Peri-interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and derivatives

Article abstract of DOI:10.1002/zaac.201300272

The syntheses and full characterizations of the peri-substituted naphthalenes (Nap) and acenaphthenes (Ace) 1-Br-8-(Ph₂P)-Nap (1a) and 5-Br-6-(Ph₂P)-Ace (1b), as well as their derivatives 1-Br-8- [Ph₂P(E)]-Nap [E = CH₃ + (counterion I-) (2a); E = O (3a); E = S (4a); E = Se (5a)] and 5-Br-6-[Ph₂P(E)]-Ace [E = CH ₃ + (counterion I-) (2b); E = O (3b); E = S (4b); E = Se (5b)] are reported. In order to quantify the energetic and electronic effects of the peri-interactions, an additional set of molecules, 1c-5c, with the bromine atom and the Ph₂P(E) fragment on opposite sides of the naphthalene group was generated, which serves as reference because 1c-5c exhibit negligible peri-interactions. The molecular arrangements of all 15 compounds were optimized at the B3PW91/6-311+G(2df,p) level of theory. The analysis of the peri-interactions was not only based on the inspection of the molecular arrangement and energies alone, but extended to a set of real-space bonding indicators (RSBI). These indicators were derived from theoretically calculated electron densities and pair densities, respectively. Particularly, the stockholder, Atoms-In-Molecules (AIM) and Electron-Localizability-Indicator (ELI-D) space partitioning schemes were used to produce Hirshfeld surfaces (HS), bond topological properties and basins of localized bonding and nonbonding electron pairs. Since 1c-5c are 35-58 kJ·mol-1 lower in energy than their counterparts 1a-5a, the hypothesis of a mainly repulsive peri-interaction in 1a/b-5a/b was confirmed. The shapes and contact patterns of the HSs of atoms and fragments involved in the peri-interactions (Br, P, E = CH₃ +, O, S, Se) reveal that only in 1a and 1b are peri-interactions exhibited between the bromine and the phosphorus atoms. In all other cases (2a/b-5a/b), the interaction mainly occurs between the bromine atom and the E atom/fragment. According to the bond topological properties and the electron populations within the (non)bonding ELI-D basins, which both are almost unaffected by the Br-P/E periinteraction, sterical interactions are characterized essentially by geometrical and energetical changes.

Full text of DOI:10.1002/zaac.201300272

ARTICLE
DOI: 10.1002/zaac.201300272
Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene,
6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
Jens Beckmann,*[a] Truong Giang Do,[a] Simon Grabowsky,[b] Emanuel Hupf,[a]
Enno Lork,[a] and Stefan Mebs*[c]
Keywords: Peri-interactions; Naphtalenes; Bromium; Density functional calculations; X-ray diffraction
Abstract. The syntheses and full characterizations of the peri-substi- respectively. Particularly, the stockholder, Atoms-In-Molecules (AIM)
tuted naphthalenes (Nap) and acenaphthenes (Ace) 1-Br-8-(Ph2P)-Nap and Electron-Localizability-Indicator (ELI-D) space partitioning
(1a) and 5-Br-6-(Ph2P)-Ace (1b), as well as their derivatives 1-Br-8- schemes were used to produce Hirshfeld surfaces (HS), bond topologi-
[Ph2P(E)]-Nap [E = CH3+ (counterion I–) (2a); E = O (3a); E = S (4a);
E = Se (5a)] and 5-Br-6-[Ph2P(E)]-Ace [E = CH3+ (counterion I–) (2b);
E = O (3b); E = S (4b); E = Se (5b)] are reported. In order to quantify
the energetic and electronic effects of the peri-interactions, an ad-
cal properties and basins of localized bonding and nonbonding electron
pairs. Since 1c–5c are 35–58 kJ·mol–1 lower in energy than their coun-
terparts 1a–5a, the hypothesis of a mainly repulsive peri-interaction in
1a/b–5a/b was confirmed. The shapes and contact patterns of the HSs
ditional set of molecules, 1c–5c, with the bromine atom and the of atoms and fragments involved in the peri-interactions (Br, P, E =
Ph2P(E) fragment on opposite sides of the naphthalene group was gen-
CH3+, O, S, Se) reveal that only in 1a and 1b are peri-interactions
erated, which serves as reference because 1c–5c exhibit negligible exhibited between the bromine and the phosphorus atoms. In all other
peri-interactions. The molecular arrangements of all 15 compounds cases (2a/b–5a/b), the interaction mainly occurs between the bromine
were optimized at the B3PW91/6-311+G(2df,p) level of theory. The
atom and the E atom/fragment. According to the bond topological
analysis of the peri-interactions was not only based on the inspection
properties and the electron populations within the (non)bonding
of the molecular arrangement and energies alone, but extended to a set ELI-D basins, which both are almost unaffected by the Br-P/E peri-
of real-space bonding indicators (RSBI). These indicators were derived interaction, sterical interactions are characterized essentially by geo-
from theoretically calculated electron densities and pair densities, metrical and energetical changes.
1,8-dimethylaminonapththalene, (1,8-Me2N)2-Nap (A), which
Introduction
has found applications as a proton sponge (Scheme 1).[4]
Peri-substituted naphthalenes (Nap) and acenaphthenes
(Ace) feature prominent transannular interactions between the
substituents in 1,8- and 5,6-positions that can be repulsive due
to steric congestion or attractive due to weak or strong bond-
ing. The close proximity of the peri-substituents may also give
rise to cooperative effects, for instance in the concomitant
binding of other atoms in a chelating mode.[1–3] Much of the
earlier work on peri-substituted naphthalenes revolved around
The facile C–H lithiation of dimethylnaphthylamine Me2N–
Nap (B) using n-butyllithium[5] and subsequent salt metathesis
with (organo)element halides proved to be a straight-forward
route for the synthesis of intramolecularly coordinating 8-di-
methylaminonaphthyl-element species 1-(RnE)-8-(Me2N)-Nap
(C) featuring the elements E = B,[6,7] Al,[8–12] Ga,[10] In,[10,13]
Tl,[13] Si,[14–20] Sn,[14,21–24] P,[25–28] As,[30,31] Sb,[31,32] Bi,[31,33]
S,[34–38] Se,[39–41] and Te.[30–48] Within these compounds, short
E···N transannular distances are frequently observed, which are
indicative of strong attractive interactions.
A natural progression of this chemistry involves the replace-
ment of nitrogen by phosphorus. Consequently, a vast number
of 1,8-diphosphino-substituted naphthalenes, (1,8-X2P)2-Nap,
(D) (X = R, H, Cl, OR, NR2) has been prepared over the
years.[49–61] Amongst those, 1,8-(Ph2P)2-Nap is the most prom-
inent example, and has been utilized as chelating ligand for a
number of transition metals.[62,63] Unlike B, the C–H lithiation
of diphenylphosphinonaphthalene[64] (E) with various organo-
lithium species is not a feasible strategy for the preparation of
the intramolecularly coordinated 8-diphenylphosphinonaph-
thylelement species 1-(RnE)-8-(Ph2P)-Nap (F), which is pre-
sumably the reason why the chemistry of these derivatives has
not been extensively investigated. In fact, we are aware of only
* Prof. Dr. J. Beckmann
E-Mail: j.beckmann@uni-bremen.de
* Dr. S. Mebs
E-Mail: stebs@chemie.fu-berlin.de
[a] Institut für Anorganische Chemie
Universität Bremen
Leobener Straße
28359 Bremen, Germany
[b] School of Chemistry and Biochemistry
The University of Western Australia
35 Stirling Highway,
Crawley WA 6009, Australia
[c] Institut für Chemie und Biochemie
Freie Universität Berlin
Fabeckstraße 36a
14195 Berlin, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300272 or from the au-
thor.
Z. Anorg. Allg. Chem. 2013, 639, (12-13), 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2233

J. Beckmann, S. Mebs et al.
ARTICLE
Scheme 1. Peri-substituted naphthalenes and acenaphthenes.
a few examples of type F compounds bearing E = Si,[65] O, S, ever, the analysis of so-called real-space bonding indicators
and Se.[66,67] The recently introduced 5,6-disubstituted acen- derived either from the electron density (ED) or from the pair
aphthenes[68–72] provide an alternative to 1,8-disubstituted density (or density matrix) provides complementary infor-
naphthalenes since they offer the advantage that the starting mation. Most common indicators are related to the Atoms-In-
material 5,6-dibromoacenaphthene is much easier to obtain Molecules theory (AIM),[76] the stockholder partitioning,[77]
than 1,8-dibromonaphthalene, which is usually prepared by a and the localization functions ELF[78] and ELI.[79] Utilizing
tedious Sandmeyer reaction.[73,74] Furthermore, the tricyclic the AIM theory, a rigorous definition of chemical bonding
acenaphthene ring system is more rigid and possesses smaller based on the electron density is available. Atomic basins and
conformational flexibility than the bicyclic naphthalene ring a corresponding pattern of bond paths as well as bond-, ring-
system, which gives rise to slightly different peri-distances of and cage-critical points (bcp’s, rcp’s, ccp’s) are generated by
approximately 2.5 than 2.7 Å for the parent compounds introducing surfaces of zero electron flux, which provides con-
(Scheme 1).[3] This slight variation allows the study of minute sistent atomic as well as bonding properties. This space-filling
effects of the bonding situation encountered for peri-bonded topological approach has found wide application as a comple-
elements by choosing the same substituents in order to mini- ment to molecular orbital analyses, because the electron den-
mize electronic differences. Surprisingly, 1,8-disubstituted sity can in principle be obtained from both theoretical calcula-
naphthalenes and 5,6-disubstituted acenaphthenes with the tions and high-resolution X-ray diffraction data.[80] The Elec-
same substituents in the peri-positions have not yet been inves- tron Localizability Indicator (ELI) is a further development of
tigated in a comparative study. In the presented work we de- the electron localization function (ELF). Both concepts divide
scribe the synthesis and structural characterization of both 1- space into regions of localized electron pairs instead of atoms
Br-8-(Ph2P)-Nap (1a) and 5-Br-6-(Ph2P)-Ace (1b), as well as and therefore eminently complement AIM theory. The mathe-
+
their derivatives 1-Br-8-[Ph2P(E)]-Nap [E = CH3 (2a); E = O matical method of space partitioning is equivalent to the one
(3a); E = S (4a); E = Se (5a)] and 5-Br-6-[Ph2P(E)]-Ace [E = used in AIM theory. Therefore, the partitioning is likewise
+
CH3 (2b); E = O (3b); E = S (4b); E = Se (5b)] (Scheme 2), space filling and discrete, providing consistent integrated elec-
which hold potential as starting materials for compounds of tron counts of both core shells and (non)bonded valence elec-
type F and related acenaphthene derivatives.
trons. For the interpretation of atom–atom interactions, the cal-
The bonding situation in sterically crowded molecular sys- culation of overlap of ELI valence basins with AIM atoms is
tems is almost exclusively interpreted in terms of molecular very helpful. It was developed by Raub and Jansen based on
arrangements, occasionally supported by NBO (natural bond the ELF and used primarily for the estimation of bond polarit-
orbital) analysis from density functional calculations.[75] How- ies.[81] The visualization of density-based surfaces of atoms,
2234
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
Scheme 2. Syntheses and 31P NMR chemical shifts (CDCl3) of 1a–5a and 1b–5b.
functional groups and molecules in crystals aids understanding tures and theoretically obtained real-space bonding indicators
of steric demands, while mapping electronic properties (e.g. derived from the AIM and ELI-D partitioning schemes. Due
the electrostatic potential; ESP) onto the same surfaces pro- to the significant out-of-plane shifts of the bromine and phos-
vides insight into the electron distribution. The most prominent phorus atoms, the peri-interaction is assumed to be mainly of
surface types are the zfs-boundaries within the AIM scheme, repulsive character in 1a–5a and 1b–5b. In order to quantify
the 001-isosurface of the electron density (the ED is cut at these effects a comparative analysis of the naphthalene and
0.001 au) and the Hirshfeld Surface,[82] which is defined by acenaphthene derivatives is extended to include an analysis of
stockholder partitioning.
the 1,5-bis-substituted naphthalene compounds 1c–5c. They
In this work, the peri-interactions between the bromine atom serve as reference molecules (hereafter abbreviated “Ref”) be-
+
and the PPh2E fragment (E = none, CH3 , O, S, Se) of 1a– cause they are considered to have “standard” (and much
5a and 1b–5b are analyzed in terms of experimentally and weaker) peri-interactions between the bromine and the hydro-
theoretically obtained molecular arrangements, Hirshfeld sur- gen atoms as well as between the PPh2E fragments and the
faces based on experimental geometries from the crystal struc- hydrogen atoms (Scheme 3).
Scheme 3. Computed 1,5-substituted naphthalenes used as reference (Ref) compounds.
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2235

J. Beckmann, S. Mebs et al.
ARTICLE
course. In this work, we describe the properties of those
compounds bearing phosphorus atoms in the 6- and 8-posi-
tions. 1a and 1b were reacted with methyl iodide to produce
the corresponding methylphosphonium iodides [1-Br-8-
(Ph2PCH3)-Nap]I (2a·I) and [1-Br-8-(Ph2PCH3)-Ace]I (2b·I)
in 79 and 89% yield (Scheme 2).
Results and Discussion
Synthetic Aspects
1,8-Dibromonaphthalene was prepared by the reaction of
1,8-bis(tributylstannyl)naphthalene[83] with bromine in 67%
yield. We found this procedure more convenient than the more
usual Sandmeyer reaction,[73,74] which has been noted as being
painstaking.[3,62] 5,6-Dibromoacenaphthene was readily avail-
able by bromination of the parent acenaphthene.[84] The lithi-
ation of 1,8-dibromonaphthalene and 5,6-dibromoacenaph-
thene using n-butyllithium at –78 °C proceeded with a single
metal-halide exchange.
The subsequent reaction with diphenylchlorophosphine af-
forded 8-diphenylphosphino-1-bromonaphthalene, 1-Br-8-
(Ph2P)-Nap (1a), and 6-diphenylphosphino-5-bromonaphthal-
ene, 6-Br-5-(Ph2P)-Ace (1b), in 51% and 54% yield
(Scheme 2).
The oxidation of 1a and 1b with hydrogen peroxide, sulfur
and selenium powder gave rise to the formation of the phos-
phine oxides 1-Br-8-(Ph2PO)-Nap (3a) and 6-Br-5-(Ph2PO)-
Ace (3b) in 77 and 96% yield, the phosphine sulfides 1-Br-8-
(Ph2PS)-Nap (4a) and 6-Br-5-(Ph2PS)-Ace (4b) in 50 and 77%
yield, and the phosphine selenides 1-Br-8-(Ph2PSe)-Nap (5a)
and 6-Br-5-(Ph2PSe)-Ace (5b) in 38 and 67% yield, respec-
tively (Scheme 2). Compounds 1a–5a and 1b–5b were charac-
terized by 31P NMR spectroscopy (Scheme 2) as well as 13C
1
and H NMR spectroscopy and MS spectrometry (see Experi-
mental Section).
We note that the preparation of 1a has previously been re-
ported[65,85] but apart from the 31P NMR chemical shift, nei-
ther spectroscopic nor structural data were reported at the time.
In 1a and 1b, both substituents in the peri-positions may be
Molecular Environment and Hirshfeld Surfaces
The molecular structures of 1a–5a and 1b–5b determined
susceptible to undergo chemical transformations. The bromine by X-ray crystallography are shown in Figure 1, Figure 2, Fig-
atoms in 1- and 5-positions may be replaced by other hetero- ure 3, Figure 4, and Figure 5. Additionally, the molecular
atoms, such as B, Si, Sn, Sb, Te, and Hg. However, the chemis- structures of 1a/b/c–5a/b/c were obtained by geometry optimi-
try of these compounds will be reported elsewhere in due zation at the DFT/B3PW91/TZ level of theory. Figures of these
Figure 1. Molecular structures of 1a and 1b showing 30% probability ellipsoids and the crystallographic numbering scheme.
Figure 2. Molecular structures of 2a and 2b showing 30% probability ellipsoids and the crystallographic numbering scheme.
2236 www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
Figure 3. Molecular structure of 3a and 3b showing 30% probability ellipsoids and the crystallographic numbering scheme.
Figure 4. Molecular structures of 4a and 4b showing 30% probability ellipsoids and the crystallographic numbering scheme.
Figure 5. Molecular structure of 5a and 5b showing 30% probability ellipsoids and the crystallographic numbering scheme.
theoretical models are given in the Supporting Information. Table 1. Considering the five reference compounds 1c–5c, the
Experimentally and computationally obtained geometric pa- given geometrical parameters reveal almost unstrained arran-
rameters, which were introduced by Woollins and co-workers gements with Br(1)–C(10)–C(19) and P(1)–C(18)–C(19)
and are typically reported for structural analyses of this com- angles close to 120°. Accordingly, the C(10)–C(19)–C(18) an-
pound class (see for example Ref. [86]) are collected in gle is ca. 123° and the torsion angles C(13)–C(14)–C(19)–
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2237

J. Beckmann, S. Mebs et al.
Table 1. Selected experimental (first row) and computational (second row, italics) distances /Å and angles /° for 1a–5a, 1b–5b, and 1c–5c.
ARTICLE
1a
2a·I–
3a
4a
5a
E
–
CH3
O
S
Se
Peri-region-distances
P(1)–Br(1)
3.139(2)
3.350(2)
3.302(1)
3.417(2), 3.386(2)
3.388(2)
3.147
3.386
3.297
3.391
3.399
Peri-region bond angles
Br(1)–C(10)–C(19)
124.2(3)
123.52
126.8(4)
127.66
123.3(3)
123.52
374(1)
374.70
14
122.6(4)
122.75
129.2(5)
128.59
127.0(4)
127.55
379(2)
378.89
19
123.5(2)
123.30
128.5(3)
127.84
125.0(2)
125.56
377.0(7)
376.70
17
122.7(3), 122.9(3)
123.20
128.8(4), 128.2(4)
128.11
125.4(3), 126.2(3)
125.76
377(2), 377(2)
377.07
17, 17
123.2(3)
123.14
128.4(3)
128.13
126.3(3)
123.14
377.9(9)
374.41
17.9
C(10)–C(19)–C(18)
P(1)–C(18)–C(19)
Σ of bay angles
a)
Splay angle
14.70
101.1(3)
18.89
107.8(3)
16.70
103.8(2)
17.07
105.3(3), 104.7(2)
14.41
102.9(3)
C(20)–P(1)–C(30)
101.48
106.67
103.21
102.22
102.23
Out-of-plane displacement
P(1)
–0.364(2)
0.420
0.548(2)
0.666
–0.571(1)
0.639
–0.701(2), –0.640(2)
0.777
0.570(2)
0.786
Br(1)
0.472(1)
–0.268
–0.557(1)
–0.581
0.431(1)
–0.504
0.691(1), 0.645(1)
–0.601
–0.636(1)
–0.606
Central naphthalene ring torsion angles
C:(13)-(14)-(19)-(18)
174.2(4)
–176.46
174.6(5)
–175.88
172.3(7)
–173.01
172.4(7)
–170.01
178.0(4)
–173.42
173.4(3)
–172.15
171.6(5), 173.1(5)
–172.34
169.3(5), 169.8(5)
–170.41
176.0(4)
–172.29
172.5(5)
–170.26
C:(15)-(14)-(19)-(10)
1b
2b·I–
3b
4b
5b
E
–
CH3
O
S
Se
Peri-region-distances
P(1)–Br(1)
3.225(2), 3.212(2)
3.435(4)
3.372(2)
3.445(1)
3.442(3)
3.213
3.460
3.353
3.449
3.460
Peri-region bond angles
Br(1)–C(10)–C(19)
122.8(3), 123.1(3)
123.51
131.1(3), 131.3(3)
131.08
124.1(3), 123.0(3)
123.65
378.0(9), 377.4(9)
378.24
18, 17
121.5(9)
123.73
132(1)
132.40
126.1(9)
127.87
380(3)
384.00
20
122.9(2)
124.05
131.9(3)
131.58
125.9(2)
126.89
380.7(7)
382.52
20.7
124.9(3)
124.28
132.3(3)
131.96
127.1(2)
126.58
384.3(8)
382.82
24.3
125.7(4)
124.23
131.7(5)
131.98
127.0(4)
126.62
384(2)
382.83
24
C(10)–C(19)–C(18)
P(1)–C(18)–C(19)
Σ of bay angles
a)
Splay angle
18.24
100.3(3), 100.9(2)
24.00
107.8(5)
22.52
102.8(2)
22.82
101.0(2)
22.83
102.2(2)
C(20)–P(1)–C(30)
101.46
106.47
102.75
101.71
101.74
Out-of-plane displacement
P(1)
0.208(2), 0.219(1)
0.177
0.671(4)
0.395
–0.466(1)
0.151
–0.050(1)
0.476
0.074(2)
0.505
Br(1)
0.019(1), –0.195(1)
–0.043
–0.370(2)
–0.347
0.146(1)
–0.056
0.251(1)
–0.314
0.011(1)
–0.338
Central acenaphthalene ring torsion angles
C:(13)-(14)-(19)-(18)
180.0(4), 179.4(4)
–179.16
174(2)
–176.71
173(2)
178.5(4)
–179.22
174.6(4)
–179.38
177.0(3)
–176.48
179.2(3)
–175.27
176.3(6)
–176.23
176.7(6)
–174.84
C:(15)-(14)-(19)-(10)
179.2(4), 177.0(4)
–179.66
–174.19
1c
2c·I–
3c
4c
5c
+
E
–
CH3
O
S
Se
Peri-region bond angles
Br(1)–C(10)–C(19)
C(10)–C(19)–C(18)
P(1)–C(18)–C(19)
C(20)–P(1)–C(30)
Out-of-plane displacement
P(1)
120.24
123.18
118.60
102.43
120.52
122.45
122.06
108.74
120.33
123.03
120.09
106.04
120.35
122.80
121.24
104.45
120.35
122.75
121.48
104.35
b)
0.024
–0.027
–0.146
–0.024
0.104
0.027
–0.020
0.021
–0.033
0.019
Br(1)
Central acenaphthalene ring torsion angles
C:(13)-(14)-(19)-(18)
C:(15)-(14)-(19)-(10)
–178.71
–178.89
–179.22
–178.18
–178.76
–178.76
–179.08
–179.07
–179.23
–179.04
a) Splay angle: Σ of the three bay region angles – 360. b) (Br)–CCC.
C(18) and C(15)–C(14)–C(19)–C(10) are ca. 179°. In contrast, and acenaphthene derivatives. However, in 1a/b–5a/b this an-
the C(20)–P(1)–C(30) angle shows a dependency against the gle is slightly smaller, which may be related to the peri-interac-
nature of E, which follows the same trend as in the naphthalene tions as it is found for both the experimental and theoretically-
2238
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
+
optimized geometries. In cases of E = CH3 (2c) and O (3c), atoms can be identified, delineated by the darker colored
considerable out-of-plane-shifts d(P) of ca. 0.1 Å are observed edges. Interestingly, in all other compounds except 1a and 1b,
for the phosphorus atoms. In all other cases, the d(P) and d(Br) there is no contact patch between the bromine and phosphorus
values are below 0.04 Å.
atoms, and the surface shape is rather convex for the phos-
In comparison to the reference values for 1c to 5c, system- phorus atom facing the bromine atom (wedge shape), as exem-
atic changes of some geometric parameters are observed for plified for 5b in Figure 6b and shown in the Supporting Infor-
the naphthalenes and acenaphthenes 1a/b–5a/b: The Br(1)– mation for the remaining compounds. The absence of a contact
C(10)–C(19) and P(1)–C(18)–C(19) angles are about 2–6° patch between two atoms being in such close proximity is very
larger, whereas the intra-annulene torsions angles C(13)– unusual – we are not aware of another example where this
C(14)–C(19)–C(18) and C(15)–C(14)–C(19)–C(10) are phenomenon has been observed. This means that the situation
smaller by 3–10° in most cases. All geometrical results com- occurring in 2a/b to 5a/b, where two atoms try to avoid con-
pare very well with 1-SePh-8-[Ph2P(E)]-Nap (E = O, S, Se), tact, implies the interaction is strongly repulsive as expected.
which were recently published by Woollins and co-workers.[67] The intramolecular through-space contacts are mainly ob-
As expected, the phenyl group attached to the selenium atom served between the bromine and the selenium atoms (Fig-
does not increase the steric strain, as it is not directed towards ure 6c) and the bromine atom and the equatorial phenyl ring
the peri-region. Due to the ethylene bridge on the opposite side (not shown). This is supported by the bond topologies (see
of the peri-interaction, the bay angle C(10)–C(19)–C(18) is below).
always larger in the acenaphthene than in naphthalene spe-
cies.[3] In the presented compounds, this angle is ca. 5° larger
for the naphthalenes and 9° for the acenaphthenes than ob-
Energies
served in the reference compounds 1c–5c. The out-of-plane
The bond topologies, the shapes of the ELI-basins (see be-
shifts of the bromine and phosphorus atoms show a significant low) and to a lesser degree the molecular arrangements reveal
increase of up to 0.79 Å for d(P) in 5a (theoretically optimized that in the reference species a weak peri-interaction is exhib-
geometry). With few exceptions, both the d(P) and d(Br) val- ited between the bromine and hydrogen atom as well as be-
ues from theoretical models of 1a/b to 5a/b follow a trend tween the PPh2E fragment and the hydrogen atom opposite to
+
depending on the nature of E: none Ͻ O Ͻ CH3 Ͻ S Ͻ Se. the bromine atom. However, since the naphthalene fragments
However, in the experimentally obtained X-ray structures no are almost planar in the reference cases (1c–5c), these effects
such trend is found. Due to the ca. 0.05 Å larger peri-distance are negligible. Accordingly, for the estimation of relative ener-
in the acenaphthenes compared to the naphthalenes, out-of- gies of the steric stress introduced by close proximity of the
plane shifts are much less pronounced in the former. In case bromine atoms to the PPh2E fragment, species 1c–5c serve as
of 1 only a very small shift from 0.027 Å (1c) to 0.043 Å (1b, references. Disregarding 2a, which is only 35.05 kJ·mol–1
theoretical model) is observed for d(Br) which points to a weak higher in energy than 2c, the other compounds follow the same
peri-interaction between bromine and phosphorus in this com- trend to that of the geometrical changes: 1a/c (38.59 kJ·mol–1)
pound. In the experimental solid-state structure of 1b two mo- Ͻ 3a/c (52.92 kJ·mol–1) Ͻ 4a/c (58.49 kJ·mol–1). The lower
lecules are located in the unit cell. The corresponding d(P) energy difference between 2a and 2c may be the result of a
values are 0.019 and –0.195 Å, which points towards an influ- weak attractive interaction between the bromine atom and an
ence of the crystalline environment.
hydrogen atom of the methyl group in 2a. Due to the larger
The surface curvedness mapped on the Hirshfeld surfaces of peri-distance in the acenaphthene derivatives, these differences
atomic fragments derived from the experimental crystal struc- in energy are expected to be lower.
tures of compounds 1a and 5b are displayed in Figure 6.[82]
Considering 1a, the atomic Hirshfeld surfaces of the bromine
and the phosphorus atoms are found to be in contact with each
Bond Topology
other as expected for two atoms being in close proximity (Fig-
The relevant bond topological properties for 6 of the 15
ure 6a). Further intermolecular contact sites of the bromine theoretically analyzed models 1a–1c and 5a–5c are collected
Figure 6. Curvedness mapped on the Hirshfeld surfaces of atomic fragments derived from the experimental crystal structures of compounds 1a
(a) and 5b (b,c). In (a) and (b), the surfaces are shown for the Br and the P atoms; in (c), the surfaces are shown for the Br and the Se atoms.
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2239

J. Beckmann, S. Mebs et al.
ARTICLE
a)
Table 2. Bond topological parameters of computed 1a–1c and 5a–5c.
Atom–Atom
ρ(r)bcp /e·Å–3 Δρ(r)bcp /e·Å–5 d1 /Å
d2 /Å
ε
G/ρ(r)bcp /he–1 H/ρ(r)bcp /he–1 d /Å
1a
Br–C10
P–C18
P–C20
P–C30
Br–P
Br–P (rcp)
Br–C10
P–C18
P–C20
P–C30
Br–P
Br–P (rcp)
C20–H17
C20–H17 (rcp) 0.11
Br–C13
P–C18
1.10
1.03
1.07
1.08
0.13
0.08
1.10
1.04
1.07
1.08
0.12
0.07
0.11
–3.8
–6.4
–6.3
–6.3
1.0
1.045
0.762
0.744
0.739
1.639
–
1.045
0.748
0.739
0.738
1.667
–
0.856
1.099
1.099
1.098
1.516
–
0.855
1.106
1.103
1.100
1.556
–
0.07
0.14
0.16
0.16
0.09
–
0.07
0.16
0.16
0.15
0.09
–
0.35
0.49
0.55
0.97
0.56
0.90
0.35
0.54
0.57
0.57
0.56
0.88
0.78
0.83
0.35
0.56
0.59
0.57
0.77
0.70
0.88
0.82
0.35
0.38
0.45
0.48
0.42
0.63
0.64
0.65
0.81
0.76
0.86
0.35
0.36
0.42
0.48
0.42
0.62
0.64
0.82
0.57
0.59
0.75
0.88
0.35
0.49
0.47
0.48
0.41
0.76
0.70
0.89
0.77
–0.59
–0.92
–0.96
–0.56
–0.01
0.19
–0.59
–0.94
–0.96
–0.97
0.01
0.20
0.14
0.15
–0.59
–0.96
–0.97
–0.97
0.14
0.10
0.17
1.900
1.861
1.844
1.837
3.147
–
1.900
1.854
1.843
1.838
3.213
–
1.2
1b
–3.8
–6.0
–6.0
–6.1
1.0
1.1
1.4
1.430
–
1.042
–
3.86
–
2.359
–
1.5
1c
5a
1.10
1.07
1.08
1.08
0.10
0.10
0.10
0.10
1.12
1.08
1.12
1.15
0.93
0.08
0.08
0.08
0.06
0.12
–3.8
–6.0
–6.0
–6.1
1.2
1.1
1.4
1.047
0.742
0.736
0.739
1.673
1.567
–
0.855
1.102
1.101
1.100
1.046
1.047
–
0.07
0.17
0.14
0.15
1.71
1.53
–
1.902
1.844
1.836
1.839
2.690
2.594
–
P–C20
P–C30
Br–H15
P–H10
Br–H15 (rcp)
P–H10 (rcp)
Br–C10
P–C18
P–C20
P–C30
P–Se
Br–P
Br–P (r)
Br–C30
Br–C30 (rcp)
C20–H17
1.3
–
–
–
0.14
–
–3.9
–8.4
–8.4
–8.5
–2.3
0.8
0.8
0.9
0.9
1.5
1.037
0.777
0.754
0.744
1.065
1.786
–
1.778
–
1.382
–
1.037
0.785
0.761
0.744
1.065
1.782
1.782
–
1.803
–
1.369
–
0.856
1.079
1.088
1.083
1.045
1.632
–
1.528
–
0.977
–
0.856
1.062
1.082
1.084
1.046
1.691
1.500
–
1.992
–
0.944
–
0.07
0.06
0.05
0.06
0.03
20.65
–
5.04
–
1.68
–
0.07
0.07
0.05
0.07
0.01
2.20
1.56
–
50.20
–
0.99
–
–0.60
–0.93
–0.98
–1.00
–0.59
0.08
0.09
0.13
0.18
0.13
1.893
1.855
1.841
1.827
2.110
3.399
–
3.264
–
2.324
–
1.893
1.847
1.843
1.827
2.111
3.460
3.272
–
3.666
–
2.291
–
C20–H17 (rcp) 0.11
1.6
0.14
5b
Br–C10
P–C18
P–C20
P–C30
P–Se
Br–P (vir)
Br–C30
Br–C30 (rcp)
Br–Se
Br–Se (rcp)
C20–H17
C20–H17 (rcp) 0.12
Br–C10
P–C18
P–C20
P–C30
1.12
1.10
1.12
1.15
0.93
0.07
0.08
0.06
0.07
0.07
0.12
–3.9
–8.7
–8.6
–8.5
–2.3
0.7
0.9
0.8
0.7
0.7
–0.60
–0.92
–0.96
–1.00
–0.59
0.09
0.13
0.20
0.09
0.08
b)
1.5
1.7
0.12
0.14
5c
1.10
1.13
1.13
1.14
0.93
0.10
0.08
0.10
0.08
–3.8
–8.1
–8.4
–8.3
–2.3
1.3
0.9
1.5
1.0
1.047
0.744
0.748
0.744
1.065
1.667
1.651
–
0.854
1.089
1.084
1.085
1.048
1.034
1.091
–
0.07
0.07
0.05
0.07
0.01
1.41
4.51
–
–0.59
–0.99
–0.99
–1.00
–0.59
0.14
0.11
0.17
0.13
1.901
1.833
1.832
1.828
2.113
2.674
2.716
–
P–Se
Br–H15
P–H10
Br–H15 (rcp)
P–H10 (rcp)
–
–
–
–
a) For all bonds, ρ(r)bcp is the electron density at the bond critical point, Δρ(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; λ1/2: curvatures perpendicular to the bond path), G/ρ(r)bcp and
H/ρ(r)bcp are the kinetic and total energy density over ρ(r)bcp ratios. Results obtained by an analysis of the wavefunction files with AIM2000[90]
b) In the corresponding viral field a Br–P bond critical point is observed.
.
in Table 2. The corresponding molecular graphs are shown in tically analyzed models are virtually identical, although the
Figure 7. Topological properties and molecular graphs of the bromine atom lies in the naphthalene plane in the reference
remaining models are given in the supporting information. All species and significantly out-of-plane for naphthalene and
Br–C and P–C bond topological properties show the character- acenaphthene derivatives (up to 0.606 Å for 5a). This observa-
istics of polar-covalent interactions. The electron density at the tion points towards a quite flexible Br–C bond character with
bcp varies between ca. 1.1 to 1.2 e·Å–3 for all cases. Interest- delocalization of the bromine valence electrons and leads to
ingly, the Br–C bond topological parameters of the 15 theore- the assumption that the energy costs of an out-of-plane shift of
2240
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
Figure 7. AIM bond topology of compounds 1a–c and 5a–c.
Table 3. Atomic/fragmental AIM Q(001) charges (in e) of the theoretical models.
a)
Nap / Ace
Ph(ax)
Ph(eq)
Br
P
E
1a
1b
1c
2a
2b
2c
3a
3b
3c
4a
4b
4c
5a
5b
5c
–0.17
–0.13
–0.18
0.00
–0.40
–0.30
–0.30
–0.19
–0.21
–0.17
–0.31
–0.33
–0.29
–0.24
–0.30
–0.24
–0.24
–0.28
–0.23
–0.33
–0.33
–0.31
–0.19
–0.28
–0.19
–0.31
–0.31
–0.30
–0.27
–0.24
–0.28
–0.25
–0.33
–0.26
0.01
0.00
0.00
0.00
0.00
0.07
0.03
0.03
0.00
0.01
0.00
0.01
0.00
–0.01
0.00
1.47
1.50
1.50
2.35
2.37
2.41
2.92
2.93
2.94
2.02
2.01
2.08
1.73
1.74
1.79
–
–
–
–0.27
–0.29
–0.29
–1.45
–1.45
–1.46
–0.65
–0.66
–0.66
–0.62
–0.56
–0.40
0.07
–0.09
–0.17
–0.12
–0.19
–0.12
–0.06
–0.16
–0.11
–0.07
–0.14
a) Naphthyl or acenaphthyl fragment.
the bromine atom are also quite low. In contrast, the P–C(naph- Atomic Properties
thyl) bond lengths depend slightly on the steric strain as they
are ca. 0.02 Å shorter in the relaxed geometries of 1c–5c.
Like for the AIM bond topology, the steric strain has only
However, these effects are small. Moreover, the P–E bonds a small influence on the atomic AIM charges. The charges of
+
(E = CH3 , O, S, Se) are also completely unaffected by the the relevant fragments – the naphthyl ring, the axial and equa-
structural variation so it can be concluded that the steric strain torial phenyl rings, the bromine atom, the phosphorus atom
+
is barely observable within the AIM-topology. In all models and the E fragment (E = CH3 , O, S, Se) – are collected in
Br–P, Br–E, Br–C(phenyl) and/or Br–H(methyl) contacts are Table 3.
observed because of the presence of bond critical points. As
As expected, the charge of the phosphorus atom shows pro-
expected, they show small electron density values of 0.05– nounced effects depending on the nature of the E atom/frag-
0.13 e·Å–3 at the bcp and a positive Laplacian close to zero. ment attached to it, but the effect of the increased steric hin-
Their extraordinarily large bond ellipticities reflect a somewhat drance within the series Ref Ͻ Ace Ͻ Nap is hardly distin-
smeared electron density between the bromine atom and its guishable. Pertaining to the charges of the E atom/fragment,
sterically close neighbors.
only when E = Se a small increase of charge is observed (Ref
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.zaac.wiley-vch.de 2241

J. Beckmann, S. Mebs et al.
ARTICLE
= –0.40 e Ͻ Ace = –0.56 e Ͻ Nap = –0.62 e). However, the compounds 2a and 2b as mentioned above. Inspection of the
three organic residues (naphthyl ring, axial/equatorial phenyl remaining basin types uncovers distinct effects depending on
ring) are almost unaffected by both the nature of E and by the the nature of E, but the differences between the trans-species
magnitude of steric hindrance. The same is true for the bro- and the naphthalene and acenaphthene derivatives are negligi-
mine atoms.
ELI-D Analysis
Since all non-terminal atoms are by definition involved in
more than one chemical contact, atomic AIM charges may in
some cases hinder the evaluation of substituent effects because
shifts of electron populations may cancel out and produce sim-
ilar atomic AIM charges despite different chemical environ-
ments. However, a more detailed view is provided by the
analysis of integrated electron populations within distinct
bonding or lone pair basins generated by space partitioning
according to the ELI-D scheme. In this work, the analysis is
divided into two parts: first, the bonding and lone pair basins
of the bromine atoms and the PPh2E fragments are analyzed,
and second, the C–C bonds in the naphthalene and acenaph-
thene groups are analyzed. The electron populations of the
ELI-D basins in the Br–C bond, the summed values of the lone
pairs of the bromine atoms, the values of the three P–C bonds,
the summed values of the P–E bonds, the summed values of
the lone pairs of the E atoms (for E = O, S, Se) and the
summed values of the populations of the hydrogen atoms for
+
E = CH3 are listed in Table 4. The number of contributing
basins is additionally given for the lone pairs and the P–E
bonds. With regards to the Br–C bond and the lone pairs of
the bromine atom, the observed changes in the electron popula-
tions are remarkably small. The maximum change for these
basin types is 0.03 e. This is especially noteworthy for the
summed electron populations in the lone pairs of the bromine
atom, which seem to be totally unaffected by the nature of E in
the PPh2E fragment and the degree of geometrical distortion.
Compound 2 is an exception, for which a slight decrease in
Figure 8. ELI-D iso-surface representations (side and top view) of
compounds 1a (first row), 2a (second row) and 5c (third row). The
surfaces are color-coded according to the basin size: light gray (small)
through to dark gray (large). For clarity, protonated valence basins
the Br–C bond population is accompanied by a corresponding
increase in the lone pair population. This is in accordance with
the assumption of a weak attractive interaction between the
bromine atom and a hydrogen atom of the methyl group in (hydrogen atoms) are in transparent.
Table 4. Electron populations (in e) of the bonding and lone pair basins of the Br atom and the PPh2E fragment in the theoretical models.
Model
Br–C10
Σ LP(Br)
No.
P–C18
P–C20
P–C30
P–E/LP
No.
Σ LP(E)/H No.
1a
1b
1c
2a
2b
2c
3a
3b
3c
4a
4b
4c
5a
5b
5c
1.55
1.54
1.54
1.54
1.53
1.60
1.58
1.57
1.54
1.58
1.57
1.54
1.58
1.57
1.54
6.54
6.55
6.55
6.56
6.57
6.50
6.53
6.53
6.55
6.56
6.55
6.55
6.54
6.55
6.54
3
3
3
3
3
2
1
3
3
2
2
3
2
2
3
2.16
2.17
2.15
2.28
2.30
2.28
2.28
2.28
2.26
2.25
2.25
2.22
2.24
2.24
2.22
2.15
2.15
2.14
2.23
2.24
2.26
2.24
2.25
2.25
2.20
2.21
2.21
2.19
2.20
2.20
2.15
2.15
2.14
2.25
2.25
2.25
2.25
2.24
2.25
2.21
2.20
2.22
2.20
2.19
2.21
2.05
2.06
2.05
1.99
1.99
1.99
1.61
1.58
1.60
2.02
2.01
2.00
2.16
2.16
2.14
1
1
1
1
1
1
2
2
1
1
1
1
1
1
1
–
–
–
–
–
–
3
3
3
2
2
2
2
3
3
2
3
3
5.87
5.86
5.85
6.13
6.15
6.13
5.76
5.77
5.78
5.93
5.92
5.94
2242
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
ble. Up to this point the results indicate that significant geo- the annulene ring system indicates that the mesomeric structure
metrical changes are accompanied by negligible changes in the shown in Figure 9 is the dominant one for all cases. The cen-
electron densities and pair densities in the peri-region which tral bond connecting the two rings is similar, however, to the
we assert is characteristic of any type of repulsive interaction. four C–C bonds attached to it and therefore no double bond
This is supported by the combined analysis of the AIM and has been drawn here. The dELI values are in the range of
ELI-D space partitioning schemes: The partial electron popula- 0.002–0.030 Å for the almost planar reference species and with
tion of the P or E atoms lone pair ELI-D basins within the few exceptions increases for the strained C–C bonds. The
AIM bromine atom never exceeds 1% of the total value.
This means that sterically repelling atoms are characterized
by an almost similar location and shape of both the AIM zero-
flux-surfaces and the boundaries of the ELI-D basins. Iso-sur-
face representations (Y = 1.3) of the ELI-D for compounds 1a,
2a, and 5c are shown in Figure 8. A characteristic feature of
the peri-interaction is the fact that the lone-pair basins of the
bromine atom are split into two to three fragments with one or
two small and flattened parts pointing towards the peri-part-
ners (H, P, E, equatorial phenyl ring) and a larger part pointing
to the opposite site. In addition, the basins of the peri-partners
are also flattened in direction of the bromine atom. The degree
of flattening depends on the electronegativity of atom E and is
only very small for E = O (see Supporting Information for the
remaining ELI-D figures).
largest value found is 0.067 Å for the C(10)–C(19) bond in 5b.
Figure 9. Dominant mesomeric structure in compounds 1a–5c.
Conclusions
Two related series of peri-substituted naphthalenes 1-Br-8-
+
[Ph2P(E)]-Nap [E = none (1a); E = CH3 (2a); E = O (3a);
In the following, the electronic properties of the C–C bond- E = S (4a); E = Se (5a)] acenaphthenes 5-Br-6-[Ph2P(E)]-Ace
+
ing basins of the naphthalene fragments will be analyzed in [E = none (1b); E = CH3 (2b); E = O (3b); E = S (4b); E =
order to uncover the effects of the geometrical distortion. The Se (5b)] were prepared and fully characterized. Sterical inter-
basin volumes and electron populations both with a 0.001 a.u. actions between the substituents in 1,8- and 5,6-positons lead
cutoff, the ELI-D value at the attractor position (max), and the to considerable geometrical distortions, which are the subject
perpendicular distance of the attractor position to the C–C axis of a large range of experimental studies. In a Hirshfeld surface
(dELI) are reported in Table 5. The electron distribution within analysis, which is based on only geometry and promolecule
a)
Table 5. ELI-D properties of the C–C bonding basins of the naphthalene and acenaphthene fragments in the theoretical models
.
Bond
V(001)
N(001)
Ymax
dELI
V(001)
N(001)
Ymax
dELI
V(001)
N(001)
Ymax
dELI
1a
1b
1c
C10–C19
C19–C18
C17–C18
C17–C16
C15–C16
C14–C15
C14–C13
C13–C12
C10–C12
C10–C11
C14–C19
6.5
6.5
10.2
6.6
9.2
5.7
6.6
10.2
6.7
9.8
6.7
2.65
2.58
2.95
2.56
2.94
2.52
2.60
2.95
2.57
3.08
2.57
1.86
1.88
1.82
1.87
1.80
1.86
1.88
1.82
1.86
1.81
1.87
0.030
0.010
0.005
0.010
0.003
0.010
0.006
0.010
0.007
0.020
0.001
7.0
6.3
9.0
6.7
10.2
6.2
6.5
10.0
6.9
9.7
6.5
2.68
2.55
2.94
2.58
3.00
2.56
2.59
2.99
2.60
3.08
2.58
1.86
1.86
1.80
1.86
1.82
1.88
1.87
1.82
1.86
1.81
1.87
0.063
0.045
0.023
0.006
0.040
0.035
0.038
0.039
0.003
0.004
0.003
6.9
6.5
8.6
6.6
10.2
6.2
6.4
10.1
6.8
9.5
6.7
2.68
2.55
2.92
2.56
2.96
2.55
2.58
2.95
2.59
3.06
2.57
1.86
1.86
1.80
1.87
1.82
1.88
1.88
1.82
1.86
1.81
1.86
0.051
0.033
0.035
0.012
0.016
0.013
0.012
0.020
0.016
0.028
0.002
5a
5b
5c
C10–C19
C19–C18
C17–C18
C17–C16
C15–C16
C14–C15
C14–C13
C13–C12
C11–C12
C10–C11
C14–C19
6.5
6.5
10.2
6.5
9.4
5.7
6.6
10.1
6.7
9.7
6.8
2.65
2.57
2.95
2.55
2.95
2.52
2.60
2.94
2.57
3.08
2.58
1.87
1.88
1.82
1.87
1.80
1.86
1.88
1.82
1.86
1.81
1.87
0.029
0.007
0.006
0.006
0.019
0.016
0.008
0.010
0.006
0.020
0.002
7.1
6.2
9.4
6.6
10.1
6.2
6.5
9.9
7.0
9.5
6.6
2.70
2.52
2.96
2.57
2.99
2.55
2.60
2.97
2.62
3.05
2.58
1.86
1.86
1.80
1.87
1.82
1.88
1.87
1.82
1.86
1.81
1.87
0.067
0.052
0.048
0.020
0.042
0.039
0.039
0.043
0.018
0.027
0.004
6.6
6.1
9.1
6.5
10.2
6.1
6.5
10.0
6.9
9.4
6.9
2.68
2.52
2.95
2.54
2.96
2.54
2.58
2.94
2.59
3.04
2.59
1.86
1.86
1.80
1.87
1.82
1.89
1.88
1.82
1.86
1.82
1.86
0.056
0.040
0.064
0.037
0.036
0.025
0.016
0.039
0.033
0.050
0.005
a) For all basins, V(001) is the basin volume cut at 0.001 a.u., N(001) is the corresponding electron population in that volume, Ymax is the ELI-D
value at the attractor position, dELI is the perpendicular distance of the attractor position to the atom–atom line. Results obtained by analysis of
grid-files using DGRID-4.5.[91] The grid step size is 0.04 bohr.
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2243

J. Beckmann, S. Mebs et al.
ARTICLE
(20 mL) at –78 °C. After 1 h Ph2PCl (1.16 g, 5.25 mmol) was added
and stirring was continued at –78 °C for 60 min. The mixture was
allowed to warm to room temp. overnight. The solvent was removed
and CH2Cl2 (30 mL) was added. The resulting suspension was washed
three times with water. The organic layer was separated, dried with
Mg2SO4, and the solvent was removed by rotary evaporation. The re-
sulting yellow precipitate was recrystallized by CH2Cl2/n-hexane af-
fording 1-Br-8-(Ph2P)-Nap (1a) as pale yellow crystals (1.04 g,
densities, these distortions clearly are the result of two neigh-
boring atoms avoiding each other intramolecularly, which can
be interpreted in terms of pronounced repulsion. Such strong
distortions are also expected to be paralleled by concomitant
changes in real-space bonding descriptors derived from the
electron or pair densities. But this study reveals that for purely
repulsive interactions these changes are very small in spite of
the significant geometrical distortions. In the compounds pre-
sented, steric repulsion is characterized solely by geometrical
1
2.66 mmol, 51%). H NMR: δ = 7.88–7.81 (m, 3 H), 7.36–7.29 (m,
2
13 H). 13C{1H} NMR: δ = 139.3 [d, J(31P-13C) = 14 Hz, C7), 137.2
4
3
and Hirshfeld surface changes and is not paralleled by elec- [d, J(31P-13C) = 1 Hz, C5), 136.4 [d, J(31P-13C) = 3 Hz, Cb], 134.7
[d, 1J(31P-13C) = 17 Hz, C8], 134.1 [d, 2J(31P-13C) = 21 Hz, Co], 131.6
tronic bonding properties. Hence, for future studies on strained
1
4
[d, J(31P-13C) = 31 Hz, Ci], 130.6 (s, C2 or C3), 129.4 [d, J(31P-13C)
= 1 Hz, C4], 128.5 [d, 3J(31P-13C) = 7 Hz, Cm], 128.4 (s, Cp), 125.8
[d, 3J(31P-13C) = 15 Hz, C6], 120.8 [d, 3J(31P-13C) = 1 Hz, C1].
31P{1H} NMR: δ = –5.3 (s) ppm. MS (EI+): m/z: 390 [M+].
molecular systems atom–atom repulsion may be distinguished
from atom–atom attraction by a combined analysis of the mo-
lecular geometries, the molecular energies referenced to corre-
sponding unstrained models (if possible) and details in real-
space bonding indicators. Starting from 1a–5a and 1b–5b we
are currently preparing naphthalenes of type F (Scheme 1) and
related acenaphthenes containing attractive and repulsive peri-
interactions between phosphorus and elements (e.g. E = B, Si,
Sn, Sb, Te, Hg) other than bromine.
Synthesis of 5-Bromo-6-diphenylphosphino-acenaphthene (1b): To
a suspension of 5,6-dibromoacenaphthene (4.00 g, 12.8 mmol) in di-
ethyl ether (40 mL), n-butyllithium (12.8 mmol, 2.5 m in n-hexane)
was added at –78 °C. After 1 h Ph2PCl (2.83 g, 12.8 mmol) was added
dropwise. Stirring was continued for 1 h at –78 °C and the suspension
was allowed to warm to room temperature overnight. The solvent was
removed under vacuum and CH2Cl2 (50 mL) was added. After aqueous
workup the solvent was concentrated by rotary evaporation and the
solution was left for crystallization. The resulting pale yellow crystals
were filtered, washed with n-hexane and dried in vacuo affording 5-
Br-6-(Ph2P)-Ace (1b), as yellow crystals (2.87 g, 6.88 mmol, 54%).
1H NMR: δ = 7.74 [d, J = 7 Hz, 1 H), 7.38–7.36 (m, 10 H), 7.16–
7.11 (m, 3 H), 3.35 ppm (s, 4 H, H-1,2). 13C{1H} NMR: δ = 148.4 (s,
Experimental Section
General: Reagents were obtained commercially (Sigma-Aldrich, Ger-
many) and were used as received. Dry solvents were collected from a
SPS800 mBraun solvent system.
1,8-Bis(tributylstannyl)naphthalene[83] and 5,6-dibromoacenaph-
thene[84] were prepared according to literature procedures. 1H-, 13C-,
31P- and 77Se-NMR spectra were recorded in CDCl3 at room temp.
with a Bruker Avance-360 spectrometer and are referenced to tet-
ramethylsilane (1H, 13C), phosphoric acid (85% in water) (31P) and
diphenyldiselenide (77Se). Chemical shifts are reported in parts per
million (ppm) and coupling constants (J) are given in Hertz (Hz). Elec-
tron impact mass spectroscopy (EIMS) was carried out with a Finnigan
MAT 95. The ESI MS spectra were obtained with a Bruker Esquire-LC
MS. Methanol solutions (unless otherwise stated, c = 1ϫ10–6 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 nebuliz-
ation 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 1ϫ10–5 mbar. Spectra were collected for one minute and
averaged. The nozzle-skimmer voltage was adjusted individually for
each measurement.
4
4
Cb), 146.7 [d, J(31P-13C) = 2 Hz, Cd], 141.4 [d, J(31P-13C) = 4 Hz,
2
Cc], 139.1 [d, J(31P-13C) = 13 Hz, C7], 137.7 (s, C3 or C4), 134.6 (s,
C3 or C4), 134.1 [d, J(31P-13C) = 20 Hz, Co], 133.2 [d, J(31P-13C) =
2
1
19 Hz, C6], 129.8 [d, 1J(31P-13C) = 29 Hz, Ci], 128.4 [d, 3J(31P-13C) =
7 Hz, Cm], 128.3 (s, Cp), 120.4 [d, J(31P-13C) = 23 Hz, C8], 115.7 (s,
3
C5), 30.0 (s, C1 or C2), 29.8 ppm (s, C1 or C2). 31P{1H} NMR: δ =
–8.1 (s) ppm. MS (EI+): m/z: 416 [M+].
Synthesis of 1-Bromo-8-naphthyl-methyldiphenylphosphonium
Iodide (2a): Methyl iodide (23.4 mg, 0.16 mmol) was added to a solu-
tion of 1a (54.5 mg, 0.14 mmol) in toluene (2 mL) and stirred at room
temperature overnight. The precipitate was filtered, washed three times
with toluene and dried in vacuo yielding [1-Br-8-Ph2P(CH3)-Nap]+I–
(2a) as a yellow solid (68.6 mg, 0.11 mmol, 79%). Crystals suitable for
X-ray crystallography were obtained by recrystallization by CH2Cl2/
1
toluene. H NMR: δ = 8.32 (d, J = 8 Hz, 1 H), 8.10 (d, J = 8 Hz, 1
H), 7.89–7.50 (m, 14 H), 3.30 [d, 2J(1H-31P) = 13 Hz, 3 H, CH3].
2
4
13C{1H} NMR: 142.9 [d, J(31P-13C) = 12 Hz, C7], 138.2 [d, J(31P-
13C) = 3 Hz, C5], 136.9 [d, 3J(31P-13C) = 9 Hz, Cb], 136.0 (s, C2),
Synthesis of 1,8-Dibromonaphthalene: Bromine (250 mg,
1.57 mmol) was added to a solution of 1,8-bis(tributylstannyl)naphth-
alene (500 mg, 0.71 mmol) in n-hexane (5 mL) at room temp. and
stirred overnight. The solvent was removed by rotary evaporation and
the residue was left for crystallization at 5 °C. The obtained crystals
were filtered, washed with cold n-hexane and dried in vacuo yielding
1,8-Br2-Nap as colorless crystals (100 mg, 0.48 mmol, 67%). 1H
NMR: δ = 7.96 [dd, 3J(1H-1H) = 7, 4J(1H-1H) = 2 Hz, 2 H, H-2,7],
134.1 [d, J(31P-13C) = 3 Hz, Cp], 132.3 [d, J(31P-13C) = 10 Hz, Co],
4
2
130.9 [d, J(31P-13C) = 1 Hz, C4], 130.1 [d, J(31P-13C) = 13 Hz, Cm],
4
3
128.3 (s, C3), 125.4 [d, 3J(31P-13C) = 15 Hz, C6], 123.6 [d, 1J(31P-13C)
= 91 Hz, Ci], 117.3 [d, J(31P-13C) = 4 Hz, C1], 113.8 [d, J(31P-13C)
3
1
= 86 Hz, C8], 16.6 [d, J(31P-13C) = 60 Hz, CH3]. 31P{1H} NMR: δ =
1
29.7 (s) ppm. ESI MS (MeOH, positive mode): m/z = 405.3
(C23H19BrP) for [1-Br-8-Ph2PCH3–C10H6]+ (2a).
3
4
7.83 [dd, J(1H-1H) = 8, J(1H-1H) = 1 Hz, 2 H, H-4,5]; 7.28 ppm (t,
3J(1H-1H) = 8 Hz, 2 H, H-3,6). 13C{1H} NMR: δ = 136.8 (s, Cb),
135.1 (s, C2 and C7), 129.4 (s, C4 and C5), 128.6 (s, Ca), 126.2 (s, C3
and C6), 119.3 (s, C1 and C8) ppm. MS (EI+): m/z: 284 [M+].
Synthesis of 5-Bromo-6-acenaphthyl-methyldiphenylphosphonium
Iodide (2b): Methyl iodide (340 mg, 2.40 mmol) was added to a solu-
tion of 1b (1.00 g, 2.40 mmol) in toluene (10 mL) and stirred at room
temperature overnight. The precipitate was filtered, washed three times
Synthesis of 1-Bromo-8-diphenylphosphino-naphthalene (1a): n- with toluene and dried in vacuo yielding [5-Br-6-Ph2P(CH3)-Ace]+I–
Butyllithium (5.25 mmol, 2.5 m in n-hexane) was added to a solution (2b) as colorless solid (1.19 g, 2.13 mmol, 89%). Crystals suitable for
of 1,8-dibromonaphthalene (1.50 g, 5.25 mmol) in diethyl ether X-ray crystallography were obtained by recrystallization by CH2Cl2/
2244
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
n-hexane. 1H NMR: δ = 7.75–7.48 (m, 10 H), 7.39–7.31 (m, 2 H), (100 mg, 0.24 mmol) in THF (2 mL) and stirred at room temperature
7.12–7.02 (m, 2 H), 3.40 (m, 4 H, H-1,2), 3.24 [d, 2J(1H-31P) = 13 Hz, overnight. The solvent was removed by rotary evaporation and the
3 H, CH3]. 13C{1H} NMR: δ = 157.9 [d, 4J(31P-13C) = 3 Hz, Cd],
residue was recrystallized from CH2Cl2/n-hexane affording 5-Br-6-
Ph2P(S)-Ace (4b) as yellow crystals (82.2 mg, 0.19 mmol, 77%). H
1
148.7 (s, Cb), 143.7 [d, 2J(31P-13C) = 13 Hz, C7], 141.8 [d, 4J(31P-13C)
4
= 10 Hz, Cc], 137.2 (s, C4), 134.0 [d, J(31P-13C) = 3 Hz, Cp], 132.3 NMR: δ = 7.89–7.75 (m, 5 H), 7.53–7.34 (m, 7 H), 7.20 [d, J = 7 Hz,
2
2
[d, J(31P-13C) = 10 Hz, Co], 130.8 [d, J(31P-13C) = 7 Hz, Ca], 129.9 1 H), 7.10 (d, J = 7 Hz, 1 H), 3.34 ppm (s, 4 H, H-1,2). 13C{1H} NMR:
[d, 3J(31P-13C) = 13 Hz, Cm], 123.2 [d, 1J(31P-13C) = 91 Hz, Ci], 123.1
(s, C3), 120.0 [d, 3J(31P-13C) = 15 Hz, C8], 112.0 [d, 3J(31P-13C) =
3 Hz, C5], 107.7 [d, 1J(31P-13C) = 88 Hz, C6], 30.4 (s, C1 or C2),
δ = 152.9 [d, J(31P-13C) = 3 Hz, Cd], 145.0 (s, Cb), 142.1 [d, J(31P-
4
4
13C) = 9 Hz, Cc], 139.4 [d, 2J(31P-13C) = 13 Hz, C7], 136.7 (s, C4),
136.2 [d, 1J(31P-13C) = 87 Hz, Ci], 132.0 [d, J(31P-13C) = 10 Hz, Co],
2
29.6 (s, C1 or C2), 16.3 [d, 1J(31P-13C) = 60 Hz, CH3]. 31P{1H} NMR: 131.4 [d, 2J(31P-13C) = 7 Hz, Ca], 130.8 [d, J(31P-13C) = 3 Hz, Cp],
4
δ = 27.7 (s) ppm. ESI MS (MeOH, positive mode): m/z = 431.1
128.3 [d, 3J(31P-13C) = 13 Hz, Cm], 124.7 [d, 1J(31P-13C) = 83 Hz, C6],
121.7 (s, C3), 118.8 [d, 3J(31P-13C) = 14 Hz, C8], 114.7 [d, 3J(31P-13C)
= 3 Hz, C5], 30.1 (s, C1 or C2), 29.6 ppm (s, C1 or C2). 31P{1H} NMR:
δ = 50.2 (s) ppm. MS (EI+): m/z: 369 [M-Br]+.
(C25H21BrP) for [5-Br-6-Ph2PCH3–C12H8]+ (2b).
Synthesis of 5-Bromo-6-diphenyloxophosphino-naphthalene (3a):
Hydrogen peroxide (100 μL, 30% solution) was added to a solution
of 1a (50.2 mg, 0.13 mmol) in THF (2 mL) and stirred at room tem-
perature overnight. The solvent was removed by rotary evaporation
and the residue was recrystallized by CH2Cl2/n-hexane affording 1-Br-
8-Ph2P(O)-Nap (3a) as colorless crystals (42.4 mg, 0.10 mmol, 77%).
1H NMR: δ = 7.98 (d, J = 8 Hz, 1 H), 7.88 (d, J = 8 Hz, 2 H), 7.67–
7.58 (m, 5 H), 7.54–7.27 (m, 8 H). 13C{1H} NMR: δ = 139.1 [d,
Synthesis of 8-Bromo-1-diphenylselenidophosphino-naphthalene
(5a): Selenium (12.6 mg, 0.16 mmol) was added to a solution of 1a
(51.9 mg, 0.13 mmol) in THF (2 mL) and stirred at room temperature
overnight. The solvent was removed by rotary evaporation and the
residue was recrystallized by CH2Cl2/n-hexane affording 1-Br-8-
1
Ph2P(Se)-Nap (5a) as yellow crystals (22.9 mg, 0.05 mmol, 38%). H
1
2J(31P-13C) = 13 Hz, C7], 136.5 [d, J(31P-13C) = 108 Hz, Ci], 136.6
NMR: δ = 7.96–7.80 (m, 7 H), 7.53–7.23 (m, 9 H). 13C{1H} NMR:
[d, 3J(31P-13C) = 8 Hz, Cb], 135.1 (s, C2), 134.5 [d, 4J(31P-13C) = 3 Hz,
2
3
δ = 138.2 [d, J(31P-13C) = 11 Hz, C7], 137.0 [d, J(31P-13C) = 8 Hz,
2
2
C5], 133.9 [d, J(31P-13C) = 6 Hz, Ca], 131.5 [d, J(31P-13C) = 9 Hz,
Cb], 135.3 (s, C2), 135.2 [d, 1J(31P-13C) = 79 Hz, Ci], 134.2 [d, 4J(31P-
4
4
Co], 131.1 [d, J(31P-13C) = 3 Hz, Cp], 129.3 [d, J(31P-13C) = 1 Hz,
C4], 128.5 [d, 1J(31P-13C) = 98 Hz, C8], 128.3 [d, 3J(31P-13C) = 12 Hz,
Cm], 126.8 (s, C3), 124.2 [d, 3J(31P-13C) = 15 Hz, C6], 120.2 [d, 3J(31P-
13C) = 4 Hz, C1]. 31P{1H} NMR: δ = 36.8 (s) ppm. MS (EI+): m/z:
327 [M-Br]+.
13C) = 3 Hz, C5], 132.9 [d, J(31P-13C) = 6 Hz, Ca], 132.5 [d, J(31P-
2
2
13C) = 10 Hz, Co], 131.0 [d, J(31P-13C) = 3 Hz, Cp], 129.5 [d, 4J(31P-
4
13C) = 1 Hz, C4], 128.4 [d, 1J(31P-13C) = 71 Hz, C8], 128.3 [d, 3J(31P-
13C) = 13 Hz, Cm], 126.9 (s, C3), 124.2 [d, J(31P-13C) = 14 Hz, C6],
3
120.1 ppm [d, 3J(31P-13C) = 4 Hz, C1]. 31P{1H} NMR: δ = 42.9 [s,
1J(77Se-31P) = 742 Hz]. 77Se{1H} NMR: δ = –178.3 [d, 1J(31P-77Se) =
746 Hz] ppm. MS (EI+): m/z: 391 [M-Br]+.
Synthesis of 5-Bromo-6-diphenyloxophosphino-acenaphthene (3b):
Hydrogen peroxide (200 μL, 30% solution) was added to a solution
of 1b (100 mg, 0.24 mmol) in THF (2 mL) and stirred at room tem-
perature overnight. The solvent was removed by rotary evaporation Synthesis of 5-Bromo-6-diphenylselenidophosphino-acenaph-
and the residue was recrystallized by CH2Cl2/n-hexane affording 5-Br- thalene (5b): Selenium (23.0 mg, 0.29 mmol) was added to a solution
6-Ph2P(O)-Ace (3b) as colorless crystals (100 mg, 0.23 mmol, 96%).
1H NMR: δ = 7.77 (d, J = 7 Hz, 1 H), 7.68–7.37 (m, 11 H), 7.21–
7.11 (m, 2 H), 3.36 ppm (s, 4 H, H-1,2). 13C{1H} NMR: δ = 153.3 [d,
4J(31P-13C) = 2 Hz, Cd], 146.8 (s, Cb), 141.7 [d, 4J(31P-13C) = 9 Hz,
of 1b (100 mg, 0.24 mmol) in THF (2 mL) and stirred at room tem-
perature overnight. The solvent was removed by rotary evaporation
and the residue was recrystallized by CH2Cl2/n-hexane affording 5-Br-
6-Ph2P(Se)-Ace (5b) as yellow crystals (80.0 mg, 0.16 mmol, 67%).
Cc], 140.5 [d, 2J(31P-13C) = 14 Hz, C7], 136.3 (s, C4), 136.0 [d, 1J(31P- 1H NMR: δ = 7.93–7.83 (m, 4 H), 7.77 (d, J = 7 Hz, 1 H), 7.52–7.30
13C) = 108 Hz, Ci], 132.5 [d, 2J(31P-13C) = 7 Hz, Ca], 131.7 [d, 2J(31P- (m, 7 H), 7.20 [d, J = 7 Hz, 1 H), 7.10 [d, J = 7 Hz, 1 H), 3.34 ppm (s,
4
3
13C) = 9 Hz, Co], 131.1 [d, J(31P-13C) = 2 Hz, Cp], 128.3 [d, J(31P- 4 H, H-1,2). 13C{1H} NMR: δ = 153.1 [d, 4J(31P-13C) = 3 Hz, Cd],
13C) = 12 Hz, Cm], 123.4 [d, J(31P-13C) = 102 Hz, C6], 121.7 (s, C3),
147.0 (s, Cb), 142.2 [d, 4J(31P-13C) = 10 Hz, Cc], 139.3 [d, 2J(31P-13C)
1
118.7 [d, J(31P-13C) = 15 Hz, C8], 115.0 [d, J(31P-13C) = 4 Hz, C5], = 12 Hz, C7], 136.9 (s, C4), 134.9 [d, J(31P-13C) = 79 Hz, Ci], 132.6
3
3
1
30.2 (s, C1 or C2), 29.6 ppm (s, C1 or C2). 31P{1H} NMR: δ = 36.3 [d, J(31P-13C) = 10 Hz, Co], 131.3 [d, J(31P-13C) = 8 Hz, Ca], 130.9
2
2
(s) ppm. MS (EI+): m/z: 353 [M-Br]+.
[d, J(31P-13C) = 3 Hz, Cp], 128.3 [d, J(31P-13C) = 13 Hz, Cm], 123.5
[d, 1J(31P-13C) = 72 Hz, C6], 121.8 (s, C3), 118.9 [d, 3J(31P-13C) =
14 Hz, C8], 114.6 [d, 3J(31P-13C) = 3 Hz, C5], 30.1 (s, C1 or C2),
29.7 ppm (s, C1 or C2). 31P{1H} NMR: δ = 40.7 [s, 1J(77Se-31P) =
4
3
Synthesis of 1-Bromo-8-diphenylsulfidophosphino-naphthalene
(4a): Sulfur (9.83 mg, 0.31 mmol) was added to a solution of 1a
(50.0 mg, 0.14 mmol) in THF (2 mL) and stirred at room temperature
overnight. The solvent was removed by rotary evaporation and the
residue was recrystallized by CH2Cl2/n-hexane affording 1-Br-8-
Ph2P(S)-Nap (4a) as colorless crystals (30.9 mg, 0.07 mmol, 50%). 1H
NMR: δ = 7.94–7.76 (m, 7 H), 7.55–7.20 (m, 7 H). 13C{1H} NMR:
735 Hz]. 77Se{1H} NMR: δ = –170.5 ppm [d, J(31P-77Se) = 721 Hz]
1
ppm. ESI MS (CH2Cl2/MeOH 1:10, positive mode): m/z = 479.0
(C24H19BrPSe) for [5-Br-6-Ph2PSe-C12H8+H]+.
X-ray Crystallography: Intensity data were collected with a STOE
IPDS 2T area detector (3a, 3b, 4a, 5a) and a Siemens P4 dif-
fractometer (1a, 1b, 2a, 2b, 4b, 5b) fitted with a Siemens LTII at
173 K with graphite-monochromated Mo-Kα (0.7107 Å) radiation. All
structures were solved by direct methods and refined based on F2 using
the SHELX program package.[87] All non-hydrogen atoms were re-
fined using anisotropic displacement parameters. Hydrogen atoms at-
tached to carbon atoms were included in geometrically calculated posi-
tions using a riding model. Crystal and refinement data are collected
in Table 6 (1a, 1b, 2a, 2b), Table 7 (3a, 3b, 4a, 4b), and Table 8 (5a,
5b). Figures were created using ORTEP.[88]
2
3
δ = 138.3 [d, J(31P-13C) = 11 Hz, C7], 136.9 [d, J(31P-13C) = 8 Hz,
Cb], 136.4 [d, 1J(31P-13C) = 88 Hz, Ci], 135.1 (s, C2), 134.1 [d, 4J(31P-
13C) = 3 Hz, C5], 132.9 [d, J(31P-13C) = 6 Hz, Ca], 131.8 [d, J(31P-
2
2
13C) = 10 Hz, Co], 130.8 [d, J(31P-13C) = 3 Hz, Cp], 129.5 [d, 1J(31P-
4
13C) = 80 Hz, C8], 129.4 [d, 4J(31P-13C) = 1 Hz, C4], 128.2 [d, 3J(31P-
13C) = 13 Hz, Cm], 126.8 (s, C3), 124.2 [d, J(31P-13C) = 14 Hz, C6],
3
120.0 [d, J(31P-13C) = 4 Hz, C1]. 31P{1H} NMR: δ = 52.0 (s) ppm.
3
MS (EI+): m/z: 343 [M-Br]+.
Synthesis of 5-Bromo-6-diphenylsulfidophosphino-acenaphthene
(4b): Sulfur (10.0 mg, 0.29 mmol) was added to a solution of 1b
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2245

J. Beckmann, S. Mebs et al.
ARTICLE
Table 6. Crystal data and structure refinement of 1a, 1b, 2a, and 2b.
1a
1b
2a·0.5hexane
2b·0.5CH2Cl2
Formula
C22H16BrP
391.23
C24H18BrP
417.26
C27H24BrIP
586.24
C25.5H22BrClIP
601.66
Formula weight /g·mol–1
Crystal system
Crystal size /mm
Space group
a /Å
b /Å
c /Å
monoclinic
1.0ϫ0.8ϫ0.6
P21/c
10.486(3)
15.687(3)
10.854(2)
90
105.95(2)
90
1716.7(7)
4
triclinic
0.8ϫ0.5ϫ0.3
¯
P1
monoclinic
1.0ϫ0.6ϫ0.5
C2/c
23.430(5)
10.232(4)
20.461(4)
90
98.05(1)
90
4857(2)
8
monoclinic
1.0ϫ0.2ϫ0.1
C2/c
14.399(5)
20.559(7)
16.379(8)
90.00
96.84(4)
90.00
4814(3)
8
9.646(2)
12.110(2)
17.271(2)
80.88(1)
83.34(1)
70.84(1)
1877.2(5)
4
α /°
β /°
γ /°
V /Å3
Z
ρcalcd /Mg·m–3
μ (Mo-Kα) /mm–1
F(000)
1.514
2.487
792
1.476
2.279
848
1.603
3.042
2312
1.660
3.178
2360
θ range /°
Index ranges
2.60 to 27.50
–13 Յ h Յ 13
0 Յ k Յ 20
0 Յ l Յ 14
3902
2.61 to 27.50
–12 Յ h Յ 12
–15 Յ k Յ 15
0 Յ l Յ 22
8525
2.85 to 27.50
–8 Յ h Յ 30
–13 Յ k Յ 13
–26 Յ l Յ 26
6690
2.50 to 22.51
–15 Յ h Յ 9
–6 Յ k Յ 22
–17 Յ l Յ 17
3904
No. of reflns collected
Completeness to θ
98.9%
98.7%
98.8%
99.5%
max
No. indep. reflns
3902
8525
5523
3148
No. obsd reflns with [I Ͼ 2σ(I)]
No. refined parameters
GooF (F2)
2692
217
0.840
6099
469
1.075
4102
268
1.024
1876
282
0.971
R1 (F) [I Ͼ 2σ(I)]
0.0558
0.1776
0.635 / –0.922
941919
0.0530
0.1492
0.707 / –1.348
941220
0.0557
0.1578
0.710 / –2.595
941221
0.0670
0.1643
0.802 / –0.897
941222
wR2 (F2) (all data)
Largest diff peak/hole /e·Å–3
CCDC number
Table 7. Crystal data and structure refinement of 3a, 3b, 4a, and 4b.
3a
3b·0.5hexane
4a
4b
Formula
C22H16BrOP
407.23
C27H25BrOP
476.35
C22H16BrPS
423.29
C24H18BrPS
449.32
Formula weight /g·mol–1
Crystal system
Crystal size /mm
Space group
a /Å
b /Å
c /Å
monoclinic
0.4ϫ0.3ϫ0.2
P21/c
8.6407(17)
17.282(4)
12.599(3)
90
monoclinic
0.4ϫ0.3ϫ0.2
P21/c
18.085(3)
10.2819(19)
12.056(4)
90
monoclinic
0.5ϫ0.4ϫ0.3
P21/c
18.539(4)
12.063(2)
17.930(4)
90
orthorhombic
0.9ϫ0.6ϫ0.6
Pna21
7.8916(9)
14.148(5)
17.6186(18)
90
α /°
β /°
110.04(3)
90
1767.4(6)
4
1.530
2.423
98.293(17)
90
2218.4(9)
4
1.426
1.942
108.63(3)
90
3799.8(13)
8
1.480
2.359
90
90
1967.1(8)
4
1.517
γ /°
V /Å3
Z
ρcalcd /Mg·m–3
μ (Mo-Kα) /mm–1
F(000)
2.283
912
824
980
1712
θ range /°
Index ranges
0.94 to 25.96
–10 Յ h Յ 15
–21 Յ k Յ 21
–15 Յ l Յ 15
14718
0.98 to 25.99
–22 Յ h Յ 22
–12 Յ k Յ 12
–14 Յ l Յ 14
15717
2.05 to 26.01
–21 Յ h Յ 22
–14 Յ k Յ 14
–20 Յ l Յ 21
28478
2.88 to 27.51
0 Յ h Յ 10
0 Յ k Յ 18
–22 Յ l Յ 22
4517
No. of reflns collected
Completeness to θ
94.0%
97.9%
92.7%
99.8%
max
No. indep. reflns
3257
4281
6930
4517
No. obsd reflns with [I Ͼ 2σ(I)]
No. refined parameters
GooF (F2)
2475
226
0.965
3240
272
1.002
4332
451
0.886
3888
244
1.005
R1 (F) [I Ͼ 2σ(I)9
wR2 (F2) (all data)
Largest diff peak/hole /e·Å–3
CCDC number
0.0354
0.0987
0.407 / –0.704
941223
0.0388
0.0458
0.1116
0.662 / –0.339
941225
0.0345
0.0806
0.298 / –0.586
941226
0. 0966
1.311 / –0.559
941224
2246
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
Table 8. Crystal data and structure refinement of 5a and 5b.
Acknowledgements
5a
5b
We thank Dr. Michael J. Turner for his critical assessment of the manu-
script. The Deutsche Forschungsgemeinschaft (DFG) and the Austra-
lian Research Council (ARC) are gratefully acknowledged for funding.
Formula
C22H16BrPSe
470.19
monoclinic
0.5ϫ0.4ϫ0.3
P21/n
9.5117(19)
11.662(2)
16.926(3)
90
98.46(3)
90
C24H18BrPSe
496.22
triclinic
0.9ϫ0.6ϫ0.4
¯
P1
9.076(2)
10.387(3)
11.791(4)
70.100(10)
72.480(10)
78.880(10)
991.6(5)
2
Formula weight /g·mol–1
Crystal system
Crystal size, mm
Space group
a /Å
References
b /Å
c /Å)
α /°
β /°
[1] V. Balasubramaniyan, Chem. Rev. 1966, 66, 567–641 and refer-
ences cited therein.
[2] J. D. Hoefelmeyer, M. Schulte, M. Tschinkl, F. P. Gabbai, Coord.
Chem. Rev. 2002, 235, 93–103 and references cited therein.
[3] P. Kilian, F. R. Knight, J. D. Woollins, Chem. Eur. J. 2011, 17,
2302–2328 and references cited therein.
γ /°
V /Å3
1857.1(6)
4
1.682
Z
[4] R. W. Alder, J. Chem. Soc. Perkin Trans. 1 1981, 2840–2847 and
ρcalcd /Mg·m–3
μ (Mo-Kα) /mm–1
F(000)
θ range /°
Index ranges
1.662
3.995
references cited therein.
4.261
[5] J. T. B. H. Jastrzebski, G. Van Koten, K. Goubitz, C. Arlen, M.
Pfeffer, J. Organomet. Chem. 1983, 246, C75-C79.
[6] A. J. Kirby, J. M. Percy, Tetrahedron 1988, 44, 6903–6910.
[7] R. L. Giles, j. A. K. Howard, L. G. F. Patrick, M. R. Probert, G. E.
Smith, A. Whiting, J. Organomet. Chem. 2003, 680, 257–262.
[8] J. Blum, D. Gelman, W. Baidossi, E. Shakh, A. Rosenfeld, Z.
Aizenshtat, B. C. Wassermann, M. Frick, B. Heymer, S. Schutte,
S. Wernik, H. Schumann, J. Org. Chem. 1997, 62, 8681–8686.
[9] C. Boker, M. Noltemeyer, H. Gornitzka, B. O. Kneisel, M. Teich-
ert, R. Herbst-Irmer, A. Meller, Main Group Met. Chem. 1998,
21, 565–578.
928
492
2.13 to 26.00
–11 Յ h Յ 11
–14 Յ k Յ 14
–20 Յ l Յ 20
17491
2.13 to 26.00
–11 Յ h Յ 11
–12 Յ k Յ 12
0 Յ l Յ 15
4446
97.5%
4446
3487
244
1.022
0.0644
0.1735
1.916 / –1.554
941228
No. of reflns collected
Completeness to θ
No. indep. reflns
No. obsd reflns with [I Ͼ 2σ(I)] 2708
98.0%
3579
max
No. refined parameters
226
0.794
0.0354
0.1110
0.560 / –0.469
941227
GooF (F2)
[10] G. S. Hair, S. L. Battle, A. Decken, A. H. Cowley, R. A. Jones,
Inorg. Chem. 2000, 39, 27–31.
R1 (F) [I Ͼ 2σ(I)]
wR2 (F2) (all data)
Largest diff peak/hole /e·Å–3
CCDC number
[11] H. Schumann, B. C. Wassermann, S. Schutte, B. Heymer, S.
Nickel, T. D. Seuss, S. Wernik, J. Demtschuk, F. Girgsdies, R.
Weimann, Z. Anorg. Allg. Chem. 2000, 626, 2081–2095.
[12] H. Schumann, S. Dechert, M. Hummert, K. C. H. Lange, S.
Schutte, B. C. Wassermann, K. Koehler, J. Eichhorn, Z. Anorg.
Allg. Chem. 2004, 630, 1196–1204.
[13] S. U. Ahmad, J. Beckmann, Main Group Met. Chem. 2012, 35,
29–33.
[14] J. T. B. H. Jastrzebski, C. T. Knaap, G. Van Koten, J. Organomet.
Chem. 1983, 255, 287–293.
[15] R. J. P. Corriu, G. F. Lanneau, M. Perrot, Tetrahedron Lett. 1987,
28, 3941–3944.
[16] C. Breliere, F. Carre, R. J. P. Corriu, M. Poirier, G. Royo, J.
Zwecker, Organometallics 1989, 8, 1831–1883.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-941919, -941920, -941921, -941922, -941923,
-941924, -941925, -941926, -941927, and -941928 (Fax: +44-1223-
336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.
ac.uk).
[17] C. Breliere, R. J. P. Corriu, G. Royo, J. Zwecker, Organometallics
1989, 8, 1834–1836.
[18] C. Breliere, R. J. P. Corriu, G. Royo, M. W. Chi Man, J. Zwecker,
Organometallics 1990, 9, 2633–2635.
[19] R. J. P. Corriu, C. Guerin, B. J. L. Henner, Q. Wang, Organome-
tallics 1991, 10, 3574–3581.
[20] C. Breliere, F. Carre, R. J. P. Corriu, W. E. Douglas, M. Poirier,
G. Royo, M. W. Chi Man, Organometallics 1992, 11, 1586–1593.
[21] J. T. B. H. Jastrzebski, P. A. Van der Schaaf, J. Boersma, G.
Van Koten, D. Heijdenrijk, K. Goubitz, D. J. A. De Ridder, J. Or-
ganomet. Chem. 1989, 367, 55–68.
[22] J. T. B. H. Jastrzebski, J. Boersma, P. M. Esch, G. Van Koten, Or-
ganometallics 1991, 10, 930–935.
Theoretical Calculations: For all 15 models, the molecular geome-
tries were optimized at the B3PW91/6-311++G(2df,p) level of theory
using GAUSSIAN09.[89] Frequency calculations were carried out to
check that all optimized geometries correspond to energy minima.
The wavefunctions were analyzed with AIM2000[90] and DGRID-
4.6[91] in order to obtain all the required real-space bonding indicators
based on the AIM and ELI-D space partitioning. The Hirshfeld sur-
faces were generated with the program CrystalExplorer[92] from the
promolecule densities. Isosurface representations of the ELI-D were
made using the program MOLISO.[93]
[23] J. T. B. H. Jastrzebski, P. A. Van der Schaaf, J. Boersma, G.
Van Koten, M. De Wit, Y. Wang, D. Heijdenrijk, C. H. Stam, J.
Organomet. Chem. 1991, 407, 301–311.
[24] J. T. B. H. Jastrzebski, P. A. Van der Schaaf, J. Boersma, G.
Van Koten, D. J. A. De Ridder, D. Heijdenrijk, Organometallics
1992, 11, 1521–1526.
[25] C. Chuit, R. J. P. Corriu, P. Monforte, C. Reye, J. P. Declercq, A.
Dubourg, Angew. Chem. Int. Ed. Engl. 1993, 32, 1430–1432.
[26] C. Chuit, R. J. P. Corriu, P. Monforte, C. Reye, J. P. Declercq, A.
Dubourg, J. Organomet. Chem. 1996, 511, 171–175.
[27] M. Chauhan, C. Chuit, A. Fruchier, C. Reye, Inorg. Chem. 1999,
38, 1336–1339.
Supporting Information (see footnote on the first page of this article):
Bond topologies of the theoretically optimized structures of com-
pounds 1a–c, 2a–c, 3a–c, 4 a–c, 5 a–c. Atomic Hirshfeld surfaces of
the theoretically optimized structures of compounds 1a–c, 2a–c, 3a–c,
4 a–c, 5 a–c. ELI-D isosurface representation of the theoretically opti-
mized structures of 1a–b, 2a–b, 3a–b, 4 a–b, 5 a–b. Bond topological
properties of the theoretically optimized structures of compounds 1a–
c, 2a–c, 3a–c, 4 a–c, 5 a–c.
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2247

J. Beckmann, S. Mebs et al.
[28] A. Chandrasekaran, N. V. Timosheva, R. O. Day, R. R. Holmes, [62] P. Kilian, F. R. Knight, J. D. Woollins, Coord. Chem. Rev. 2011,
ARTICLE
Inorg. Chem. 2000, 39, 1338–1339.
255, 1387–1413 and references cited therein.
[63] C. Taouss, P. G. Jones, Dalton Trans. 2011, 40, 11687–11689.
[64] K. Issleib, H. Volker, Chem. Ber. 1961, 94, 392–397.
[65] A. Toshimitsu, T. Saeki, K. Tamao, J. Am. Chem. Soc. 2001, 123,
9210–9211.
[66] F. R. Knight, A. L. Fuller, A. M. Z. Slawin, J. D. Woollins, Poly-
hedron 2010, 29, 1849–1853.
[67] F. R. Knight, A. L. Fuller, M. Bühl, A. M. Z. Slawin, J. D. Wool-
lins, Chem. Eur. J. 2010, 16, 7617–7634.
[68] P. Wawrzyniak, A. L. Fuller, A. M. Z. Slawin, P. Kilian, Inorg.
Chem. 2009, 48, 2500–2506.
[29] F. H. Carre, C. Chuit, R. J. P. Corriu, W. E. Douglas, D. M. H.
Guy, C. Reye, Eur. J. Inorg. Chem. 2000, 647–653.
[30] S. Kamepalli, C. J. Carmalt, R. D. Culp, A. H. Cowley, R. A.
Jones, N. C. Norman, Inorg. Chem. 1996, 35, 6179–6183.
[31] C. J. Carmalt, A. H. Cowley, R. D. Culp, R. A. Jones, S. Kame-
palli, N. C. Norman, Inorg. Chem. 1997, 36, 2770–2776.
[32] T. Tokunaga, H. Seki, S. Yasuike, M. Ikoma, J. Kurita, K. Yamag-
uchi, Tetrahedron 2000, 56, 8833–8839.
[33] H. Suzuki, T. Murafuji, Y. Matano, N. Azuma, J. Chem. Soc.
Perkin Trans. 1 1993, 2969–2973.
[69] M.-L. Lechner, K. S. A. Arachchige, R. A. M. Randall, F. R.
Knight, M. Bühl, A. M. Z. Slawin, J. D. Woollins, Organometal-
lics 2012, 31, 2922–2930.
[70] L. K. Aschenbach, F. R. Knight, R. A. M. Randall, D. B. Cordes,
A. Baggott, M. Bühl, A. M. Z. Slawin, J. D. Woollins, Dalton
Trans. 2012, 41, 3141–3153.
[71] B. A. Surgenor, M. Bühl, A. M. Z. Slawin, J. D. Woollins, P. Kil-
ian, Angew. Chem. Int. Ed. 2012, 51, 10150–10153.
[72] F. R. Knight, R. A. M. Randall, K. S. Athukorala, L. Wakefield,
J. M. Griffin, S. E. Ashbrook, M. Bühl, A. M. Z. Slawin, J. D.
Woollins, Inorg. Chem. 2012, 51, 11087–11097.
[34] E. M. Kosower, H. Kanety, J. Am. Chem. Soc. 1983, 105, 6236–
6243.
[35] P. A. van der Schaaf, R. A. T. M. Abbenhuis, W. P. A.
van der Noort, R. de Graaf, D. M. Grove, W. J. J. Smeets, A. L.
Spek, G. van Koten, Organometallics 1994, 13, 1433–1444.
[36] M. van Klaveren, F. Lambert, D. J. F. M. Eijkelkamp, D. M.
Grove, G. van Koten, Tetrahedron Lett. 1994, 35, 6135–6138.
[37] E. S. M. Persson, M. van Klaveren, D. M. Grove, J. E. Baeckvall,
G. van Koten, Chem. Eur. J. 1995, 1, 351–359.
[38] M. Kuti, J. Rabai, I. Kapovits, I. Jalsovszky, G. Argay, A. Kal-
man, L. Parkanyi, J. Mol. Struct. 1996, 382, 1–11.
[39] H. Fujihara, H. Tanaka, N. Furukawa, J. Chem. Soc. Perkin Trans.
1 1995, 19, 2375–2377.
[73] D. Seyferth, S. C. Vick, J. Organomet. Chem. 1977, 141, 173–
187.
[74] I. P. Beletskaya, A. S. Sigeev, A. S. Peregudov, P. V. Petrovskii,
Synthesis 2007, 16, 2534–2538.
[40] A. Panda, G. Mugesh, H. B. Singh, R. J. Butcher, Organometal-
lics 1999, 18, 1986–1993.
[75] a) S. Bontemps, M. Devillard, S. Mallet-Ladeira, G. Bouhadir, K.
Miqueu, D. Bourissou, Inorg. Chem. 2013, 52, 4714–4720; b)
C. R. Wade, M. R. Saber, F. Gabbaï, Heteroat. Chem. 2011, 22,
500–505; c) F. P. Gabbaï, H. Zhao, Nature Chem. 2010, 984–990;
d) C. R. Wade, F. P. Gabbaï, Organometallics 2011, 30, 4479–
4481; e) H. Zhao, F. P. Gabbaï, Org. Lett. 2011, 13, 1444–1446.
[76] R. F. W. Bader, Atoms in Molecules, A Quantum Theory, Cam-
bridge University Press, Oxford U. K., 1991.
[77] a) F. L. Hirshfeld, Theor. Chim. Acta 1977, 44, 129–139; b) M. A.
Spackman, P. G. Byrom, Chem. Phys. Lett. 1997, 267, 215–220.
[78] a) A. D. Becke, K. E. Edgecombe, J. Chem. Phys. 1990, 92,
5397–5403; b) B. Silvi, A. Savin, Nature 1994, 371, 683–686.
[79] a) M. Kohout, Int. J. Quantum Chem. 2004, 97, 651–658; b) M.
Kohout, F. R. Wagner, Y. Grin, Theor. Chem. Acc. 2008, 119,
413–420.
[80] a) T. Koritsnszky, P. Coppens, Chem. Rev. 2001, 101, 1583–1628;
b) P. Macchi, A. Sironi, Coord. Chem. Rev. 2003, 238–239, 383–
412; c) C. Gatti, Z. Kristallogr. 2005, 220, 399–457.
[81] a) S. Raub, G. Jansen, Theor. Chem. Acc. 2001, 106, 223–232; b)
I. Vidal, S. Melchor, J. A. Dobado, J. Phys. Chem. A 2005, 109,
7500–7508.
[82] a) M. A. Spackman, P. G. Byrom, Chem. Phys. Lett. 1997, 267,
215–220; b) J. J. McKinnon, M. A. Spackman, A. S. Mitchell,
Acta Crystallogr., Sect. B 2004, 60, 627–668; c) M. A. Spackman,
D. Jayatilaka, CrystEngComm 2009, 11, 19–32.
[41] H. Taka, A. Matsumoto, T. Shimizu, N. Kamigata, Heteroat.
Chem. 2001, 12, 227–237.
[42] S. C. Menon, H. B. Singh, J. M. Jasinski, J. P. Jasinski, R. J.
Butcher, Organometallics 1996, 15, 1707–1712.
[43] J. Beckmann, J. Bolsinger, A. Duthie, Organometallics 2009, 28,
4610–4612.
[44] J. Beckmann, J. Bolsinger, Z. Anorg. Allg. Chem. 2011, 637, 29.
[45] J. Beckmann, J. Bolsinger, A. Duthie, Chem. Eur. J. 2011, 17,
930–940.
[46] J. Beckmann, J. Bolsinger, A. Duthie, P. Finke, Organometallics
2012, 31, 238–245.
[47] J. Beckmann, A. Duthie, T. M. Gesing, T. Koehne, E. Lork, Orga-
nometallics 2012, 31, 3451–3454.
[48] J. Beckmann, J. Bolsinger, A. Duthie, P. Finke Dalton Trans.
2013, 42, 12193.
[49] T. Costa, H. Schmidbaur, Chem. Ber. 1982, 115, 1374–1378.
[50] R. D. Jackson, S. James, A. G. Orpen, P. G. Pringle, J. Or-
ganomet. Chem. 1993, 458, C3-C4.
[51] A. Karaçar, H. Thönnessen, P. G. Jones, R. Bartsch, R.
Schmutzler, Heteroat. Chem. 1997, 8, 539–549.
[52] A. Karaçar, M. Freytag, H. Thönnessen, J. Omelanczuk, P. G.
Jones, R. Bartsch, R. Schmutzler, Heteroat. Chem. 2001, 12, 102–
113.
[53] A. Karaçar, M. Freytag, P. G. Jones, R. Bartsch, R. Schmutzler,
Z. Anorg. Allg. Chem. 2002, 628, 533–544.
[54] P. Kilian, D. Philp, A. M. Z. Slawin, J. D. Woollins, Eur. J. Inorg.
Chem. 2003, 249–254.
[55] P. Kilian, A. M. Z. Slawin, J. D. Woollins, Chem. Eur. J. 2003, 9,
215–222.
[56] P. Kilian, A. M. Z. Slawin, J. D. Woollins, Dalton Trans. 2003,
3876–3885.
[57] P. Kilian, H. L. Milton, A. M. Z. Slawin, J. D. Woollins, Inorg.
Chem. 2004, 43, 2252–2260.
[83] J. Beckmann, E. Hupf, E. Lork Main Group Met. Chem. 2013, in
press.
[84] W. D. Neudorff, D. Lentz, M. Anibarro, A. D. Schlüter, Chem.
Eur. J. 2003, 9, 2745–2757.
[85] G. P. Schiemenz, Phosphorus Sulfur Silicon Relat. Elem. 2000,
163, 185–202.
[86] F. R. Knight, A. L. Fuller, A. M. Z. Slawin, J. D. Woollins, Chem.
Eur. J. 2010, 16, 7503–7516.
[87] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
[88] M. N. Burnett, C. K. Johnson, ORTEP-III, Oak Ridge Thermal
Ellipsoid Plotting Program for Crystal Structure Illustrations. Re-
port ORNL-6895; Oak Ridge National Laboratory: Tennessee,
TN, 1996.
[58] S. A. Reiter, S. N. Nogai, K. Karaghiosoff, H. Schmidbaur, J. Am.
Chem. Soc. 2004, 126, 15833–15843.
[59] P. Kilian, S. Parveen, A. L. Fuller, A. M. Z. Slawin, J. D. Wool-
lins, Dalton Trans. 2008, 1908–1916.
[60] K. Owsianik, R. Chauvin, A. Balin´ska, M. Wieczorek, M. Cyp-
ryk, M. Mikołajczyk, Organometallics 2009, 28, 4929–4937.
[61] D. M. U. K. Somisara, M. Bühl, T. Lebl, N. V. Richardson,
A. M. Z. Slawin, J. D. Woollins, P. Kilian, Chem. Eur. J. 2011,
17, 2666–2677.
[89] Gaussian 09, Revision A.1, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scal-
mani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M.
Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G.
Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fu-
2248
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 2233–2249

Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
kuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, [90] F. Biegler-König, J. Schönbohm, D. Bayles, J. Comput. Chem.
H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogli-
aro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Sta-
roverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell,
J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M.
Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Aus-
tin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Mo-
rokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannen-
berg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V.
Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford
CT, 2009.
2001, 22, 545 –559.
[91] M. Kohout, DGrid, version 4.5/4.6; Radebeul, Germany, 2011.
[92] CrystalExplorer (Version 3.0), S. K. Wolff, D. J. Grimwood, J. J.
McKinnon, M. J. Turner, D. Jayatilaka, M. A. Spackman, Univer-
sity of Western Australia, 2012.
[93] C. B. Hübschle, P. Luger, J. Appl. Crystallogr. 2006, 39, 901–
904.
Received: June 4, 2013
Published Online: August 15, 2013
Z. Anorg. Allg. Chem. 2013, 2233–2249
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2249