(59.63 MHz, CDCl
NMR (111.91, CDCl
o
), 138.4 ( J( C−
Sn) = 536/562 Hz, C ). Si{ H} NMR
i
27
2
29
117/119
119
1
IUCr rules have been employed.
3
): δ 15.1 ( J( Si−
): δ −67 (92%, J( Sn− CCH2) = 263 Hz,
Sn) = 30 Hz). Sn{ H}
1
119
13
Synthesis of Diphenylgermanium Oxide, Ph GeO. A solution
3
2
1
119
13
of sodium hydroxide (300 mg, 7.5 mmol) in a mixture of water (15
mL) and ethanol (10 mL) was added to a solution of Ph GeCl (280
J( Sn− C ) = 561 Hz), −7 (1%), −60 (3%), −114 (2%, Ph SnI),
Ph
3
2
2
−217 (2%, Me (i-PrO)SiCH PhSnI ). Electrospray MS: m/z (%),
2
2
2
positive mode, calcd for [O(Me SiCH SnPh ) + OH]+
mg, 0.94 mmol) in CH Cl (15 mL). The reaction mixture was stirred
2
2
2 2 2 2
for 3 days at room temperature before CH Cl and ethanol were
+
2
2
(C H O Si Sn ) 723.0380, found 723.1.
30 37 2 2 2
evaporated. The residue was extracted with CH Cl . The organic
2
2
Synthesis of a Mixture Consisting of {Me (i-PrO)SiCH }t-
2
2 2
phase was separated, and CH Cl was evaporated to give Ph GeO
Bu SnX (3, X = Cl; 3′, X = OH). A Grignard reagent prepared from
2
2
2
(
0.21 g, 92%) as a white solid with mp 148 °C.
Me (i-PrO)SiCH Cl (2.19 g, 13.16 mmol) and magnesium turnings
2
2
1
H NMR (400.13 MHz, C D ): δ 7.30−7.63 (m, 10H, Ar H).
(0.35 g, 14.48 mmol) in THF (30 mL) was added dropwise at −50 °C
over a period of 1 h to a solution of t-Bu SnCl (4.00 g, 13.16 mmol)
6
6
1
3
1
C{ H} NMR (75.48 MHz, C D ): δ 128.2 (C ), 130.3 (C ), 133.6
6
6
m
p
2
2
C ), 135.9 (C ). Electrospray MS: m/z (%), positive mode, calcd for
in THF (15 mL), and the mixture was warmed to room temperature
and stirred overnight. The solvent was evaporated, hexane (100 mL)
was added, and the mixture was stirred for 15 min before it was filtered
under inert conditions. Hexane was evaporated, and the residue was
distilled at 133−138 °C in vacuo (9 mbar), giving 3.95 g of a mixture
of two compounds with a ratio (4:1) according to the Sn NMR
spectrum that could be related to compounds 3 and 3′ (resulting from
hydrolysis of compound 3). No attempts were made to separate the
two compounds, and the mixture was used for the synthesis of
o
i
+
+
2 3 36 31 3 3
12
10
9.5, H, 4.2.
Synthesis of Me (i-PrO)SiCH SnPh (1). A solution of
2
2
3
1
19
2
2
compound 7 (see below).
1
Compound 3. H NMR (400.13 MHz, CDCl ): δ 0.21 (s, 6H,
3
2
1
117/119
Me Si), 0.29 (s, 2H, J( H−
Sn) = 64.2/66.8 Hz, SiCH Sn), 1.15
2
2
3
1
1
3
1
117/119
(d, 6H, J( H− H) = 6.3 Hz, Me CH), 1.32 (s, 18H, J( H−
Sn)
2
3
1
1
(121.30 g, 93%) was obtained as a colorless liquid.
= 80.8/84.8 Hz, t-Bu Sn), 4.01 (m, 1H, J( H− H) = 6.0 Hz, CHO).
2
1
13 1 1 13
117/119
13 29
H NMR (300.13 MHz, C D ): δ 0.16 (s, 6H, Me Si), 0.55 (s, 2H,
C{ H} NMR (100.63 MHz, CDCl ): δ −0.1 ( J( C−
Sn) =
6
6
2
3
1
117/119
3
1
1
1
13
29
1
Sn) = 75.1/77.2 Hz, SiCH Sn), 1.08 (d, 6H, J( H− H)
2
111/115 Hz, J( C− Si) = 58 Hz, SiCH Sn), 1.1 ( J( C− Si) = 58
3 13 117/119
2
5.8 Hz, Me CH), 3.87 (m, 1H, CHO), 7.27−7.77 (m, 15H, Ar H).
Hz, J( C−
Sn) = 9 Hz, Me Si), 25.8 (Me CH), 29.9 (Me C),
2
2 2 3
1
1
13
29
1
13
117/119
C{ H} NMR (75.48 MHz, C D ): δ −3.7 ( J( C− Si) = 60 Hz,
34.9 ( J( C−
Sn) = 371/389 Hz, Me CSn), 65.1 (CHO).
3
6
6
13
117/119
1
13
29
29
1
2
29
117/119
Sn) = 258/270 Hz, SiCH Sn), 1.9 ( J( C− Si) = 58
Si{ H} NMR (59.63 MHz, CDCl ): δ 14.66 ( J( Si−
Sn) = 16
2
3
H
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
1
29
13
119
1
29
1
Hz, J( Si− C) = 58 Hz). Sn{ H} NMR (111.92 MHz, CDCl ): δ
Me CSn).
Si{ H} NMR (59.63 MHz, CDCl ): δ 1.8
3
3
3
2
29
117/119
2
29
117/119
119
1
22 (80%).
( J( Si−
Sn) = 46 Hz, J( Si−
Sn) = 56/60 Hz). Sn-
1
1
1
119
13
Compound 3′. H NMR (400.13 MHz, CDCl ): δ 0.21 (s, 6H,
{ H} NMR (111.92 MHz, CDCl ): δ 34 ( J( Sn− CCH ) = 198
3
3
2
2
1
117/119
1
119
13
2
119
29
Me Si), 0.35 (s, 2H, J( H−
Sn) = 62.8/65.0 Hz, SiCH Sn), 1.15
Hz, J( Sn− Ct-Bu) = 428 Hz, J( Sn− Si) = 48 Hz,
2 119 29
2
2
3
1
1
3
1
117/119
(
d, 6H, J( H− H) = 6.3 Hz, Me CH), 1.33 (s, 18H, J( H−
Sn)
J( Sn− Si) = 60 Hz). Electrospray MS: m/z (%), positive mode,
+ +
2
3
1
1
=
81.8/85.3 Hz, t-Bu Sn), 4.01 (m, 1H, J( H− H) = 6.0 Hz, CHO).
calcd for [6 + H] (C H O Si Sn ) 643.1630, found 643.2; calcd for
22 53 2 2 2
2
1
3
1
1
13
117/119
13 29
+
+
C{ H} NMR (100.63 MHz, CDCl ): δ 0.0 ( J( C−
Sn) =
[Me (HO)SiCH (t-Bu )Sn] (C H OSiSn ) 323.0854, found 323.0.
Anal. Calcd for C22
Found: C, 41.1; H, 8.2.
Synthesis of cyclo-[{Me
Elemental iodine (0.76 g, 3.00 mmol) was added in portions at 0
°C to a solution of compound 4 (1.47 g, 3.00 mmol) in CH Cl (50
mL). After the addition was complete, the mixture was warmed to
room temperature and stirred overnight, before the solvent and
iodobenzene were removed in vacuo to give [Me (i-PrO)SiCH ]-
3
2
2
2
11 27
1
13
29
1
1
03/107 Hz, J( C− Si) = 58 Hz, SiCH Sn), 1.2 ( J( C− Si) = 58
H
52
O
2
Si
Sn
2
2
(642.20 g/mol): C, 41.14; H, 8.16.
2
3
13
117/119
Hz, J( C−
Sn) = 9 Hz, Me Si), 25.8 (Me CH), 30.0 (Me C),
Sn) = 361/378 Hz, Me CSn), 65.1 (CHO).
2
2
3
1
13
117/119
3
4.6 ( J( C−
2
N(CH
2
)
3
}PhSnOSi(Me
2
)CH
2
]
2
(7).
3
2
1
9
1
1
29
13
Si{ H} NMR (59.63 MHz, CDCl ): δ 14.71 ( J( Si− C) = 58 Hz).
3
19
1
Sn{ H} NMR (111.92 MHz, CDCl ): δ 128 (20%). Electrospray
2
2
3
+
MS: m/z (%), positive mode, calcd for [Me (i-PrO)SiCH (t-Bu )Sn]
2
2
2
+
(
C H OSiSn ) 365.1324, found 365.1.
14 33
2
2
Synthesis of {Me (i-PrO)SiCH }{Me N(CH ) }SnPh (4). A
Grignard reagent prepared from Me N(CH ) Cl (610 mg, 5.00
2
2
2
2 3
2
PhRSnI (R = Me N(CH ) , 1.40 g, 86%) as a yellowish viscous oil that
was not purified further. Its Si{ H} NMR spectrum (59.63 MHz,
2
2 3
2
2
3
29
1
mmol) and magnesium turnings (134 mg, 5.50 mmol) in THF (10
mL) was added at room temperature to a solution of 2 (2.12 g, 4.00
mmol) in THF (15 mL), and the mixture was stirred overnight. The
solvent was evaporated, and hexane (50 mL) was added. The mixture
obtained was filtered under inert conditions. The solvent of the filtrate
was evaporated in vacuo to give compound 4 (1.63 g, 83%) as a
colorless oil that was not purified further.
2
29
117/119
CDCl ) showed a major resonance at δ 9.4 ( J( Si−
Sn) = 20
Hz) and a minor resonance at δ 19.4. A Sn{ H} NMR spectrum
111.92 MHz, CDCl ) of the same solution revealed two signals of
3
119
1
(
3
different integral ratios at δ 3 (87%) and −4 (13%), respectively.
A solution of sodium hydroxide (0.55 g, 13.75 mmol) in water (40
mL) and ethanol (10 mL) was added to a solution of [Me (i-
]PhRSnI (1.40 g, 2.60 mmol) in CH
mixture was stirred for 3 days at room temperature before CH
ethanol were evaporated in vacuo. The residue was extracted with
CH Cl . The organic phase was separated, and the solvent was
evaporated to give compound 7 (0.89 g, 92%) as a light yellowish
2
1
PrO)SiCH
2
2
Cl
2
(25 mL), and the
H NMR (300.13 MHz, CDCl ): δ 0.06 (s, 6H, Me Si), 0.32 (s, 2H,
3
2
2
1
117/119
3
1
1
2
Cl and
2
J( H−
Sn) = 73.6 Hz, SiCH Sn), 1.11 (d, 6H, J( H− H) = 5.8
2
Hz, Me CH), 1.31 (t, 2H, CH CH Sn), 1.81 (m, 2H, CH CH CH ),
2
2
2
2
2
2
2
2
2
7
(
.17 (s, 6H, Me N), 2.28 (t, 2H, CH N), 3.98 (m, 1H, CHO), 7.34−
2
2
29 1
.63 (m, 10H, Ar H). Si{ H} NMR (59.63 MHz, CDCl ): δ 15.1
3
solid. Recrystallization from CHCl afforded colorless single crystals
2
29
117/119
119
1
3
J( Si−
Sn) = 18 Hz). Sn{ H} NMR (111.92 MHz, CDCl ):
3
with mp 142.5−144.5 °C suitable for X-ray diffraction analysis.
δ −62.
1
H NMR (400.25 MHz, C D ): δ 0.14 (complex pattern, 4H), 0.29
6
6
Synthesis of cyclo-[Ph SnOSi(Me )CH ] (5). A solution of
2
2
2 2
(
s, 3H, SiCH ), 0.32 (s, 3H, SiCH ), 0.47 (s, 3H, SiCH ), 0.51 (s, 3H,
3 3 3
sodium hydroxide (0.90 g, 22.6 mmol) in water (50 mL) and ethanol
10 mL) was added to a solution of 2 (1.50 g, 2.82 mmol) in CH Cl
25 mL), and the mixture was stirred for 3 days at room temperature
before CH Cl and ethanol were evaporated in vacuo. The residue was
extracted with CH Cl . The organic phase was separated, and the
solvent was evaporated. The residue was recrystallized from a solution
in CH Cl /hexane to give 0.98 g (96%) of 5 as colorless crystals with
SiCH ), 1.44 (s, 12H, NCH ) 1.22−2.00 (complex patterns, 12H,
3
3
(
(
2 2
SnCH CH CH N), 7.21−7.32 (complex pattern, 6H, Ph-H , ), 7.66
2
2
2
m p
(
complex pattern, 1H, Ph-H ), 7.68 (complex pattern, 1H, Ph-H ),
o
o
2
2
7.75 (complex pattern, 1H, Ph-H ), 7.77 (complex pattern, 1H, Ph-
o
13
1
1
13
117/119
2
2
Ho). C{ H} NMR (150.94 MHz, C D ): δ 3.68 ( J( C−
Sn) =
7
8
1
13
117/119
3
61/379 Hz, SiCH Sn), 3.89 ( J( C−
Sn) = 365/382 Hz,
2
2
2
SiCH Sn), 5.40 (MeSi), 5.70 (MeSi), 5.75 (MeSi), 6.08 (MeSi), 14.83
2
mp 167−169 °C suitable for X-ray diffraction analysis.
1
13
117/119
(
J( C−
117/119
Sn)
= 528/554 Hz, CH CH Sn), 14.97
2 2
1
H NMR (300.13 MHz, CDCl ): δ 0.15 (s, 12H, Me Si), 0.58 (s,
1
13
3
2
( J( C−
Sn) = 531/567 Hz, CH CH Sn), 22.65 (CH CH CH ),
2
2
2
2
2
2
1
117/119
Sn) = 73.6/76.5 Hz, SiCH Sn), 7.37−7.78 (m, 20H,
1 1 13 29
4
H, J( H−
2
22.76 (CH CH CH ), 46.02 (Me N), 46.05 (Me N), 61.49 (CH N),
2 2 2 2 2 2
13
Ar H). C{ H} NMR (75.48 MHz, CDCl ): δ 3.3 ( J( C− Si) = 84
3
61.55 (CH N), 128.05 (C ), 128.20 (C ), 128.21 (C ), 135.82 (C ),
2 m p p o
1
13
117/119
1
13
29
Hz, J( C−
Sn) = 326/341 Hz, SiCH Sn), 4.5 ( J( C− Si) =
1
13
117/119
2
135.94 (C ), 147.58 ( J( C−
Sn) = 592/619 Hz, C ), 146.7
o
i
3
13
117/119
3
13
117/119
5
5
(
9 Hz, J( C−
Sn) = 18 Hz, Me Si), 128.4 ( J( C−
Sn) =
1
13
117/119
29
29
1
2
( J( C−
Sn) = 586/614 Hz, C ). Si{ H} NMR (79.52, CDCl ):
δ 1.4 ( J( Si−
i
3
4
13
117/119
2
117/119
2
29
117/119
8 Hz, C ), 129.4 ( J( C−
Sn) = 12 Hz, C ), 135.9
m
p
Sn) = 39/47 Hz), 1.0 ( J( Si−
Sn) = 40/48
2
13
117/119
1
13
117/119
Hz), 4.7. 29Si{ H} NMR (79.52 MHz, C D ): δ −0.4, −0.9. Sn{ H}
1
119
1
J( C−
Sn) = 46 Hz, C ), 142.1 ( J( C−
Sn) = 572/
o
7
8
2
9
1
2 119 29
5
99 Hz, C ). Si{ H} NMR (59.63 MHz, CDCl ): δ 8.6
i
3
NMR (149.26 MHz, C D ): T = 298 K, δ −62.6 (45%, J( Sn− Si)
7
8
2
29
117/119
2
29
117/119
1
29
13
2
119
29
(
J( Si−
Sn) = 33 Hz, J( Si−
Sn) = 54 Hz, J( Si− C)
=
46 Hz), −62.8 (52%, J( Sn− Si) = 46 Hz), 70.4 (3%); T = 333
1
19
1
119 1
=
(
87 Hz).
Sn{ H} NMR (111.92 MHz, CDCl ): δ −31
K, δ −54.2 (45%), −54.4 (52%), −64.0 (3%).
Sn{ H} NMR
3
1J( Sn− CH ) = 341 Hz, J( Sn− Ci) = 598 Hz). Electrospray
119
13
1
119
13
2
119
29
2
(111.92 MHz, CDCl ): δ −55 (50%, J( Sn− Si) = 48 Hz), −53
3
+
+
2
2 119 29
MS: m/z (%), positive mode, calcd for [5 + H] (C H O Si Sn )
(43%, J( Sn − Si) = 48 Hz), −66 (4%), 4 (3%). Electrospray MS:
30
37
2
2
+
+
7
23.0380, found 723.1. Anal. Calcd for C H O Si Sn (722.20 g/
m/z (%), positive mode, calcd for [7 + H] (C H N O Si Sn )
28 51 2 2 2 2
30
36
2
2
2
mol): C, 49.89; H, 5.02. Found: C, 49.8; H, 5.1.
Synthesis of cyclo-[t-Bu SnOSi(Me )CH ] (6). A solution of
741.1536, found 741.2; calcd for [{Me (OH)SiCH }{Me N(CH ) }-
2 2 2 2 3
+
+
2
2
2 2
PhSn + 4H O] (C H NO SiSn ) 444.1230, found 444.1. Anal.
2
14 34
5
sodium hydroxide (0.32 g, 8.0 mmol) in water (15 mL) and ethanol
10 mL) was added to a solution of the 3/3′ mixture (0.396 g, 1.0
Calcd for C H N O Si Sn (740.266 g/mol): C, 45.43; H, 6.81; N,
3.78. Found: C, 45.1; H, 7.2; N, 4.1.
28 50 2 2 2 2
(
+
mmol based on [Me (i-PrO)SiCH Sn(t-Bu) ] ) in CH Cl (15 mL)
Synthesis of cyclo-[Me2SiCH2(Ph) SnO-t-Bu SnO] (8). A
2
2
2
2
2
2
2
and the mixture was stirred for 3 days at room temperature before
CH Cl and ethanol were evaporated. The residue was extracted with
mixture of di-tert-butyltin oxide (100 mg, 0.40 mmol) and 5 (145
mg, 0.20 mmol) in CH Cl (3 mL) was stirred for 10 min at room
2
2
2
2
CH Cl . The organic phase was separated, and the solvent was
temperature. Then the solvent was evaporated, giving a white solid
2
2
evaporated before the residue was recrystallized from a solution in
with mp 145−149 °C.
1
CH Cl /hexane to give 0.29 g (90%) of 6 as colorless crystals with mp
H NMR (400.13 MHz, CDCl ): δ 0.18 (s, 6H, Me Si), 0.56 (s, 2H,
2
2
3
2
2
3
1
117/119
1
00.5−102.5 °C suitable for X-ray diffraction analysis.
J( H−
Sn) = 71.3/73.8 Hz, SiCH Sn), 1.36 (s, 18H,
2
1
H NMR (400.13 MHz, CDCl ): δ −0.10 (s, 4H, J( H−117/119Sn)
2
1
1
117/119
1
3
J( H−
Sn) = 91.4/95.9 Hz, Me3CSn), 7.37−7.73 (m, 10H, Ar
H). 13C{ H} NMR (100.63 MHz, CDCl ): δ 3.0 ( J( C−
1
13
117/119
Sn) =
Sn)
=
55.0 Hz, SiCH Sn), 0.12 (s, 12H, Me Si), 1.2 (s, 36H,
2
2
3
3
1
117/119
13
1
1
13
29
3
13
117/119
J( H−
Sn) = 71.8/75.3 Hz, Me CSn). C{ H} NMR (100.63
282/295 Hz, SiCH2Sn), 4.4 ( J( C− Si) = 59 Hz, J( C−
3
1
13
117/119
29
1
13
29
MHz, CDCl ): δ −0.8 ( J( C−
Sn) = 190/198 Hz, J( C− Si)
= 17 Hz, Me Si), 29.8 (Me3C), 38.4 (Me3CSn), 128.4
3
2
1
13
3
13
117/119
3
13
117/119
2
4
13
117/119
1
=
54 Hz, SiCH Sn), 5.4 ( J( C− Si) = 59 Hz, J( C−
Sn) = 15
( J( C−
Sn) = 57 Hz, Cm), 129.3 ( J( C−
Sn) = 13 Hz,
2
1
13
117/119
13
117/119
13
117
Hz, Me Si), 30.0 (Me C), 31.5 ( J( C−
Sn) = 409/428 Hz,
Cp), 135.7 ( J( C−
Sn) = 47 Hz, Co), 142.5 ( J( C− Sn) =
2
3
I
DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
1
13
119
29
1
29
1
2
29
117/119
5
68 Hz, J( C− Sn) = 595 Hz, Ci). Si{ H} NMR (59.63 MHz,
Si{ H} NMR (59.63 MHz, CDCl ): δ 8.5 ( J( Si−
Sn) =
3
2
29
117/119
1
2
29
117/119
2
29
117/119
119
29
1
CDCl ): δ 5.9 ( J( Si−
Snt-Bu) = 43 Hz, J( Si−
SnPh) =
33/54 Hz, 5), −2.4 ( J( Si−
(111.92 MHz, CDCl ): δ −219 [29%, J( Snendo− Si) = 41 Hz,
Sn) = 40/69 Hz). Sn{ H} NMR
3
1
19
2
119
119
4
9 Hz), 8.5 (5). Sn{ H} NMR (111.91 MHz, CDCl ): δ −13
3
3
2
119
117
2
119
119
2
119
29
2
119
117/119
2
117
[
J( Sn− Sn) = 317 Hz, J( Sn− Sn) = 334 Hz, J( Sn− Si)
J( Snendo
−
Snexo) = 228/242 Hz, J( Snendo
−
Snendo) = 82
2
119
117
2
119
29
2
119
117/119
=
51 Hz, CH Sn(Ph )O], −93 [ J( Sn− Sn) = 317 Hz,
Hz], −260 [29%, J( Sn − Si) = 71 Hz, J( Snexo
−
Snendo
Snexo) = 84 Hz], −31 [25%,
J( Sn− Si) = 34, 55 Hz, 5], −38 (11%), −54 (6%). Electrospray
+
)
2
2
exo
2
119
119
2
119
29
= 228/242 Hz, J(119Snexo
−
4
117
J( Sn− Sn) = 337 Hz, J( Sn− Si) = 44 Hz, OSn(t-Bu )O],
2
2
119
29
−
31 (3%, 5), −84 (5%, (t-Bu2SnO)3). Electrospray MS: m/z (%),
+ +
positive mode, calcd for [8 + H] (C H O SiSn ) 611.0609, found
MS: m/z (%), positive mode, calcd for [12 − OH]
2
3
37
2
2
−
−
+
6
3
11.1; calcd for [Me (OH)SiCH (Ph )Sn(OH) ] (C H O SiSn )
97.0284, found 397.0. Anal. Calcd for C H O SiSn (610.04 g/
mol): C, 45.28; H, 5.95. Found: C, 45.3; H, 5.9.
Synthesis of cyclo-[Me2SiCH2(t-Bu) SnO-t-Bu SnO] (9). A
mixture of di-tert-butyltin oxide (60 mg, 0.24 mmol) and 6 (77 mg,
(C34
H
63
O
5
Si
sufficient amount of these crystals to perform elemental analyses.
Formation of the Ladder-Type Cluster [t-Bu (μ-OH)Sn(μ -
2 4
Sn ) 1083.0314, found 1083.1. There was not a
2
2
2
2
15 21
3
2
3
36
2
2
2
3
O)SnPh(CH Me SiO)Sn-t-Bu (μ -O)] (13). A solution containing
the compounds 8 (93%), 6 (4%), and (t-Bu SnO) (3%) in CDCl in
a not completely closed NMR tube was allowed to evaporate slowly,
providing a single crystal of 13. The identity of 13 was established by
single-crystal X-ray diffraction analysis. No further analytical methods
were applied.
2
2
2
3
2
2
2
2
3
3
0
.12 mmol) in CHCl (25 mL) was heated at reflux for 5 h. The
3
mixture was cooled to room temperature, and the solvent was
evaporated in vacuo to give a white solid.
1
H NMR (300.13 MHz, CDCl ): δ −0.00 (s, 2H, J( H−117/119Sn)
2
1
3
=
57.0 Hz, SiCH Sn), 0.17 (s, 6H, Me Si), 1.27 (s, 18H,
2
2
3
1
117/119
ASSOCIATED CONTENT
Supporting Information
J( H−
J( H−
Sn) = 72.7/74.6 Hz, Me CSn), 1.33 (s, 18H,
■
3
3
1
117/119
13
1
S
*
Sn) = 89.3/93.7 Hz, Me CSn). C{ H} NMR (75.47
3
3
13
117/119
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.5b00768.
MHz, CDCl ): δ −1.4 (SnCH Si), 5.0 ( J( C−
Me Si), 30.1 (Me C), 30.4 (Me C), 32.3 (Me CSn), 38.0 (Me CSn).
Si{ H} NMR (59.63 MHz, CDCl ): δ 5.2 ( J( Si−
Hz), 1.8 (6).
Sn) = 9 Hz,
3
2
2
3
3
3
3
2
9
1
2
29
117/119
Sn) = 42
3
119
1
Sn{ H} NMR (111.92 MHz, CDCl ): δ −98
3
NMR spectra and crystallographic data (PDF)
Crystallographic data for 5−7, 12, and 13 (CIF)
2
2
119
117/119
Sn) = 351/367 Hz, 2 J( Sn− Si) = 44 Hz), 49
117/119 119 29
2 119 29
(
(
(
J( Sn−
J( Sn−
119
Sn) = 351/367 Hz, J( Sn− Si) = 41 Hz), −83
3
5%, (t-Bu SnO) ), 34 (5% of the major resonances, 6). Electrospray
2
−
−
AUTHOR INFORMATION
MS: m/z (%), negative mode, calcd for [9 + OH] (C H O SiSn )
87.1183, found 587.1. Anal. Calcd for C H O SiSn (570.06 g/
mol): C, 40.03; H, 7.78. Found: C, 39.7; H, 7.7.
Synthesis of cyclo-[Me2SiCH2{Me N(CH ) }PhSnO-t-Bu SnO]
10). A mixture of di-tert-butyltin oxide (60 mg, 0.240 mmol) and 7
19
45
3
2
■
5
Corresponding Author
E-mail for K.J.: klaus.jurkschat@tu-dortmund.de.
1
9
44
2
2
*
2
2 3
2
Notes
(
(
The authors declare no competing financial interest.
100 mg, 0.135 mmol) in CHCl (25 mL) was heated at reflux for 5 h.
3
The mixture was cooled to room temperature, and the solvent was
evaporated in vacuo, giving a white yellowish solid.
ACKNOWLEDGMENTS
S.B.H. is grateful to Damascus University for a scholarship.
■
29
Si{ H} NMR (59.63 MHz, CDCl ): δ 6.5 ( J( Si−117/119Sn) = 40
1
2
29
3
1
19
1
Hz), 4.5, 1.3, 1.3, 0.9, 3.3. Sn{ H} NMR (111.92 MHz, CDCl ): δ
3
Thomas Zo
diffraction data for compound 13.
̈
ller is acknowledged for recording the X-ray
2
119
117/119
−
23 (45%, J( Sn−
Sn) = 292 Hz), −89 (45%,
2
119
117/119
J( Sn−
Sn) = 292 Hz), −55 (4%, 7), −54 (3%, 7), −66
+
(
(
3%). Electrospray MS: m/z (%), positive mode, calcd for [10 + H]
REFERENCES
+
■
C H NO SiSn ) 620.1187, found 620.1. Anal. Calcd for
2
2
44
2
2
(
1) (a) Chojnowski, J. J. Inorg. Organomet. Polym. 1991, 1, 299−323.
(b) Priegert, A. M.; Rawe, B. W.; Serin, S. C.; Gates, D. P. Chem. Soc.
Rev. 2016, DOI: 10.1039/C5CS00725A.
2) (a) Beckmann, J.; Jurkschat, K. Coord. Chem. Rev. 2001, 215,
67−300 and references cited therein. (b) Fridrichova, A.;
Mairychova, B.; Padelkova, Z.; Lycka, A.; Jurkschat, K.; Jambor, R.;
C H NO SiSn (619.00 g/mol): C, 42.68; H, 7.00; N, 2.26.
2
2
43
2
2
119
Found: C, 42.0; H, 7.0; N, 2.2. As evidenced by
Sn NMR
spectroscopy (additional resonance at δ −66 (3%)), the compound
measured contained a second species, the identity of which could not
be established. This is the origin for the discrepancy between
calculated and measured elemental analyses.
(
2
Dostal, L. Dalton Trans. 2013, 42, 16403−16411.
3) (a) Murugavel, R.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W.
Synthesis of cyclo-[Me2SiCH2{Me N(CH ) }PhSnOPh GeO]
2
2 3
2
(
(
11). A mixture of Ph GeO (56 mg, 0.230 mmol) and 7 (85 mg,
2
Chem. Rev. 1996, 96, 2205−2236. (b) Gates, D. P.; Manners, I. J.
0
.115 mmol) in CHCl (20 mL) was heated at reflux for 5 h. The
3
Chem. Soc., Dalton Trans. 1997, 2525−2532.
mixture was cooled to room temperature, and the solvent was
evaporated in vacuo to give a yellowish oil.
(
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DOI: 10.1021/acs.organomet.5b00768
Organometallics XXXX, XXX, XXX−XXX