Intramolecularly coordinated (6-(Diphenylphosphino)acenaphth-5-yl) stannanes. Repulsion vs attraction of P- and Sn-containing substituents in the peri positions

Article abstract of DOI:10.1021/om500133a

The intramolecularly coordinated (6-(diphenylphosphino)acenaphth-5-yl) stannanes ArSnBu₃ (1), ArSnPh₃ (2), ArSnPh₂Cl (3), ArSnPhCl₂ (4), ArSnCl₃ (5), Ar₂SnCl ₂ (6), ArSnPh₂O₃SCF₃ (7), and ArSnPh₂F (8) were synthesized and fully characterized by multinuclear NMR spectroscopy (¹¹⁹Sn, ³¹P, ¹⁹F, ¹³C, ¹H) and X-ray crystallography (Ar = 6-Ph ₂P-Ace-5-). Due to the different substituents, the Lewis acidities of the Sn atoms of 1-8 vary substantially, which is reflected in the different P-Sn peri distances lying in the range from 2.7032(9) to 3.332(2) A. In MeCN, 7 undergoes electrolytic dissociation into solvated triarylstannyl cations and triflate anions. The gas-phase structures of 2-5, 8, and the triarylstannyl cations ArPh₂Sn⁺ (7a) and [ArPh₂Sn· NCMe]⁺ (7b) were obtained by geometry optimization at the B3PW91/TZ level of theory. A detailed analysis of a set of real-space bonding indicators (RSBI) derived from the electron and pair densities following the atoms in molecules (AIM) and electron localizability indicator (ELI-D) topological approaches, respectively, uncovers the Sn-P peri interaction in 2 to be in the border regime between nonbonding and weakly ionic. With an increasing number of Cl atoms attached to the Sn atom, the Sn-P bond becomes considerably shorter and exhibits a decreasingly polar covalent interaction. As expected, this trend is significantly enhanced for the Sn-P interactions in the charged compounds 7a,b. The Sn-P bond properties of 8, however, very much resemble those of 3, which means that the electronic impact of the F atom in the axial position is comparable to that of the axial Cl atom.

Full text of DOI:10.1021/om500133a

Article
pubs.acs.org/Organometallics
Intramolecularly Coordinated (6-(Diphenylphosphino)acenaphth-5-
yl)stannanes. Repulsion vs Attraction of P- and Sn-Containing
Substituents in the peri Positions
Emanuel Hupf,† Enno Lork,† Stefan Mebs,*,‡ and Jens Beckmann*,†
†Institut fur Anorganische Chemie, Universitat Bremen, Leobener Straße, 28359 Bremen, Germany
̈
̈
̈
‡Institut fur Chemie und Biochemie, Freie Universitat Berlin, Fabeckstraße 36a, 14195 Berlin, Germany
̈
S
* Supporting Information
ABSTRACT: The intramolecularly coordinated (6-
(diphenylphosphino)acenaphth-5-yl)stannanes ArSnBu3 (1),
ArSnPh3 (2), ArSnPh2Cl (3), ArSnPhCl2 (4), ArSnCl3 (5),
Ar2SnCl2 (6), ArSnPh2O3SCF3 (7), and ArSnPh2F (8) were
synthesized and fully characterized by multinuclear NMR
1
spectroscopy (119Sn, 31P, 19F, 13C, H) and X-ray crystallog-
raphy (Ar = 6-Ph2P-Ace-5-). Due to the different substituents,
the Lewis acidities of the Sn atoms of 1−8 vary substantially,
which is reflected in the different P−Sn peri distances lying in
the range from 2.7032(9) to 3.332(2) Å. In MeCN, 7
undergoes electrolytic dissociation into solvated triarylstannyl cations and triflate anions. The gas-phase structures of 2−5, 8, and
the triarylstannyl cations ArPh2Sn+ (7a) and [ArPh2Sn·NCMe]+ (7b) were obtained by geometry optimization at the B3PW91/
TZ level of theory. A detailed analysis of a set of real-space bonding indicators (RSBI) derived from the electron and pair
densities following the atoms in molecules (AIM) and electron localizability indicator (ELI-D) topological approaches,
respectively, uncovers the Sn−P peri interaction in 2 to be in the border regime between nonbonding and weakly ionic. With an
increasing number of Cl atoms attached to the Sn atom, the Sn−P bond becomes considerably shorter and exhibits a
decreasingly polar covalent interaction. As expected, this trend is significantly enhanced for the Sn−P interactions in the charged
compounds 7a,b. The Sn−P bond properties of 8, however, very much resemble those of 3, which means that the electronic
impact of the F atom in the axial position is comparable to that of the axial Cl atom.
interaction (Scheme 1).5,6 However, the closely related (5-
INTRODUCTION
■
(diphenylphosphino)acenaphth-6-yl)dimesitylborane (V; 5-
(Ph2P)-6-(Mes2B)-Ace) comprises a frustrated Lewis pair
(FLP) with a long peri distance (3.050(3) Å).6 In this case
the predominantly repulsive interaction stems from the
conformational rigidity of the acenaphthene moiety, which
outweighs the attraction between the donor and the acceptor
atoms. For the heavier heteroatoms the steric congestion will
arguably increase along with the covalent radii; however, the
consequences for the nature of the interactions are not
apparent. With the elongation of the heteroatom−carbon
bond the conformational flexibility will also increase, which
might in fact reduce the repulsion between the peri
substituents.7 (8-(Dimethylamino)naphthyl)stannanes R3Sn-8-
Me2N-Nap (VI)8 and 6-(bromoacenaphth-5-yl)stannanes 5-
R3Sn-6-Br-Ace (VII)9 are significant subclasses of heavily
substituted naphthalenes and acenaphthenes, in which the N−
Sn and Br−Sn peri interactions are indisputable due to the
119Sn NMR chemical shifts, which are indicative of hyper-
coordinated Sn atoms (R = Cl, Br, I, alkyl, aryl). In general,
Peri-substituted naphthalenes (Nap) and acenaphthenes (Ace)
feature constrained interactions between the substituents in 1,8-
and 5,6-positions that can be either repulsive due to steric
congestion or attractive due to weak or strong bonding.1 With
few exceptions, the peri interactions were analyzed solely by the
inspection of geometrical bond parameters, which provide a
good impression of the (non)bonding character for clear-cut
cases. 1,8-Bis(trimethylsilyl)naphthalene (I; 1,8-(Me3Si)2-Nap),
possessing an extremely long peri distance (3.803(4) Å), is a
compelling example for strongly repulsive interactions (Scheme
1).2 1,8-Bis(diphenylphosphino)naphthalene (II; 1,8-(Ph2P)2-
Nap) is another straightforward case in which the two lone
pairs impose repulsion, leading to a moderately long peri
distance (3.052(2) Å).3 In contrast, the related 5-(dichloro-
phosphino)-6-(diisopropylphosphino)acenaphthene (III; 5-
(Cl2P)-6-(i-Pr2P)-Ace) gives rise to a short peri distance
(2.257(1) Å) due to the different substituents attached to the P
atoms, pointing to a strongly attractive interaction.4
In (1-(diphenylphosphino)naphth-8-yl)dimesitylborane (IV;
1-(Ph2P)-8-(Mes2B)-Nap) the combination of a donor and an
acceptor atom affords a Lewis pair with a short peri distance
(2.162(2) Å) that is indicative of a strongly attractive
Received: February 12, 2014
© XXXX American Chemical Society
A
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Scheme 1. peri-Substituted Naphthalenes I, II, IV, and VI as well as Acenaphthenes III, V, VII, and VIII and Selected peri
Distances
Scheme 2. Synthesis and Selected NMR Parameters (CDCl3) of 1−3
intramolecularly coordinated organostannanes containing N
and O donor atoms have received tremendous interest in the
last three decades,10−12 e.g. due to their relevance as isolable
intermediates of substitution reactions. In a classic paper,
Britton and Dunitz investigated the structural correlation of
pentacoordinated organostannanes with the trajectory of the
SN2 reaction pathway.13 Although it has been recently
challenged, a simplistic bond model describes the axial
substituents of the trigonal bipyramid, representing the entering
group and the leaving group, as three-center−four-electron (3c-
4e) bonds involving the pz orbital of the Sn atom.14 Bonding of
the three equatorial substituents of the group 14 element has
been attributed to three sp2 orbitals. At the preliminary stage of
the SN2 reaction pathway often complexes weakly associated
with the entering group are formed, in which the sp3
hybridization of the group 14 compound is still retained.
These interactions are commonly referred to as σ-hole
bonding.15 The peri distances of compound classes VI and
VII vary within a large range (2.426(9)−3.394(5) Å). Whether
or not these peri interactions are attractive or even repulsive is
ambiguous and might greatly depend on the Lewis acidity,
which in turn is influenced by the three remaining substituents
attached to the Sn atoms. For those cases the sole inspection of
the molecular geometries cannot provide an insight into the
bonding character. This holds particularly true for the transition
from a nonbonding state to a weakly coordinating state.
Detailed bonding information can be obtained by means of
computational chemistry. However, standard calculation of the
molecular wave function and subsequent analysis of the
molecular orbitals (MO) and/or natural bond orbitals
(NBO) often fail to provide a clear picture for the heavier
elements, particularly when the interactions involved are weak.
Another approach entails topological analysis of the electron
densities (ED) according to the atoms in molecules (AIM)
theory,16 which affords reliable atomic properties such as
charges and volumes as well as bonding properties in terms of
so-called bond critical points (bcp). The ED can be extracted
from the calculated wave functions but also determined
experimentally by high-resolution X-ray diffraction of the
solid-state structures, which is an advantage over all other
theoretical methods.17 A complementary set of bonding
descriptors is provided by topological analysis of the
corresponding electron pair densities according to the electron
localization function18 (ELF) or the more advanced electron
localizability indicator (ELI-D).19 Both concepts divide space
into basins of localized electron pairs (e.g. bonding basins, lone
pairs) and can only be obtained from theoretical calculations. In
this study, the ELI-D is applied. A tool for estimation of bond
polarities is the Raub−Jansen index (RJI),20 which was
invented for the ELF but was also later used for the ELI-D
(to discriminate dative bonds from polar-covalent interac-
tions).21 With this tool the electron population within an ELF/
ELI-D bonding basin connecting two or more atoms is
fragmented into particular contributions of the two or more
AIM atomic basins enclosing this bond. For a homopolar bond
the RJI equals 50% and it increases with increasing bond
polarity.
In this work we describe the synthesis and characterization of
a series of (6-(diphenylphosphino)acenaphth-5-yl)stannanes 5-
R3Sn-6-Ph2P-Ace (VIII), whereby we varied the nature of the
B
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Scheme 3. Synthesis and Selected NMR Parameters (CDCl3) of 3−5
substituents (R = Bu, Ph, Cl, O3SCF3, F).22 The character-
Scheme 4. Synthesis and Selected NMR Parameters
(CD2Cl2) of 6
ization was achieved by multinuclear NMR spectroscopy (119Sn,
31P, 19F, 13C, 1H) and X-ray crystallography. Real-space bonding
descriptors were derived from AIM and ELI-D analyses of
selected gas-phase structures optimized at the B3PW91/TZ
level of theory, which unraveled the bond character of the P−
Sn peri interactions.
RESULTS AND DISCUSSION
■
Synthetic Aspects. The reaction of 5-bromo-6-
(diphenylphosphino)acenaphthene (ArBr) with n-butyllithium
and N,N,N′,N′-tetramethylethylendiamine (TMEDA) at −78
°C proceeded with facile metal halide exchange and gave rise to
the formation of the corresponding lithium organyl ArLi (Ar =
6-Ph2P-Ace-5-). The subsequent salt metathesis reaction with
tributyltin chloride, triphenyltin chloride, and diphenyltin
dichloride at room temperature provided (6-
(diphenylphosphino)acenaphth-5-yl)tributyltin (1; ArSnBu3),
(6-(diphenylphosphino)acenaphth-5-yl)triphenyltin (2;
ArSnPh3), and (6-(diphenylphosphino)acenaphth-5-yl)-
diphenyltin chloride (3; ArSnPh2Cl), which were isolated in
71%, 74%, and 35% yields, respectively (Scheme 2).
Scheme 5. Synthesis and Selected NMR Parameters (CDCl3)
of 7
The aryltributylstannane 1 proved to be a precursor for the
transmetalation reaction with diphenyltin dichloride, phenyltin
trichloride, and tin(IV) chloride, affording (6-
(diphenylphosphino)acenaphth-5-yl)diphenyltin chloride (3;
ArSnPh2Cl), (6-(diphenylphosphino)acenaphth-5-yl)phenyltin
dichloride (4; ArSnPhCl2), and (6-(diphenylphosphino)-
acenaphth-5-yl)tin trichloride (5; ArSnCl3) in 15%, 85%, and
97% yields, respectively (Scheme 3). The reaction of the
lithium organyl ArLi with tin tetrachloride at −78 °C at a molar
ratio of 1:2 produced the disubstituted product bis(6-
(diphenylphosphino)acenaphth-5-yl)tin dichloride (6;
Ar2SnCl2) in 14% yield (Scheme 4). Treatment of ArSnPh3
(2) with triflic acid provided (6-(diphenylphosphino)-
acenaphth-5-yl)diphenylstannyl triflate (7; ArSnPh2O3SCF3)
after recrystallization in 40% yield (Scheme 5).
The reaction of ArSnPh2Cl (3) with KF in DMF proceeded
with chloride/fluoride exchange and gave rise to the formation
of (6-(diphenylphosphino)acenaphth-5-yl)diphenyltin fluoride
(8; ArSnPh2F) in 89% yield (Scheme 6). Compounds 1−8
were obtained as colorless crystals that are, with the exception
of 5, reasonably stable toward moist air.
Solid-State Structures. The molecular structures of 1−8
established by X-ray crystallography are shown in Figure 1. The
first coordination sphere of the Sn atoms is defined by C4,
C3Cl, C2Cl2, CCl3, C3O, and C3F donor sets. Related bond
C
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= 6-Ph2P-Ace-5). The P−Sn peri distance of 2.918(2) Å for the
hexacoordinated 6 lies about midway between the values of 2
and 3. Within the series ArSnPh2X the P−Sn peri distance
decreases with the decreasing donor strength of the group X
when going from 2 (X = Ph; 3.247(2) Å) over 8 (X = F;
2.937(3) Å) and 3 (X = Cl; 2.9075(6) Å) to 7 (X = O3SCF3;
2.7032(9) Å), pointing to a trans effect of the axial substituents.
The splay angle (definition ∑(three bay region angles) −
360°)9 correlates well with the P−Sn peri distances and
decreases from 19.0° (1) to 2.9° (7); however, the out-of-plane
displacements of the Sn and P atoms appear not to follow a
trend (Table 2).
Scheme 6. Synthesis and Selected NMR Parameters
(CD2Cl2) of 8
Structures in Solution. With the exception of 6, 1−8 are
reasonably soluble in moderately polar solvents such as CHCl3
and THF. In these solvents 1−8 are nonelectrolytes, as the
conductivity is below the detection limit. The triaryltin triflate 7
is also soluble in MeCN, in which it undergoes electrolytic
dissoziation into solvated triarylstannyl and triflate ions. The
molar conductivity (MeCN, c = 5 × 10−7 mol L−1) of 7 (Λ =
360 Ω−1 cm2 mol−1) is in agreement with the presence of 1/1
electrolytes.31 The 31P NMR and 119Sn NMR chemical shifts of
7 in CDCl3 (δ −27.0/−214.8) and in MeCN (δ −24.4/−
194.8) are distinctively different, but both are in the expected
range of tetracoordinated P and pentacoordinated Sn atoms.
The 119Sn NMR chemical shift of an unsolvated tetracoordi-
nated triaryltin cation would be expected to be substantially
shifted to low field. The reasonably similar J(31P−119Sn)
couplings in CDCl3 (686 Hz) and MeCN (585 Hz) support
the assumption that the triarylstannyl cation is solvated by
MeCN. It should be noted, however, that the MeCN is lost
under ESI MS conditions (CH2Cl2/MeCN 1/10), as only the
mass cluster at m/z 611.3 indicative of the unsolvated [5-
(SnPh2)-6-(Ph2P)Ace]+ was observed. Within the series of
pentacoordinated ArSnPh3−nCln species the 119Sn NMR
chemical shifts (CDCl3) are consecutively shifted to high
field when going from 2 (n = 0; δ −157.9) over 3 (n = 1; δ
−200.8) and 4 (n = 2; δ −202.5) to 5 (n = 3; δ −259.7),
indicating the increasing coordination number of the Sn atoms.
All of these 119Sn NMR signals are shifted more to high field
than those of the phenylstannanes Ph4Sn (δ −131), Ph3SnCl (δ
−48) Ph2SnCl2 (δ −32), and PhSnCl3 (δ −63), lacking an
intramolecular donor substituent.32 Within the same series of
pentacoordinated species the 31P NMR chemical shifts
(CDCl3) are also consecutively shifted to high field when
going from 2 (n = 0; δ −30.6) over 3 (n = 1; δ −33.2) and 4 (n
= 2; δ −39.0) to 5 (n = 3; δ −42.6). The hexacoordinated
Ar2SnCl2 species 6 possesses the most high field shifted 31P
NMR signal (−45.6), while no 119Sn NMR signal was obtained
due to its low solubility. The very different J(119Sn−31P)
coupling constants of 1−8, ranging from 202 to 1011 Hz,
deserve particular attention.
parameters are collected in Table 1. The second coordination
sphere of the Sn atoms contains the P atoms situated across the
bay region of the acenaphthene moieties. Geometric parameters
associated with the P−Sn peri substitution are given in Table 2.
The spatial arrangement of the Sn atoms of 1−5, 7, and 8 lies
between a tetrahedron and a trigonal bipyramid (coordination
number 4 + 1), whereby the C and Cl atoms are situated in the
equatorial positions. The axial positions are occupied by P
atoms and C atoms (1, 2), Cl atoms (3−5), an O atom (7),
and a F atom (8).
The geometrical goodness (definition Δ∑(θ) = ∑(θeq) −
∑(θax); 0° (tetrahedron) ≤ ΔΣ(θ) ≤ 90° (trigonal
bipyramid))23 mostly depends on the second axial atom (C,
Cl, O, F) and ranges from Δ∑(θ) = 33.1° (1) and 25.6° (2)
over 69.2° (8), 69.7° (4), 73.3° (5), and 74.6° (3) to the
maximum value of 92.1° (7). Notably, the low Δ∑(θ) values of
1 and 2 may represent the bonding situation at the early stage
of the SN2 reaction pathway, which has been denoted as σ-hole
bonding,15 whereas the high Δ∑(θ) value of 7 may related to a
pentacoordinated intermediate in which the entering group and
the leaving group are almost equally bonded.14 The spatial
arrangement of the Sn atom of 6 is distorted octahedral
(coordination number 4 + 2). The Sn−C and Sn−Cl bond
lengths of 1−8 are inconspicuous and resemble values found in
other tetra-, penta-, or hexacoordinated organotin compounds.
The Sn···O bond length of 7 (2.391(3) Å) is expectedly longer
than the “standard” Sn−O bond length of Mes3SnOH
(1.999(6) Å)24 and accounts for a Pauling bond order
(definition log BO = −c(d − dst); c = 1.41, dst = 2.00)25 of
BO = 0.28. These values are consistent with weak ion pairing
between the triorganotin cation and the triflate anion of 7 and
compare well with those of other triorganotin triflates such as
the polymeric Ph3SnO3SCF3 (2.375(4) and 2.310(4) Å; BO =
0.30 and 0.37)26 and the monomeric [(Me3Si)2CH]3SnO3SCF3
(2.139(4) Å; BO = 0.64).27 The Sn−F bond length of 8
(2.005(6) Å) lies about midway between those of the
monomeric Mes3SnF (1.957(4) and 1.965(4) Å)24 containing
tetracoordinated Sn atoms and the polymeric Ph3SnF
(2.1458(3)28 containing pentacoordinated Sn atoms. It
compares best with the triphenyldifluorostannate ion
[Ph3SnF2]− (2.072(4) Å)29 containing also pentacoordinated
Sn atoms. The P−Sn peri distances of aryltin(IV) species 1−8
vary between 2.7032(9) Å (7) and 3.332(2) Å (1) and are
therefore larger than that of the recently published diaryl-
stannylene 5-(2′,4′,6′-i-Pr3C6H2Sn)-6-(i-Pr2P)-Ace (2.6362(6)
Å).30 Within the series of pentacoordinated ArSnPh3−nCln
species 2 (n = 0; 3.247(2) Å), 3 (n = 1; 2.9075(6) Å), 4, (n
= 2; 2.855(2) Å), and 5 (n = 3; 2.757(2) Å) the P−Sn peri
distance decreases with an increasing number of chlorine
atoms, reflecting the growing Lewis acidity of the Sn atoms (Ar
In cases where the Sn and P atoms are formally nonbonded,
the observed coupling constant might be a combination of a
through-space coupling and a dipole−dipole coupling mediated
through the four bonds of the acenaphthyl framework. In cases
where the Sn and P atoms are covalently bonded, the observed
coupling constant might be due to the sum of two dipole−
dipole couplings, namely, a larger 1J coupling and a substantially
smaller 4J coupling, which can be of the same or opposite sign.
For weak donor−acceptor interactions and the onset of three-
center−four-electron (3c-4e) axial bonding the situation is
ambiguous.33 There is no simple numeric correlation of the
J(119Sn−31P) coupling constants with the P−Sn peri distances.
D
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Figure 1. Molecular structures of 1−8 showing 30% probability ellipsoids and the crystallographic numbering scheme. (#) Symmetry code used to
generate equivalent atoms for 6: (a) 1 − x, y, 1.5 − z.
The smallest J values were observed for the tetraorganostan-
nanes ArSnBu3 (1; 202 Hz) and ArSnPh3 (2; 284 Hz), having
the longest P−Sn peri distances (3.332(2) and 3.2437(2) Å,
respectively). The largest J values were found for the diaryltin
dichlorides ArPhSnCl2 (4; 906 Hz) and Ar2SnCl2 (6; 1011
Hz), comprising P−Sn peri distances (2.855(2) and 2.918(2)
E
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Table 1. Experimental Bond Distances (Å) and Angles (deg) of 1−8
a
a
b
c
d
e
f
g
1
2
3
4
5
6
7
8
Sn1−C10
Sn1−X
Sn1−Y
2.191(4)
2.166(5)
2.158(5)
2.180(5)
121.2(2)
111.9(2)
104.0(2)
110.9(2)
101.1(2)
2.156(2)
2.142(2)
2.146(2)
2.167(2)
113.42(8)
106.75(9)
106.11(8)
120.48(9)
102.57(8)
106.34(8)
2.161(2)
2.4913(6)
2.142(2)
2.137(2)
123.15(8)
122.74(7)
95.83(5)
93.49(6)
94.21(6)
2.158(4)
2.451(1)
2.366(1)
2.127(4)
97.9(1)
2.130(4)
2.399(1)
2.362(1)
2.351(1)
99.2(1)
2.144(3)
2.442(1)
2.145(3)
2.391(3)
2.123(3)
2.128(3)
89.7(1)
2.161(8)
2.005(6)
2.126(12)
2.165(11)
93.1(3)
Sn1-Z
C10−Sn1−X
C10−Sn1−Y
C10−Sn1−Z
X−Sn1−Y
X−Sn1−Z
Y−Sn1−Z
100.52(8)
152.5(2)
113.9(1)
130.3(2)
93.80(5)
95.5(1)
124.8(1)
122.0(1)
91.91(5)
93.32(6)
120.0(1)
119.4(1)
86.8(1)
120.8(4)
121.5(4)
96.1(4)
98.87(8)
89.64(6)
91.4(1)
98.5(3)
105.8(2)
112.23(8)
112.7(1)
110.94(5)
d
120.6(1)
114.6(4)
a
b
c
e
X = C40, Y = C50, Z = C60. X = Cl1, Y = C40, Z = C50. X = Cl1, Y = Cl2, Z = C40. X = Cl1, Y = Cl2, Z = Cl3. X = Cl1, Y = C10a, Z = Cl1a.
Symmetry code used to generate equivalent atoms: (a) 1 − x, y, 1.5 − z. X = O1, Y = C40, Z = C50. X = F1, Y = C40, Z = C50.
f
g
36
+
Å) in the midrange. The aryltin trichloride ArSnCl3 (5),
revealing the shortest P−Sn peri distance (2.757(2) Å), gives
rise to a comparatively small J value (635 Hz) which is
comparable with that of the triaryltin chloride ArPh2SnCl (3;
622 Hz). In addition to the dependence on the P−Sn distances
the J(119Sn−31P) coupling constants might be also affected by
the “re-hybridization” upon going from a tetrahedral to a
trigonal-bipyramidal arrangement and the depleting s character
of the Sn orbitals involved in the interaction with the lone pair
of the P atom. In a tetrahedral arrangement, this Sn orbital is of
the sp3 type, whereas in the case of three-center−four-electron
(3c-4e) axial bonding of the trigonal bipyramid, the pz orbital of
the Sn atom is involved.14 Since the magnitude of J couplings
correlates with the s character of the orbitals, the “re-
hybridization” will adversely affect the shortening of the P−
Sn peri distance. Inspection of the geometrical goodness of the
five distorted-trigonal-bipyramidal structures suggests that
ArSnPhCl2 (4; Δ∑(θ) = 69.7°) has a higher s character than
ArSnPh2Cl (3; Δ∑(θ) = 74.6°) and ArSnCl3 (5; Δ∑(θ) =
73.3°), which might explain the large J value.
= none, CH3 , O, S, Se) compounds. The rather large Sn
atoms possess diffuse outer valence electrons and quite flexible
Sn−C and Sn−Cl bonds in comparison to the rather rigid P−C
bonds. As for the solid-state structures, the largest geometrical
changes are found on going from 2 to 3, which is due to the
crucial electronic and steric influence of the substituent in the
axial position.
In order to highlight the important role of the axial
substituent, parts c and d of Figure 2 show the corresponding
superpositions for the gas-phase structures of 3, 7a,b and 8,
comprising the axial substituents Cl (3), none (7a), MeCN
(7b), and F (8). As expected, the charged species 7a,b have the
shortest Sn−P peri distances of 2.596 and 2.665 Å, respectively,
which are very much like the corresponding distance in 5-
(2′,4′,6′-i-Pr3C6H2Sn)-6-(i-Pr2P)-Ace (2.6362(6) Å).30 How-
ever, at 3.038 and 3.045 Å the differences between 3 and 8 are
rather marginal. The phenyl rings attached to the Sn atoms
accommodate the sterical stress by changing their orientation,
whereas the orientation of the phenyl rings attached to the P
atom remains almost unchanged in all considered compounds,
which supports the idea that the Sn moiety is much more
flexible than the P moiety. The complementary analysis of a set
of topological and integrated real-space bonding indicators
allows the determination of the characteristics of the Sn−P peri
interaction. The topological bond paths motifs of 2, 5, and 7a,b
are displayed in Figure 3. Table 3 gives bond topological
properties derived from AIM space partitioning, a set of ELI-D
derived properties, and AIM charges of atoms and functional
groups. In all compounds a Sn−P bond critical point (bcp) is
detected which shows the typical characteristics of strongly
polar (mainly ionic) bonded atoms,18 such as a very small value
of the ED at the bcp (0.12 e Å−3 (2) to 0.46 e Å−3 (7b)), a
positive Laplacian (but close to 0), a positive kinetic energy
density to ρ(r)bcp ratio (G/ρ(r)bcp), and a total energy density
to ρ(r)bcp ratio (H/ρ(r)bcp) that is negative but close to 0.
Although it is weak, the Sn−P bond path in the electron density
is stable in all gas-phase models, as the corresponding critical
point is also found by subsequent analysis of the corresponding
potential energy density (virial field, not shown). Note that the
relative positions of the bcp are almost constant in this series
(d1/d = 47.3% (2) to 46.2% (5)). As expected, the bond
parameters of 7a,b extend the trend, which is generated by the
series 2−5, as a formal RPh2Sn+ cation is a natural extension of
a strongly polarized RPh2SmO3SCF3 (7) moiety. As a result,
the Sn−P interaction in 2 has to be considered as weakly ionic,
whereas it is of polar-covalent nature in 7a,b. In general, the
ELI-D confirms the AIM results with one exception: for 2 a so-
Despite ArPh2SnO3SCF3 (7) showing the shortest P−Sn peri
distance, the J-value is only in the midrange because the nearly
perfect trigonal-bipyramidal structure (Δ∑(θ) = 92.1°)
reduces the s character to a minimum. The geometrical
goodness values of ArSnPh2F (8; Δ∑(θ) = 69.2°) and
ArSnPhCl2 (4; Δ∑(θ) = 69.7°) are very similar, but the
different P−Sn peri distances (2.937(3) and 2.855(2) Å) might
be the reason for the fact that the J value of 8 is smaller than
that of 4. The 19F NMR signal (CD2Cl2) of the triaryltin
fluoride 8 shows a doublet centered at δ −184.9 (J(31P−19F) 84
Hz) with tin satellites (1J(119Sn−19F) 2232 Hz), which
compares reasonably well with that of the monomeric
34
1
(Me3SiCH2)3SnF (δ −207.2, J(119Sn−19F) = 2370 Hz).
Gas-Phase and Electronic Structures. Gas-phase struc-
tures of 2−5, 8, the unsolvated triarylstannyl cation ArPh2Sn+
(7a), and solvated triarylstannyl cation (ArPh2Sn·NCMe)+
(7b) were obtained by geometry optimization at the
B3PW91/6-311+G(2df,p) level of theory.35 All gas-phase
structures agree well with the corresponding solid-state
structures; however, the Sn−P peri distances are about 0.1−
0.15 Å longer. Nevertheless, all experimentally observed trends
are fully retained. Parts a and b of Figure 2 show superpositions
of the gas-phase structures of 2−5, which reveal that mainly the
Sn moiety accommodates the increasing strain on going from 5
to 2 in that only this fragment increases both its in-plane and
out-of-plane distortions. This was also found for Br atoms in a
series of 1-Br-8-[Ph2P(E)]-Nap and 5-Br-6-[Ph2P(E)]-Ace (E
F
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Table 2. Experimental and Calculated (in Italics) Interatomic Distances (Å) and Angles (deg) of 1−8
1
2
3
4
peri Region Distances
P(1)···Sn(1)
3.332(2)
3.247(2)
2.9075(6)
2.855(2)
3.310
3.038
2.990
peri Region Bond Angles
Sn(1)−C(10)−C(19)
C(10)−C(19)−C(18)
P(1)−C(18)−C(19)
∑ of bay angles
129.6(3)
128.8(4)
120.6(3)
379(1)
19
127.3(2)
122.3(2)
124.84
127.9(2)
128.42
117.8(2)
118.71
368.0(6)
371.97
8
121.2(3)
123.74
127.9(4)
128.45
118.1(3)
118.14
367(1)
370.33
7
128.90
128.3(2)
129.00
119.8(3)
120.21
375.4(7)
378.11
splay angle
15.4
18.11
11.97
10.33
C(20)−P(1)−C(30)
104.1(2)
102.0(2)
106.19(9)
104.33
105.8(2)
104.33
102.78
Out-of-Plane Displacement
0.3322(6)
a
P(1)
0.197(2)
0.243
0.0950(5)
0.178
0.083(2)
0.128
0.129
a
Sn(1)
0.2529(6)
0.400
0.4284(3)
0.2503(2)
0.282
0.1691(3)
0.203
0.227
Central Acenaphthene Ring Torsion Angles
C(13)−C(14)−C(19)−C(18)
C(15)−C(14)−C(19)−C(10)
179.6(5)
177.9(4)
5
−179.5(3)
177.11
173.8(3)
176.04
6
179.6(2)
178.65
177.3(3)
177.17
7
−179.7(5)
177.78
−179.9(4)
177.05
8
peri Region Distances
2.918(2)
P(1)···Sn(1)
2.757(2)
2.7032(9)
2.937(3)
b
2.887
2.665
3.045
peri Region Bond Angles
Sn(1)−C(10)−C(19)
C(10)−C(19)−C(18)
P(1)−C(18)−C(19)
∑ of bay angles
119.6(3)
122.01
128.2(3)
128.27
116.9(3)
117.64
364.7(9)
367.92
4.7
122.9(2)
127.7(3)
115.5(2)
366.1(7)
6.1
117.4(2)
116.79
128.4(3)
127.64
117.1(2)
117.52
362.9(7)
361.95
2.9
123.7(6)
125.82
128.0(8)
128.06
117.3(6)
118.35
369(2)
372.23
9
splay angle
7.92
8.34
8.65
C(20)−P(1)−C(30)
107.0(2)
104.93
104.4(2)
105.65
109.1(2)
107.76
105.7(4)
104.44
Out-of-Plane Displacement
0.4499(4)
a
Sn(1)
P(1)
0.0038(5)
0.237
0.0404(2)
0.213
0.1515(6)
0.235
a
0.008(2)
0.129
0.3279(8)
0.1990(8)
0.141
0.108(3)
0.140
Central Acenaphthene Ring Torsion Angles
C(13)−C(14)−C(19)−C(18)
C(15)−C(14)−C(19)−C(10)
178.3(4)
178.49
172.4(3)
179.2(3)
178.06
−180.0(8)
178.01
−179.5(4)
177.65
178.0(3)
178.7(4)
178.11
178.2(8)
178.05
b
a
Compounds 4 and 7 have a cisoid out-of-plane displacement, and 1−3, 5, 6, and 8 show a transoid out-of-plane displacement. Calculated
interatomic distances and angles of 7b.
called monosynaptic valence basin (V1(P), that is a lone pair) is
observed at the P atom instead of the expected disynaptic Sn−P
basin (V2(Sn,P)) that is found for 3−5 and 7a,b. An isosurface
representation of the ELI-D of 2, 5, and 7a,b is given in Figure
4. Since the Sn−P distances of the optimized gas-phase
geometries are 0.10−0.15 Å longer than those obtained by X-
ray crystallography, the RSBI analysis is extended to the solid-
state geometry of 2. However, all qualitative and quantitative
G
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Figure 2. Superposition of the gas-phase structures of (a, b) 2 (violet), 3 (red), 4 (orange), and 5 (yellow) and (c, d) corresponding results for 3
(red), 7a (green), 7b (blue), and 8 (brown): (left) side-on view; (right) top view. All structures are SCHAKAL representations.37
Figure 3. AIM bond paths of 2, 5, and 7a,b. Bond critical points are given as red dots. All structures are AIM2000 representations.38
results between gas-phase and solid-state geometries of 2 are
similar; hence, the topological difference between 2 and the
other compounds is not an artifact of the calculation.
Interestingly, the different kinds of ligands attached to the Sn
H
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a
Table 3. Topological and Integrated AIM and ELI-D Properties of 2−5, 7a,b, and 8
Sn−P
ρ(r)bcp
∇2ρ(r)bcp
G/ρ(r)bcp
H/ρ(r)bcp
(he−1
(e Å−3
)
(e Å−5
)
d1/d (%)
(he−1
)
)
N(001) (e) V(001) (Å3) Ymax ΔELI (Å) RJI (%)
ELI
ELI
d (Å)
2
3.310
3.247
3.038
2.990
2.887
2.596
2.665
3.045
0.12
0.13
0.19
0.22
0.27
0.46
0.41
0.19
0.7
0.8
0.8
0.8
0.7
0.8
0.9
0.8
47.3
47.2
46.4
46.4
46.2
46.6
46.3
46.5
0.45
0.47
0.44
0.42
0.41
0.46
0.46
0.43
−0.04
−0.05
−0.14
−0.17
−0.22
−0.34
−0.31
−0.14
(e)
2.06
2.06
2.04
2.05
2.07
2.05
2.05
2.04
13.4
12.6
11.7
11.6
11.3
10.6
10.8
12.1
2.43
2.41
2.31
2.29
2.23
2.03
2.10
2.33
99
98
96
94
89
79
84
95
2exp
3
0.432
0.397
0.344
0.258
0.281
0.458
4
5
7a
7b
8
AIM
Qtot
Ace
P
PPh2
Sn
Xax
Cleq
Phax
Pheq
SnXnPh3−n
2
−0.89
−0.90
−0.83
−0.81
−0.74
−0.72
−0.74
−0.83
1.48
1.50
1.52
1.52
1.53
1.58
1.53
1.49
0.50
0.50
0.58
0.60
0.60
0.82
0.73
0.55
1.61
1.63
1.66
1.76
1.85
1.48
1.58
1.79
−0.44
−0.43
−0.40, −0.42
−0.40, −0.40
−0.36, −0.36
−0.32
0.35
0.40
0.28
0.22
0.13
0.91
1.00
0.28
2exp
3
−0.66
−0.61
−0.59
4
−0.61
−0.57, −0.56
5
7a
7b
8
−0.30, −0.27
−0.30, −0.31
−0.37, −0.37
0.03
−0.77
a
For all bonds, ρ(r)bcp is the electron density at the bond critical point, ∇2ρ(r)bcp is the corresponding Laplacian, d1 and d2 are the distances from the
atom to the bond critical point, ε is the bond ellipticity (ε = λ1/λ2 − 1, where λ1 and λ2 are curvatures perpendicular to the bond path), λ3 is the
curvature along the bond path, and G/ρ(r)bcp and H/ρ(r)bcp are the ratios of kinetic and total energy density to ρ(r)bcp. For all basins, V(001)ELI is the
basin volume cut at 0.001 au, N(001)ELI is the corresponding electron population in that volume, Ymax is the ELI-D value at the attractor position, ΔELI
is the perpendicular distance of the attractor position to the atom−atom line, and RJI is the Raub−Jansen index (percentile electron population
within the AIM atom which has the larger electronegativity). Results were obtained by an analysis of the wave function files with AIM2000.36
atom have only a small effect on the corresponding V2(Sn,P)/
V1(P) basin electron populations (2.04−2.07 e) and volumes
(11.3−13.4 Å3), also in the case of the triarylstannyl cations
7a,b (2.05 e, 10.6/10.8 Å3). Some trends, however, are visible
for the topological ELI-D properties, such as the ELI-D value at
the basin attractor position (Ymax), which is an indicator of the
degree of electron delocalization, and the distance of this
attractor to the Sn−P axis (ΔELI). Large ΔELI values are a sign
for bond strain in covalent bonds and are typical for
nondirected ionic bonds in solids. Both decrease in the order
2 > 8 > 3 > 4 > 5 > 7b > 7a. With increasing strength of the
Sn−P interaction the electron localizability within the
V2(Sn,P)/V1(P) basin decreases as electrons are shared. The
ΔELI values are generally quite large, which may indicate some
strain in the Sn−P interactions. Since the Sn−P peri interaction
is established by the lone pair of the PPh2 fragment, which is in
accordance with the observation that the V2(Sn,P)/V1(P) basin
is located much closer to the P atom (see Figure 4), the RJI
helps to understand how much this “lone pair” is involved in
the interaction. As expected, the RJI is found to be 99% for 2,
which means that 99% of the ED of the V2(Sn,P) basin remains
in the AIM atomic basin of the P atom and is consistent with an
almost nonbonding scenario. For 5 and 7a,b the RJI values are
89%, 79%, and 84%, respectively, which are in the range of
polar-covalent interactions. 3, 4, and 8 are intermediate cases.
The recently introduced mapping of the ELI-D distribution on
the surface of an ELI-D basin40 is a suitable tool to uncover
weak effects of electron redistribution due to chemical bonding
and has been applied to related peri-substituted (ace)-
naphthylphosphinoboranes IV and V before (Scheme 1).6
Figure 5 shows the ELI-D distribution mapped on the V1(P)
basin in 2 and the V2(Sn,P) basins in 5 and 7a,b. Disregarding
the fact that for 2 the lone pair basin of the P atom is flattened
in the P−Sn direction and is not connected to the Sn atom in
terms of the ELI-D topology, a region of slightly increased
electron localizability directed toward the Sn atom is already
visible. This effect is significantly enhanced for the bonding
interactions in 5 and 7a,b. Thus, it can be stated that the Sn−P
contact in 2 is in a border regime between nonbonding and
weakly ionic. On the one hand, the relevant basin is assigned as
a P atom lone pair basin and the electrons of this basin remain
at 99% in the AIM P atom. On the other hand, a region of
increased localizability is visible in the Sn direction on the basin
surface and, moreover, a bcp is found in the underlying ED and
virial field. With increased Lewis acidity of the Sn atom the Sn−
P bonding becomes a strongly polar covalent interaction with
considerable covalent contributions for 5, 7b, and 7a, which is
reflected in the decreased Ymax, ΔELI, H/ρ(r)bcp, and RJI values
and increased ρ(r)bcp values. The AIM and ELI-D properties of
the P−C and Sn−C bonds are similar to those found in
previous studies.6,36,42 Consequently, it may be stated that these
bonds are only slightly affected by the (non)bonding peri
interaction. An exception is the RJI, for which considerable
changes are observed (73−78% for P−C, 68−77% for Sn−C).
These results prove the essential contributions of the combined
AIM and ELI-D bond analysis. AIM charges of all relevant
atoms and functional groups of 2−5 and 7a,b are shown in
Table 3. Going from 2 to 5, the redistribution of electrons as a
consequence of the introduction of Cl atoms becomes visible
and these effects are obviously far reaching, as all fragments are
influenced by the number of Cl atoms. The acenaphthene ring
system and the P atom each lose 0.15 e in this series, whereas
the Sn atom, which is directly bonded to the Cl atom(s), loses
0.24 e. In addition, the Cl atom AIM charges become less
negative with an increasing number of competing Cl atoms. For
comparison, Sn AIM atomic charges have also been determined
I
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Figure 4. Isosurface representations of the localization domains of the ELI-D (Y = 1.4) of 2, 5, and 7a,b. The color is coded according to the
corresponding basin volumes transforming from green (small) to blue (large). For clarity, the protonated valence basins (H atoms) are given in
transparent mode.
for the optimized gas-phase models of Ph3Sn+ and Ph3SnCl,
being 1.53 and 1.68 e, respectively. The former lies between the
results for 7a (1.48 e) and 7b (1.58 e), whereas the latter
compares well with the result for 3 (1.66 e). As expected, the
positive molecular charges in 7a,b mainly affect the SnPh2−nXn
part of the molecule. Nevertheless, the AIM charges of the Sn
atom are significantly less positive in 7a,b in comparison to all
others because of the lack of a third substituent with electron-
withdrawing properties. At 1.48 e, the Sn AIM atomic charge of
7a is even less positive than the charge of the P atom in 7a
(1.58 e). Accordingly, 7a may be regarded as a stannyl-
substituted phosphonium ion rather than a phosphine-
supported triarylstannyl cation.44
orientation of the more rigid PPh2 part remains almost
unchanged. The Lewis acidity of the Sn atom can be fine-
tuned by the choice of the substituents attached to the Sn
atom; especially the axial substituent (X) has a crucial role due
to the possible formation of 3c-4e P−Sn−X bonds. Analysis of
a set of RSBI values derived from the electron and pair densities
of the gas-phase structures showed the Sn−P peri interaction in
2 to be in the border regime between nonbonding and weakly
ionic bonding. In the order 8 < 3 < 4 < 5 < 7b < 7a the Sn−P
interaction becomes a polar-covalent interaction with a
considerable degree of covalency. We are currently using 1 as
the starting material in transmetalation reactions for the
synthesis of new peri-substituted acenaphthyl compounds
containing elements such as Hg, Au, B, Ga, In, As, Sb, and Te.
CONCLUSIONS
■
EXPERIMENTAL SECTION
The series of (6-(diphenylphosphino)acenaphth-5-yl)stannanes
ArSnBu3 (1), ArSnPh3 (2), ArSnPh2Cl (3), ArSnPhCl2 (4),
ArSnCl3 (5), Ar2SnCl2 (6), ArSnPh2O3SCF3 (7), and
ArSnPh2F (8), containing intramolecularly coordinated P
donor substituents, was prepared and fully characterized (Ar
= 6-Ph2P-Ace-5-). While hypercoordinated organostannanes
containing N and O donor substituents have been extensively
investigated,8,10,11 P donor substituents are much rarer.45
Inspection of the molecular geometries revealed that the
more flexible SnPh3−nXn part of the molecule accommodates
the steric strain due to the peri interaction, whereas the
■
General Considerations. Reagents were obtained commercially
and used as received (Sigma-Adrich, Germany). 5-Bromo-6-
(diphenylphosphino)acenaphthene was prepared according to liter-
ature procedures.36 Dry solvents were collected from a SPS800
mBraun solvent system. 1H, 13C, 19F, 31P, and 119Sn NMR spectra were
recorded at room temperature using a Bruker Avance-360
spectrometer and are referenced to tetramethylsilane (1H, 13C),
trichlorofluoromethane (19F), phosphoric acid (85% in water; 31P),
and tetramethyltin (119Sn). Chemical shifts are reported in parts per
million (ppm), and coupling constants (J) are given in hertz (Hz).
Electron impact mass spectroscopy (EIMS) was carried out using a
J
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Figure 5. ELI-D distribution mapped on (a) the P lone pair basin (V1(P)) of 2 and (b−d) the Sn−P basins (V2(Sn,P)) of (b) 5, (c) 7a, and (d) 7b.
All structures are MOLISO representations.41
Finnigan MAT 95 instrument. The ESI MS spectra were obtained with
a Bruker Esquire-LC MS instrument. Dichloromethane/acetonitrile
solutions (or otherwise stated, c = 1 × 10−6 mol L−1) were injected
directly into the spectrometer at a flow rate of 3 μL min−1.
Nitrogen was used both as a drying gas and for nebulization with
flow rates of approximately 5 L min−1 and a pressure of 5 psi,
respectively. Pressure in the mass analyzer region was usually about 1
× 10−5 mbar. Spectra were collected for 1 min and averaged.
The nozzle-skimmer voltage was adjusted individually for each
measurement. The conductivity measurement of [5-(Ph2Sn)-6-
(Ph2P)-Ace]O3SCF3 (7) was carried out with a WTW Cond 330i
instrument at 298 K.
C3), 119.5 (s, C8), 30.0 (s, C1 or C2), 29.9 (s, C2 or C1), 29.3 (d,
J(31P−13C) = 2 Hz, 2J(119/117Sn−13C) = 19 Hz, Cβ), 27.5 (s,
3J(119/117Sn−13C = 68/62 Hz, Cγ), 14.3 (d, J(31P−13C) = 21 Hz,
1J(119/117Sn−13C = 362/346 Hz, Cα), 13.7 ppm (s, CH3). 31P{1H}
NMR (CDCl3): δ −25.9 ppm (s, J(119/117Sn−31P) = 202/193 Hz).
119Sn{1H} NMR (CDCl3): δ −55.7 ppm (d, J(31P−119Sn) = 202 Hz).
MS (EI+): m/z 571 [M − C4H9]+.
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)-
triphenyltin (2). To
a suspension of 5-bromo-6-
(diphenylphosphino)acenaphthene (1.00 g, 2.40 mmol) in diethyl
ether (10 mL) were added n-butyllithium (2.88 mmol, 2.5 M in n-
hexane) and N,N,N′,N′-tetramethylethylenediamine (0.33 g, 2.88
mmol) at −78 °C. After 2 h the suspension was warmed to room
temperature and stirred for 1 h, triphenyltin chloride (1.11 g, 2.88
mmol) was added, and stirring was continued for 12 h. Dichloro-
methane was added to the suspension, and after aqueous workup the
removal of the solvent by rotary evaporation afforded a white solid,
which was recrystallized from dichloromethane and n-hexane, affording
2 as colorless crystals (1.22 g, 1.77 mmol, 74%; mp 223 °C).
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)-
tributyltin (1). n-Butyllithium (43.1 mmol, 2.5 M in n-hexane) and
N,N,N′,N′-tetramethylethylenediamine (5.01 g, 43.1 mmol) were
added at −78 °C to a suspension of 5-bromo-6-(diphenylphosphino)-
acenaphthene (15.0 g, 36.0 mmol) in diethyl ether (180 mL), and the
mixture was stirred for 2 h at this temperature. The suspension was
warmed to room temperature and stirred for 1 h, tributyltin chloride
(14.0 g, 43.1 mmol) was added dropwise, and stirring was continued
for 12 h. After aqueous workup the removal of the solvent by rotary
evaporation afforded a brownish oil which solidified upon standing.
The solid was washed intensely with acetonitrile and dried under
vacuum, affording 1 as a colorless solid (16.1 g, 25.7 mmol, 71%; mp
54 °C). Crystals suitable for X-ray crystallography were obtained by
recrystallization from toluene at 5 °C.
1H NMR (CDCl3): δ 7.95 (d, 3J(1H−1H) = 7 Hz, 3J(119/117Sn−1H)
3
4
= 67/64 Hz, 1H, H-4), 7.69 (dd, J(1H−1H) = 8 Hz, J(1H−1H) = 2
Hz, 3J(119/117Sn−1H) = 48 Hz, 6H, H−Co,Sn‑phenyl), 7.45−7.28 (m,
12H), 7.22 (t, J(1H−1H) = 7 Hz, 2H), 7.09 (dt, J(1H−1H) = 8 Hz,
3
3
3
4J(1H−1H) = 2 Hz, 4H), 6.63 (t, J(1H−1H) = 8 Hz, 4H), 3.52 ppm
(s, 4H, H-1,2). 13C{1H} NMR (CDCl3): δ 149.8 (s, J(119/117Sn−13C)
= 9 Hz, Cb or Cc), 148.5 (d, J(31P−13C) = 2 Hz, J(119/117Sn−13C) = 12
1H NMR (CDCl3): δ 7.89 (d, 3J (1H−1H) = 7 Hz, 3J(119/117Sn−1H)
= 52/50 Hz, 1H, H-4), 7.49−7.29 (m, 13H), 3.49−3.47 (m, 4H, H-
1,2), 1.65−1.57 (m, 6H, CH2-β), 1.40−1.32 (m, 6H, CH2-γ), 1.30−
Hz, Cc or Cb), 144.0 (d, J(31P−13C) = 21 Hz, J(119/117Sn−13C) =
3
1
561/536 Hz, C5), 142.0 (d, J(31P−13C) = 2 Hz, J(119/117Sn−13C) =
49 Hz, C4), 142.0 (d, 1J(31P−13C) = 29 Hz, C6 or Ci,P‑phenyl), 139.9 (d,
4
2
3
1.25 (m, 6H, CH2-α), 0.93 ppm (t, J(1H−1H) = 7.3 Hz, 9H, CH3).
2J(31P−13C) = 7 Hz, Ca or C7), 137.8 (d, J(31P−13C) = 2 Hz,
13C{1H} NMR (CDCl3): δ 149.8 (s, Cb or Cc), 147.0 (d, J(31P−13C) =
2 Hz, Cc or Cb), 142.3 (d, 1J(31P−13C) = 29 Hz, C6 or Ci,P‑phenyl), 139.7
2
C
i,Sn‑phenyl), 137.0 (s, J(119/117Sn−13C) = 35 Hz, Co,Sn‑phenyl), 136.7 (d,
2
4
2
(d, J(31P−13C) = 7 Hz, Ca or C7), 139.3 (d, J(31P−13C) = 2 Hz,
4J(31P−13C) = 7 Hz, Cd), 132.8 (d, J(31P−13C) = 17 Hz, Co,P‑phenyl),
2J(119/117Sn−13C) = 35 Hz, C4), 138.2 (d, J(31P−13C) = 10 Hz, C5),
3
130.7 (d, 1J(31P−13C) = 31 Hz, Ci,P‑phenyl or C6), 129.4 (d, 2J(31P−13C)
137.9 (d, J(31P−13C) = 2 Hz, Cd), 135.1 (d, J(31P−13C) = 26 Hz,
4
1
= 7 Hz, C7 or Ca), 128.2 (s, J(119/117Sn−13C) = 51 Hz, Cm,Sn‑phenyl),
3
Ci,P‑phenyl or C6), 132.9 (d, J(31P−13C) = 17 Hz, Co,P‑phenyl), 129.8 (d,
2
127.8 (d, J(31P−13C) = 7 Hz, Cm,P‑phenyl), 127.8 (s, Cp,Sn‑phenyl), 127.6
3
2J(31P−13C) = 9 Hz, C7 or Ca), 128.3 (d, 3J(31P−13C) = 6 Hz,
(s, Cp,P‑phenyl), 120.1 (d, J(31P−13C) = 1 Hz, J(119/117Sn−13C) = 64
5
3
Cm,P‑phenyl), 128.0 (s, Cp,P‑phenyl), 119.7 (s, J(119/117Sn−13C) = 47 Hz,
Hz, C3), 119.9 (d, J(31P−13C) = 1 Hz, C8), 30.1 (s, C1 or C2), 30.1
3
3
K
dx.doi.org/10.1021/om500133a | Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
ppm (s, C2 or C1). 31P{1H} NMR (CDCl3): δ −30.6 ppm (s,
J(119/117Sn−31P) = 284/271 Hz). 119Sn{1H} NMR (CDCl3): δ −157.9
ppm (d, J(31P−119Sn) = 284 Hz). ESI MS (CH2Cl2/MeCN 1/10,
positive mode): m/z 711.3 (NaC42H33PSn) for [5-(SnPhCl2)-6-
(Ph2P)Ace + Na+].
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)-
diphenyltin Chloride (3). Method a. A solution of (6-
(diphenylphosphino)acenaphth-5-yl)tributyltin (1; 250 mg, 0.40
mmol) in toluene (2 mL) was slowly added to a solution of
diphenyltin dichloride (137 mg, 0.40 mmol) in 2 mL of toluene. The
reaction mixture was stirred at 120 °C for 3 h, cooled to room
temperature, and stirred for a further 12 h. The precipitate was filtered,
washed three times with toluene, and dried under vacuum, affording 3
(40.2 mg, 0.06 mmol, 15%) as a white solid. Crystals suitable for X-ray
were obtained by recrystallization from dichloromethane.
C
o,P‑phenyl), 129.9 (d, J(31P−13C) = 22 Hz, C5, C6 or Ci,P‑phenyl), 129.9
4
(d, J(31P−13C) = 2 Hz, Cp,P‑phenyl), 129.6 (s, Cp,Sn‑phenyl), 128.8 (s,
3J(119/117Sn−13C) = 99/95 Hz, Cm,Sn‑phenyl), 128.6 (d, J(31P−13C) = 9
3
Hz, Cm,P‑phenyl), 122.3 (d, J(31P−13C) = 24 Hz, C5, C6 or Ci,P‑phenyl),
1
121.3 (d, 5J(31P−13C) = 5 Hz, 3J(119/117Sn−13C) = 102 Hz, C3), 120.5
(d, J(31P−13C) = 5 Hz, C8), 30.7 (s, C1 or C2), 30.3 ppm (s, C2 or
3
C1). 31P{1H} NMR (CDCl3): δ −39.0 ppm (s, J(119/117Sn−31P) =
906/866 Hz). 119Sn{1H} NMR (CDCl3): δ −202.5 ppm (d,
J(31P−119Sn) = 904 Hz). ESI MS (CH2Cl2/MeCN 1/10, positive
mode): m/z 596.2 (C30H23ClPSn) for [5-(SnPhCl2)-6-(Ph2P)Ace −
Cl−]. ESI MS (CH2Cl2/MeCN 1/10, negative mode): m/z 638.9
(C30H23Cl3PSn) for [5-(SnPhCl2)-6-(Ph2P)Ace + Cl−].
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)tin Tri-
chloride (5). To a vigorously stirred solution of tin(IV) chloride (2.00
g, 7.68 mmol) in n-hexane (20 mL) was slowly added (6-
(diphenylphosphino)acenaphth-5-yl)tributyltin (1; 2.50 g, 3.98
mmol), causing immediate precipitation of the crude product. Stirring
was continued at room temperature for 12 h. The precipitate was
filtered, washed three times with n-hexane, and dried under vacuum,
affording 5 (2.16 g, 3.85 mmol, 97%, mp 153 °C dec) as a white solid.
Crystals suitable for X-ray crystallography were obtained by
recrystallization from toluene.
Method b. n-Butyllithium (1.20 mmol, 2.5 M in n-hexane) and
N,N,N′,N′-tetramethylethylenediamine (0.14 g, 1.20 mmol) were
added at −78 °C to a suspension of 5-bromo-6-(diphenylphosphino)-
acenaphthene (0.50 g, 1.20 mmol) in diethyl ether (5 mL) and stirred
for 2 h at this temperature. The suspension was warmed to room
temperature and stirred for 1 h, diphenyltin dichloride (0.41 g, 1.20
mmol) was slowly added, and stirring was continued for 12 h. The
precipitate was allowed to settle, the solution was decanted, and the
solid was washed with diethyl ether. Dichloromethane (30 mL) was
added to the solid, and after aqueous workup the removal of the
solvent by rotary evaporation afforded a white solid. Recrystallization
from dichloromethane and n-hexane yielded 3 as colorless crystals
(272 mg, 0.42 mmol, 35%; mp 210 °C dec).
1H NMR (CDCl3): δ 8.64 (dd, 3J(1H−1H) = 7 Hz, 5J(31P−1H) = 3
Hz, 3J(119/117Sn−1H) = 144 Hz, H1, H-4), 7.65 (t, 3J(1H−1H) = 8 Hz,
2H), 7.57−7.43 (m, 11H), 3.58 ppm (s, 4H, H-1,2). 13C{1H} NMR
(CDCl3): δ 152.6 (d, J(31P−13C) = 2 Hz, Cb or Cc), 151.8 (d,
J(31P−13C) = 2 Hz, Cc or Cb), 139.5 (d, J(31P−13C) = 10 Hz, C4),
4
139.3 (s), 138.3 (d, 2J(31P−13C) = 17 Hz, Ca or C7), 137.1 (d,
4J(31P−13C) = 2 Hz, Cd), 133.7 (d, J(31P−13C) = 12 Hz, Co,P‑phenyl),
2
1H NMR (CDCl3): δ 8.98 (d, 3J(1H−1H) = 7 Hz, 3J(119/117Sn−1H)
131.1 (d, J(31P−13C) = 3 Hz, Cp,P‑phenyl), 129.0 (d, J(31P−13C) = 10
Hz, Cm,P‑phenyl), 127.2 (d, 1J(31P−13C) = 34 Hz, C6 or Ci,P‑phenyl), 121.7
(d, 5J(31P−13C) = 7 Hz, C3), 120.9 (d, 3J(31P−13C) = 6 Hz, C8), 118.7
(d, 1J(31P−13C) = 36 Hz, Ci,P‑phenyl or C6), 31.0 (s, C1 or C2), 30.4 ppm
(s, C2 or C1). 31P{1H} NMR (CDCl3): δ −42.6 ppm (s,
J(119/117Sn−31P) = 635/606 Hz). 119Sn{1H} NMR (CDCl3): δ
−259.7 ppm (d, J(31P−119Sn) = 637 Hz). MS (EI+): m/z 562 [M+].
Synthesis of Bis(6-(diphenylphosphino)acenaphth-5-yl)tin
Dichloride (6). n-Butyllithium (1.20 mmol, 2.5 M in n-hexane) and
N,N,N′,N′-tetramethylethylenediamine (0.14 g, 1.20 mmol) were
added at −78 °C to a suspension of 5-bromo-6-(diphenylphosphino)-
acenaphthene (0.50 g, 1.20 mmol) in diethyl ether (5 mL) and stirred
for 2 h at this temperature. The suspension was warmed to room
temperature, stirred for 1 h, and cooled to −78 °C. Tin(IV) chloride
(0.16 g, 0.60 mmol) was slowly added, and the mixture was warmed to
room temperature overnight. The precipitate was filtered, washed
extensively with diethyl ether, and dried in vacuo. Dichloromethane
(50 mL) was added, and the suspension was filtered. The filtrate was
reduced until the product started to precipitate (8−10 mL) and stored
at 5 °C for further precipitation. The white precipitate was filtered and
dried in vacuo, affording 6 as a colorless solid (141 mg, 0.16 mmol,
14%; mp 210 °C dec). Crystals suitable for X-ray crystallography were
obtained by recrystallization from dichloromethane under reflux.
1H NMR (CD2Cl2): δ 8.69 (d, 3J(1H−1H) = 6 Hz, 3J(119/117Sn−1H)
= 131 Hz, 2H, H-4), 7.61 (d, 3J(1H−1H) = 7 Hz, 2H), 7.51−7.44 (m,
4
3
3
= 80/77 Hz, 1H, H-4), 7.67 (d, J(1H−1H) = 7 Hz, 1H), 7.61 (dd,
3J(1H−1H) = 8 Hz, 4J(1H−1H) = 1 Hz, 3J(119/117Sn−1H) = 67 Hz, 4H,
H−Co,Sn‑phenyl), 7.46−7.37 (m, 2H), 7.26−7.15 (m, 8H), 7.07 (dt,
3J(1H−1H) = 8 Hz, 4J(1H−1H) = 2 Hz, 4H), 6.77 (dt, 3J(1H−1H) = 9
Hz, 4J(1H−1H) = 1 Hz, 4H), 3.57−3.51 ppm (m, 4H, H-1,2). 13C{1H}
NMR (CDCl3): δ 151.3 (d, J(31P−13C) = 2 Hz, Cb or Cc), 149.1 (d,
J(31P−13C) = 2 Hz, Cc or Cb), 142.3 (d, J(31P−13C) = 27 Hz, C5, C6 or
Ci,P‑phenyl), 141.4 (d, 4J(31P−13C) = 6 Hz, C4), 139.8 (d, 2J(31P−13C) =
8 Hz, Ca or C7), 137.1 (d, J(31P−13C) = 2 Hz, Ci,Sn‑phenyl), 135.9 (d,
2
J(31P−13C) = 2 Hz, J(119/117Sn−13C) = 46 Hz, Co,Sn‑phenyl), 132.8 (d,
2J(31P−13C) = 13 Hz, Co,P‑phenyl), 131.5 (d, 2J(31P−13C) = 16 Hz, C7 or
Ca), 129.8 (d, J(31P−13C) = 44 Hz, C5, C6 or Ci,P‑phenyl), 129.1 (d,
4J(31P−13C) = 1 Hz, Cp,P‑phenyl), 128.7 (s, Cp,Sn‑phenyl), 128.5 (s,
3
3J(119/117Sn−13C) = 73/70 Hz, Cm,Sn‑phenyl), 128.3 (d, J(31P−13C) = 9
1
Hz, Cm,P‑phenyl), 124.5 (d, J(31P−13C) = 18 Hz, C5, C6 or Ci,P‑phenyl),
121.4 (d, 5J(31P−13C) = 3 Hz, C3), 120.0 (d, 3J(31P−13C) = 4 Hz, C8),
30.6 (s, C1 or C2), 30.2 ppm (s, C2 or C1). 31P{1H} NMR (CDCl3): δ
−33.2 ppm (s, J(119/117Sn−31P) = 628/601 Hz). 119Sn{1H} NMR
(CDCl3): δ −200.8 ppm (d, J(31P−119Sn) = 622 Hz). ESI MS
(CH2Cl2/MeOH 1/10, positive mode): m/z 611.3 (C36H28PSn) for
[5-(SnPh2Cl)-6-(Ph2P)Ace − Cl−].
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)-
phenyltin Dichloride (4). A solution of (6-(diphenylphosphino)-
acenaphth-5-yl)tributyltin (1; 2.50 g, 3.98 mmol) in n-hexane (20 mL)
was slowly added to phenyltin trichloride (1.20 g, 3.98 mmol) and the
reaction mixture was stirred at room temperature for 12 h. The
precipitate was filtered, washed three times with n-hexane, and dried
under vacuum, affording a white solid of 4 (2.05 g, 3.39 mmol, 85%,
mp 217 °C). Crystals suitable for X-ray crystallography were obtained
by recrystallization from dichloromethane and n-hexane.
5H), 7.42−7.27 (m, 9H), 6.94 (t, J(1H−1H) = 7 Hz, 2H), 6.61 (t,
3
3J(1H−1H) = 7 Hz, 4H), 6.19 (s, 4H), 3.56 ppm (s, 8H, H-1,2).
13C{1H} NMR (CD2Cl2): δ 152.0 (s, Cb or Cc), 149.3 (s, Cc or Cb),
137.8 (s), 135.9 (broad), 133.5, 133.3, 133.2, 133.0, 129.4 (s), 128.5
(very broad), 121.9 (s), 120.4 (s), 31.1 (s, C1 or C2), 30.7 ppm (s, C2
or C1). 31P{1H} NMR (CD2Cl2): δ −45.6 ppm (s, J(119/117Sn−31P) =
1011/960 Hz). ESI MS (CH2Cl2/MeCN 1/10, positive mode): m/z
829.3 (C48H36ClPSn) for {[6-(Ph2P)-5-Ace]2SnCl2 − Cl−}.
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)-
diphenylstannyl Triflate (7). Trifluoromethanesulfonic acid (22.0
mg, 0.15 mmol) was slowly added to a solution of (6-
(diphenylphosphino)acenaphth-5-yl)triphenyltin (2; 100 g, 0.15
mmol) in dichloromethane (1.5 mL), and the reaction mixture was
stirred for 12 h. The solvent was evaporated, and the residue was
recrystallized by dichloromethane and n-hexane, affording 7 as
colorless crystals (49.2 mg, 0.06 mmol, 40%; mp 193 °C dec).
1H NMR (CDCl3): δ 8.89 (d, 3J(1H−1H) = 7 Hz, 3J(119/117Sn−13C)
= 107/104 Hz, 1H, H-4), 7.65 (d, 3J(1H−1H) = 7 Hz,
3
3J(119/117Sn−1H) = 47 Hz, 2H, H−Co,Sn‑phenyl), 7.57 (t, J(1H−1H) =
7 Hz, 1H), 7.46−7.15 (m, 15H), 3.53 ppm (s, 4H, H-1,2). 13C{1H}
NMR (CDCl3): δ 151.7 (d, J(31P−13C) = 2 Hz, Cb or Cc), 150.8 (d,
J(31P−13C) = 2 Hz, Cc or Cb), 144.3 (d, J(31P−13C) = 42 Hz, C5, C6 or
4
Ci,P‑phenyl), 140.6 (d, J(31P−13C) = 8 Hz, C4), 139.9 (d, J(31P−13C) =
22 Hz, Ca, Cd or C7), 139.7 (d, J(31P−13C) = 7 Hz, Ca, Cd or C7),
136.9 (d, J(31P−13C) = 2 Hz, Ci,Sn‑phenyl), 134.0 (d, J(31P−13C) = 2 Hz,
2J(119/117Sn−13C) = 62 Hz, Co,Sn‑phenyl), 133.1 (d, 2J(31P−13C) = 13 Hz,
L
dx.doi.org/10.1021/om500133a | Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
1H NMR (CDCl3): δ 8.71 (d, 3J(1H−1H) = 7 Hz, 3J(119/117Sn−1H)
= 73 Hz, 1H, H-4), 7.75 (d, 3J(1H−1H) = 7 Hz, 1H), 7.53 (dd,
3J(1H−1H) = 7 Hz, 4J(1H−1H) = 1 Hz, 3J(119/117Sn−1H) = 68 Hz, 4H,
H−Co,Sn‑phenyl), 7.47−7.45 (m, 2H), 7.36−7.20 (m, 8H), 7.14 (dt,
Cambridge CB2 1EZ, U.K. (fax, +44-1223-336033; e-mail, deposit@
ccdc.cam.ac.uk; web, http://www.ccdc.cam.ac.uk).
Computational Methodology. Gas-phase structures of 2−5 and
7a,b were obtained by geometry optimization at the B3PW91/6-
311+G(2df,p)35 level of theory starting from the atomic coordinates of
the X-ray structures using Gaussian09.48 For the Sn atom an effective
core potential (ECP28MDF)49 and a corresponding cc-pVTZ basis
set50 were applied. Subsequent frequency analysis proves all structures
to be local minima. The wave function files were used for a topological
analysis of the electron density (ED) according to the atoms in
molecules space-partitioning scheme16 using AIM2000,38 whereas
DGRID51 was used to generate and analyze the electron localizability
indicator (ELI-D) related real-space bonding descriptors, applying a
grid step size of 0.05 au.17
4
3
3J(1H−1H) = 8 Hz, J(1H−1H) = 2 Hz, H4), 6.88 (t, J(1H−1H) = 9
Hz, 4H), 3.61−3.54 ppm (m, 4H, H-1,2). 13C{1H} NMR (CDCl3): δ
153.0 (d, J(31P−13C) = 2 Hz, Cb or Cc), 149.6 (d, J(31P−13C) = 2 Hz,
Cc or Cb), 141.1 (d, 3J(31P−13C) = 8 Hz, C4), 139.8 (d, 2J(31P−13C) =
9 Hz, Ca or C7), 138.0 (d, J(31P−13C) = 23 Hz, C5, C6 or Ci,P‑phenyl),
136.8 (d, J(31P−13C) = 1 Hz, Ci,Sn‑phenyl), 136.2 (d, J(31P−13C) = 2 Hz,
2J(119/117Sn−13C) = 48 Hz, Co,Sn‑phenyl), 134.1 (d, 2J(31P−13C) = 12 Hz,
C7 or Ca), 132.8 (d, 2J(31P−13C) = 12 Hz, Co,P‑phenyl), 130.6 (d,
4J(31P−13C) = 2 Hz, Cp,P‑phenyl), 129.6 (s, Cp,Sn‑phenyl), 128.8 (d,
3
3J(31P−13C) = 10 Hz, Cm,P‑phenyl), 128.8 (s, J(119/117Sn−13C) = 76/73
Hz, Cm,Sn‑phenyl), 126.9 (d, J(31P−13C) = 35 Hz, C5, C6 or Ci,P‑phenyl),
122.4 (d, 5J(31P−13C) = 4 Hz, C3), 121.1 (d, J(31P−13C) = 35 Hz, C5,
C6 or Ci,P‑phenyl), 120.4 (d, 3J(31P−13C) = 6 Hz, C8), 30.8 (s, C1 or C2),
30.4 ppm (s, C2 or C1). 31P{1H} NMR (CDCl3): δ −27.0 ppm (s,
J(119/117Sn−31P) = 686/656 Hz). 31P{1H} NMR (CD3CN): δ −24.4
ppm (s, J(119/117Sn−31P) = 585/559 Hz). 119Sn{1H} NMR (CDCl3): δ
−214.8 ppm (d, J(31P−119Sn) = 687 Hz). 119Sn{1H} NMR (CD3CN):
δ −194.9 ppm (d, J(31P−119Sn) = 592 Hz). ESI MS (CH2Cl2/MeCN
1/10, positive mode): m/z 611.3 (C36H28PSn) for [5-(SnPh2)-6-
(Ph2P)Ace]+ (7). Molar conductivity (MeCN, c = 5 × 10−7 mol L−1):
Λ 360 Ω−1 cm2 mol−1.
ASSOCIATED CONTENT
■
S
* Supporting Information
Figures, tables, and CIF files giving NMR spectra of 1−8,
crystallographic data for 1−8, crystal data and structure
refinement details for 1−8, selected ELI-D properties of 2−8,
AIM bond paths and isosurface representations of the
localization domains of the ELI-D (Y = 1.4) of 3, 4, 8, 2
(experimental geometry), Ph3Sn+, and Ph3SnCl, ELI-D
distribution mapped on the Sn−P basin of 3, 4, 8, and the P
lone pair basin of 2 (experimental geometry), and Cartesian
coordinates of the optimized gas-phase structures of 2−5, 7a,b,
and 8. This material is available free of charge via the Internet at
http://pubs.acs.org.
Synthesis of (6-(Diphenylphosphino)acenaphth-5-yl)-
diphenyltin Fluoride (8). To a suspension of potassium fluoride
(45.0 mg, 0.77 mmol) and dimethylformamide (3 mL) was slowly
added 6-(diphenylphosphino)acenaphth-5-yl)diphenyltin chloride (3;
100 mg, 0.15 mmol), and the reaction mixture was stirred at room
temperature overnight. The precipitate was filtered, washed with
dimethylformamide (2 mL), and dried in vacuo, yielding 8 as a
colorless solid (87.1 mg, 0.14 mmol, 89%; mp 217 °C dec). Crystals
suitable for X-ray crystallography were obtained by recrystallization by
dimethylformamide.
AUTHOR INFORMATION
■
Notes
The authors declare no competing financial interest.
1H NMR (CD2Cl2): δ 8.60 (d, 3J(1H−1H) = 7 Hz, 3J(119/117Sn−1H)
= 69 Hz, 1H, H-4), 7.66−7.56 (m, 5H), 7.47−7.17 (m, 10H), 7.11 (dt,
ACKNOWLEDGMENTS
■
4
3
3J(1H−1H) = 8 Hz, J(1H−1H) = 2 Hz, 4H), 6.86 (t, J(1H−1H) = 8
Hz, 4H), 3.51 ppm (a, 4H, H-1,2). 13C{1H} NMR (CD2Cl2): δ 152.0
(d, J(31P−13C) = 2 Hz, Cb or Cc), 149.5 (d, J(31P−13C) = 2 Hz, Cc or
The Deutsche Forschungsgemeinschaft (DFG) is gratefully
acknowledged for financial support. We indebted to Prof. Dr.
Takahiro Sasamori, Kyoto University, for valuable comments
on the NMR parameters. Dedicated to Prof. Dr. Gerd-Volker
Cb), 140.2 (dd, J(19F−13C) = 4 Hz), J(31P−13C) = 8 Hz, Ca), 137.3
3
2
(d, J(31P or 19F−13C) = 3 Hz, Ci,Sn‑phenyl), 136.6 (d, J(31P or 19F−13C)
Roschenthalter on the occasion of his 70th birthday.
̈
= 2 Hz, 2J(119/117Sn−13C) = 43 Hz, Co,Sn‑phenyl), 133.3 (d, J(31P−13C)
2
= 14 Hz, Co,P‑phenyl), 132.1 (d, J(31P−13C) = 15 Hz, C5, C6 or
Ci,P‑phenyl), 129.6 (d, 4J(31P−13C) = 1 Hz, Cp,P‑phenyl), 129.4 (s,
Cp,Sn‑phenyl), 128.9 (d, J(31P−13C) = 22 Hz, C5, C6 or Ci,P‑phenyl), 128.8
REFERENCES
■
(1) (a) Hoefelmeyer, J. D.; Schulte, M.; Tschinkl, M.; Gabbai, F. P.
Coord. Chem. Rev. 2002, 235, 93−103. (a) Kilian, P.; Knight, F. R.;
Woollins, J. D. Chem. Eur. J. 2011, 17, 2302−2328.
(s, J(119/117Sn−13C) = 70 Hz, Cm,Sn‑phenyl), 128.8 (d, J(31P−13C) = 8
Hz, Cm,P‑phenyl), 125.1 (d, J(31P−13C) = 17 Hz, C5, C6 or Ci,P‑phenyl),
121.5 (d, J(31P or 19F−13C) = 4 Hz, C3), 120.4 (d, 3J(31P−13C) = 4 Hz,
C8), 30.9 (s, C1 or C2), 30.7 ppm (s, C2 or C1). 19F{1H} NMR
(CD2Cl2): δ −184.9 ppm (d, J(31P−19F) = 84 Hz, 1J(119/117Sn−19F) =
2232/2133 Hz). 31P{1H} NMR (CD2Cl2): δ −34.1 ppm (d,
J(19F−31P) = 84 Hz, J(119/117Sn−31P) = 712/678 Hz). 119Sn{1H}
NMR (CD2Cl2): δ −232.4 ppm (dd, 1J(19F−119Sn) = 2232 Hz),
J(31P−119Sn) = 714 Hz). MS (EI+): m/z: 611 [(M − F)+].
3
3
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