Transmetallation of Bis(6-diphenylphosphinoacenaphth-5-yl)-Mercury and -Tributyltin with Precious Metal Chlorides

Article abstract of DOI:10.1002/zaac.202000106

The reaction of bis(6-diphenylphosphinoacenapht-5yl)mercury, (6-Ph₂P-Ace-5-)₂Hg, with [(CO)₂RhCl]₂ and PtCl₂ proceeded with extrusion of mercury / mercury(I) chloride and provided the octahedral rhodium and platinum complexes (6-Ph₂P-Ace-5-)₂Rh(CO)Cl and (6-Ph₂P-Ace-5-)₂PtCl₂, respectively. The reaction of the (6-diphenylphosphinoacenapht-5yl)stannane 6-Ph₂P-Ace-5-SnBu₃ with PdCl₂ gave rise to tributyltin chloride and a dimeric arylpalladium chloride [(6-Ph₂P-Ace-5-)PdCl]₂ with a planar Pd₂Cl₂ core. Together with the previously known gold(III) complex cis- and trans-[R₂Au][Cl], the newly prepared compounds were investigated by DFT calculations. The fully optimized gas-phase structure of [(6-Ph₂P-Ace-5-)PdCl]₂ gives rise to a bend Pd₂Cl₂ core featuring a Pd···Pd palladophilic interaction. The bonding situation was studied using a set of real-space bonding indicators (RSBIs) derived from the methods Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D) and Non-Covalent Interaction (NCI) index.

Full text of DOI:10.1002/zaac.202000106

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202000106
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Transmetallation of Bis(6-diphenylphosphinoacenaphth-5-yl)-
Mercury and -Tributyltin with Precious Metal Chlorides
Sinas Furan,[a] Enno Lork,[a] Stefan Mebs,[b] Emanuel Hupf,*[a] and Jens Beckmann*[a]
Dedicated to Professor Manfred Scheer on the Occasion of his 65th Birthday
Abstract. The reaction of bis(6-diphenylphosphinoacenapht-5yl)mer- with the previously known gold(III) complex cis- and trans-
cury, (6-Ph2P-Ace-5-)2Hg, with [(CO)2RhCl]2 and PtCl2 proceeded [R2Au][Cl], the newly prepared compounds were investigated by DFT
with extrusion of mercury / mercury(I) chloride and provided the octa-
hedral rhodium and platinum complexes (6-Ph2P-Ace-5-)2Rh(CO)Cl
calculations. The fully optimized gas-phase structure of [(6-Ph2P-Ace-
5-)PdCl]2 gives rise to a bend Pd2Cl2 core featuring a Pd···Pd pallado-
and (6-Ph2P-Ace-5-)2PtCl2, respectively. The reaction of the (6-di- philic interaction. The bonding situation was studied using a set of
phenylphosphinoacenapht-5yl)stannane 6-Ph2P-Ace-5-SnBu3 with real-space bonding indicators (RSBIs) derived from the methods
PdCl2 gave rise to tributyltin chloride and a dimeric arylpalladium Atoms-In-Molecules (AIM), Electron Localizability Indicator (ELI-D)
chloride [(6-Ph2P-Ace-5-)PdCl]2 with a planar Pd2Cl2 core. Together and Non-Covalent Interaction (NCI) index.
Introduction
At present, there is great interest in peri-substituted
8-diorganophosphinonaphth-1-yl and 6-diorganophosphi-
noacenaphth-5-yl precious metal compounds of Re,[1] Ru,[2,3]
Ir,[4] Rh,[5] and particularly, Au,[6–16] which involves the syn-
thesis, bonding analysis and applications in bond activation
and catalysis. Often, the synthesis of these compounds entails
the oxidative addition of the metal to a C–H[1–5] or C–X (X =
halide) bond in peri-position to a structurally directing P atom
that takes part in coordination to the precious metal.[6–14]
Recently, we have used the well-defined 5-diorganophosphi-
noacenaphth-6-yllithium, RLi (1, R = 5-Ph2P-Ace-6-),[17] as
starting material for the synthesis of two related transmetalla-
tion reagents R2Hg (2, R = 6-Ph2P-Ace-5-)[15] and RSnBu3 (3,
R = 6-Ph2P-Ace-5-),[18] which offer the advantage to be non-
reductive and bench stable (Scheme 1).[19] The reaction of
mercury reagent 2 with (tht)AuCl gave rise to the formation
of the complex R2Hg·AuCl (4), in which the two transition
* Prof. Dr. J. Beckmann
E-Mail: j.beckmann@uni-bremen.de
* Dr. E. Hupf
E-Mail: hupf@uni-bremen.de
[a] Institut für Anorganische Chemie und Kristallographie
Universität Bremen
Leobener Straße 7
28359 Bremen, Germany
[b] Institut für Experimentalphysik
Freie Universität Berlin
Arnimallee 14
14195 Berlin, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.202000106 or from the au-
thor.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH &
Co. KGaA. · This is an open access article under the terms of the
Creative Commons Attribution License, which permits use, distri-
bution and reproduction in any medium, provided the original work
is properly cited.
Scheme 1. Formation of cis- and trans-gold compounds 5 and 6 start-
ing from mercury and tin precursors 2 and 3, respectively.[15,16]
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metals are in close proximity and engage in Au···Hg metall-
ophilic interaction (Scheme 1). During the course of a few
days, 4 converts in the cationic gold(III) complex cis-
[R2Au][Cl] (5), whereby elemental Hg was expelled
(Scheme 1).[15] The transmetallation reaction of the tin reagent
3 with (tht)AuCl3 provided the cationic gold(III) complex
trans-[R2Au][Cl] (6), the structural isomer of 5 (Scheme 1).[16]
All attempts to obtain the complexes 5 and 6 from the lithium
reagent 1 failed. In an effort to broaden the scope of the rea-
gents 2 and 3, we have now carried out a few more transmetal-
lation reactions with some precious metal chlorides leading to
the synthesis of Rh, Pt and Pd complexes, which were ana-
lyzed in this work.
Scheme 3. Synthesis of 9 starting from the tin precursor 3.
shifted in the order 7 (δ = 46.2 / 22.2 ppm) Ͼ 8 (δ = 37.2 ppm)
Ͼ 9 (δ = 17.0 ppm). The presence of 195Pt satellites in the 31P
NMR spectrum of 8 (t, 1J (31P-195Pt) = 2133.2 Hz) and the two
doublet of doublets in the spectrum of 7: δ = 46,2 (dd,
1J (103Rh-31P) = 110.7, 2J (31P-31P) = 34.8 Hz), 22.2 (dd,
2
1J (31P-103Rh) = 74.5, J (31P-31P) = 34.8 Hz) confirm the co-
Results and Discussion
ordination of the phosphines to the platinum and rhodium,
respectively. However, since the phosphorus atoms in 7 are not
chemically equivalent the signals in the 31P NMR spectrum
are split in two doublet of doublets. The IR spectrum of 7
shows the characteristic ν(CO) stretching vibration at
2071 cm–1.
The molecular structures of 7, 8, and 9, established by sin-
gle-crystal X-ray diffraction crystallography, are shown in Fig-
ure 1. Selected bond parameters are collected in Table 1.
Synthesis and Characterization
The complex (6-Ph2P-Ace-5-)2Rh(CO)Cl (7) was
prepared by the reaction of (6-Ph2P-Ace-5-)2Hg (2) with
[(CO)2RhCl]2, with formation of elemental mercury.
(6-Ph2P-Ace-5-)2PtCl2 (8) was prepared by the reaction of 2
with [PtCl2(CH3CN)2] with extrusion of mercury(I) chloride
(Scheme 2).
The
transmetallation
reaction
of
(6-Ph2P-Ace-5-)SnBu3 (3) with [PdCl2(CH3CN)2] provided
the dimeric palladium chloride [(6-Ph2P-Ace-5-)PdCl]2 (9) and
Bu3SnCl (Scheme 3).
Figure 1. Molecular structures of 7 (left), 8 (right) and 9 (bottom)
showing 50% probability ellipsoids and the crystallographic number-
ing scheme.
Scheme 2. Synthesis of 7 and 8 starting from the mercury precursor
2.
The geometrical arrangement of the metal atoms in 7 and 8
All three compounds were obtained as yellow solids in is octahedral, whereas in 9 it comprises square planar Pd
yields between 48 and 60%. They show poor solubility in atoms. Furthermore 9 forms a dimer with two bridging Cl
common organic solvents, such as THF and CHCl3. While the atoms to the Pd atoms. The P–Rh/Pt peri distances [P–Rh =
rhodium and palladium complexes decompose at higher tem- 2.3747(5) Å / 2.3813(5) Å; P–Pt = 2.372(2) Å / 2.364(2) Å]
peratures (7: 220 °C, 9: 217 °C) the platinum complex 8 show are very similar to the P–Au bond in 5 (2.3714(6) /
decomposition at relatively low temperatures of 133 °C. The 2.3702(6) Å][15] but slightly longer than the P–Au bond in 6
31P NMR chemical shifts of the compounds are downfield [2.329(3) / 2.332(3) Å].[16] In contrast, the P–Pd peri distance
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Table 1. Selected interatomic distances /Å and angles /° of 7, 8, and 9.
9 (M = Pd)
7 (M = Rh)
8 (M = Pt)
Bond lengths and angles
M(1)–C(10)
2.094(2)
2.062(2)
2.4673(5)
1.922(2)
1.101(2)
91.06(7)
89.59(5)
178.95(5)
88.96(8)
90.66(7)
2.057(2)
2.053(2)
2.443(2)
2.438(1)
2.004(2)
M(1)–C(40)
M(1)–Cl(1)
M(1)–C(5)/Cl(2)/Cl(1a)
O(1)–C(5)
C(10)–M(1)–C(40)
C(10)–M(1)–Cl(1)
C(40)–M(1)–Cl(1)
C(10)–M(1)–C(5)/Cl(2)/Cl(1a)
C(40)–M(1)–C(5)/Cl(2)/Cl(1a)
2.4135(4)
2.4346(4)
86.09(8)
172.88(5)
91.64(6)
91.78(6)
172.78(6)
95.28(5)
176.88(5)
Peri region distances
M(1)–P(1)
M(1)–P(2)
2.3747(5)
2.3813(5)
2.372(2)
2.364(2)
2.2228(4)
Peri region bond angles
M(1)–C(10)–C(19)
C(10)–C(19)–C(18)
P(1)–C(18)–C(19)
M(1)–C(40)–C(49)
C(40)–C(49)–C(48)
P(2)–C(48)–C(49)
Σ of bay angles
117.7(2)
124.2(2)
112.9(2)
116.7(3)
125.4(2)
111.7(3)
354.8(6)
353.8(8)
–5.2(6)
116.0(2)
125.3(2)
112.9(2)
115.8(2)
125.7(2)
112.2(2)
354.2(6)
353.7(6)
–5.8(6)
177.7(2)
123.4(2)
109.3(2)
350.4(6)
–9.6(6)
a)
Splay angle
–6.2(8)
–6.3(6)
Out-of-plane displacement
P(1)
P(2)
M(1)
0.1888(5)
–0.1842(4)
0.1032(4)
0.2027(4)
–0.0858(7)
–0.2021(7)
0.2897(5)
0.0940(5)
0.0480(5)
–0.2429(2)
Central acenaphthyl ring torsion angles
C: (13)–(14)–(19)–(18)
–178.5(3)
175.5(2)
179.0(2)
177.9(2)
–176.1(3)
–177.9(3)
–179.2(3)
–178.3(3)
–179.8(3)
–177.6(2)
C: (15)–(14)–(19)–(10)
C: (43)–(44)–(49)–(48)
C: (45)–(44)–(49)–(40)
a) Splay angle: sum of the three bay region angles – 360°.
Table 2. Topological and integrated bond properties of 5–9 from AIM and ELI-D.
Contact or
basin
d /Å
ρ(r) /e·Å–3
ٌ2ρ(r) /e·Å–5
ε
G/ρ(r) /a.u. H/ρ(r) /a.u. NELI /e VELI /Å3
γELI
RJI
5
6
7
Au–C1
Au–C2
Au–P1
Au–P2
Au–C1
Au–C2
Au–P1
Au–P2
Rh–C1
Rh–C2
Rh–P1
Rh–P2
Rh–Cl
2.077
2.077
2.362
2.362
2.106
2.106
2.339
2.339
2.048
2.079
2.349
2.364
2.451
1.880
2.038
2.038
2.335
2.335
2.433
2.433
1.993
2.216
2.424
2.452
1.998
2.217
2.465
2.410
2.880
0.90
0.90
0.71
0.71
0.86
0.86
0.74
0.74
0.87
0.83
0.63
0.63
0.45
1.08
0.99
0.99
0.75
0.75
0.53
0.53
0.96
0.81
0.46
0.42
0.95
0.81
0.41
0.47
0.21
2.0
2.0
1.3
1.3
2.5
2.5
0.8
0.8
2.9
3.1
3.2
2.5
4.3
11.5
1.5
1.5
1.1
1.1
4.1
4.1
3.1
1.9
4.8
4.7
2.9
2.1
4.5
4.9
2.1
0.05
0.04
0.01
0.01
0.04
0.04
0.01
0.01
0.03
0.06
0.04
0.02
0.03
0.00
0.05
0.04
0.03
0.02
0.02
0.02
0.05
0.04
0.09
0.06
0.05
0.01
0.08
0.09
0.37
0.63
0.63
0.55
0.55
0.65
0.65
0.52
0.52
0.68
0.70
0.73
0.67
0.91
1.25
0.62
0.62
0.55
0.55
0.83
0.83
0.71
0.64
0.96
0.99
0.69
0.66
0.97
0.97
0.80
–0.47
–0.47
–0.43
–0.43
–0.45
–0.45
–0.44
–0.44
–0.45
–0.43
–0.38
–0.38
–0.23
–0.50
–0.51
–0.51
–0.45
–0.45
–0.30
–0.30
–0.48
–0.48
–0.24
–0.22
–0.48
–0.48
–0.21
–0.24
–0.11
1.81
1.81
1.91
1.91
1.89
1.89
1.89
1.89
1.74
1.82
2.03
1.99
0.63
2.77
1.70
1.70
1.92
1.92
0.58
0.58
1.80
2.03
5.8
5.8
7.1
7.1
6.5
6.5
6.9
6.9
4.1
4.7
7.4
7.5
1.0
9.5
3.9
3.9
6.3
6.3
0.8
0.8
5.5
7.8
1.62
1.62
1.70
1.70
1.66
1.66
1.68
1.68
1.67
1.71
1.73
1.80
1.48
1.69
1.64
1.64
1.69
1.69
1.46
1.46
1.63
1.59
76.6
76.6
74.5
74.5
79.3
79.3
72.0
72.1
80.4
81.8
80.2
80.5
87.6
85.8
75.0
75.0
73.2
73.2
83.5
83.5
79.2
71.9
Rh–C(O)
Pt–C1
8
9
Pt–C2
Pt–P1
Pt–P2
Pt–Cl2
Pt–Cl2
Pd1–C1
Pd1–P1
Pd1–Cl1
Pd1–Cl2
Pd2–C2
Pd2–P2
Pd2–Cl1
Pd2–Cl2
Pd1–Pd2
1.78
2.06
5.4
8.0
1.63
1.60
78.8
72.1
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in 9 is significantly shorter [2.2228(4) Å]. Nevertheless, the (ECP28MDF and ECP60MDF, respectively)[22] have been
peri interactions of the presented compounds are of predomi- used. Dispersion effects have been modelled using Grimme’s
nantly attractive nature. The splay angles, which are the sum GD3BJ parameters.[23] The optimized gas-phase structures are
of the three bay region angles – 360, also indicate the attractive in good agreement with the solid-state structures for com-
nature of the peri interactions since they exhibit negative val- pounds 5–8. Interestingly, the optimized gas-phase structure
ues between –5.2 and –9.6. Furthermore, the central ace- for the palladium compound 9 differs substantially from the
naphthyl ring torsion angles for all compounds are very close solid-state structure. In contrast to the planar Pd2Cl2 core ob-
to the ideal angle of 180°, as the highest deviation is observed served in the solid-state structure with a Pd···Pd separation of
at 175.5(2)°, showing nearly perfect planarity of the ace- 3.4536(3) Å, the optimized gas-phase structure give rise to a
naphthyl backbone. In agreement, the phosphorus and metal bend Pd2Cl2 core with a short Pd···Pd distance of 2.880 Å com-
atoms show little out-of-plane displacements from the ace- prising a palladophilic interaction, vide infra. PES scans with
naphthyl planes, with the largest deviation for P being varied Pd–Cl–Pd angles of 180.0°, 161.5°, 143.0°, 124.5° and
0.2021(7) Å and for the metal 0.2897(5) Å.
106.0° revealed a relatively small energy gain of ΔE =
–18.6 kJ·mol–1 from 180.0° to 143.0°, but an additional energy
gain of ΔE = –69.4 kJ·mol–1 from 143.0° to 106.0° in the gas-
phase geometry (see Figure S4, Supporting Information). Care
Computational Analysis
Density functional theory (DFT) computations have been must be taken in assigning this energy gain to the formation
applied on the previously prepared gold compounds 5[15] and of the palladophilic interactions alone, as a recent study by
6[16] as well as for the newly synthesized compounds 7, 8, Cockroft et al.[24] on the significance of metallophilic interac-
and 9. The gas-phase structures were fully optimized using the tions shows that other effects such as electrostatic and disper-
B3PW91[20] functional with the 6-311+G(2df,p)[21] (for H, C, sion contributions have to be evaluated as well. Indeed, the
O, P and Cl) basis-set. For the transition metals Rh, Pd, Pt gas-phase structure shows intramolecular πphenyl···πacenaphthyl
and Au, the cc-pVTZ[22] basis-set with effective core potentials interactions, which are absent in the solid-state structure. As
Figure 2. RSBI analysis of 5. Top left: AIM bond paths motif with bond critical points (bcps, red spheres). Top right: NCI iso-surface at s(r) =
0.5 color coded with sign(λ2)ρ in a.u. Blue surfaces refer to attractive forces and red to repulsive forces. Green indicates weak interactions.
Bottom left: ELI-D localization domain representation at iso-value of 1.4. Basins are color coded from blue (small) to red (large) with H-Basins
given in transparent mode.
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for the isomeric gold compounds, it turned out that the cis- (H/ρ(r)bcp = –0.43 to –0.51 h·e–1). This is supported by the
[R2Au]+ cation of 5[15] is by 20.9 kJ·mol–1 more stable than Raub-Jansen-Index (RJI),[28] which varies between 75% in 8
the trans-[R2Au]+ cation of 6.[16]
(least polarized) and 82% in 7 (most polarized).
Compounds 5–9 were studied by a set of real-space bonding
The Rh–CO bond has the largest covalent and ionic bond
indicators (RSBIs). The topological and integrated bonding as contributions and the exceptional high RJI value of 85.8%,
well as atomic properties were derived from the Atoms-In- which suggest rather dative bond than polarized covalent bond
Molecules (AIM)[25] and Electron Localizability Indicator character. Respective G/ρ(r)bcp, H/ρ(r)bcp, and RJI values at
(ELI-D)[26] space-partitioning schemes, respectively, and are the bcp of the M–P bonds show slightly smaller numbers com-
summarized in Table 2. Additionally, the bonding was exam- pared to the M–C bonds, pointing towards somewhat lower
ined by computing Non-Covalent Interaction (NCI) indices.[27] covalent as well as ionic contributions in the M–P interactions,
The qualitative results of the AIM, ELI-D and NCI analyses whereas dominant ionic bond contributions are observed for
are illustrated in Figure 2, Figure 3, Figure 4, Figure 5, and the M–Cl bonds, as expected. Within the ELI-D framework,
Figure 6. Overall, the M–C (M = Rh, Pd, Pt, Au) topological the Pd–Cl bonds are assigned as ionic Pd+Cl– contacts as no
real space bonding indicators show the characteristics of polar corresponding ELI-D bonding basins are formed. The differ-
covalent bonds with electron density values at the bond critical ences between M–C and M–P bonds are further corroborated
point (bcp) ranging from 0.83 to 0.99 e·Å–3, positive Laplaci- by an inspection of the NCI analysis, which reveals red colored
ans [ٌ2ρ(r)bcp = 1.5 to 3.1 e·Å–5] and kinetic energy densities donut-shaped areas along the M–P bonds (see Figure 2,
over electron density values [G/ρ(r)bcp = 0.62 to 0.70 h·e–1] as Figure 3, Figure 4, Figure 5, and Figure 6, top right), but no
well as negative total energy densities over electron densities regions of non-covalency along the M–C bonds. In all com-
Figure 3. RSBI analysis of 6. Top left: AIM bond paths motif with bond critical points (bcps, red spheres). Top right: NCI iso-surface at s(r) =
0.5 color coded with sign(λ2)ρ in a.u. Blue surfaces refer to attractive forces and red to repulsive forces. Green indicates weak interactions.
Bottom left: ELI-D localization domain representation at iso-value of 1.4. Basins are color coded from blue (small) to red (large) with H-Basins
given in transparent mode.
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Figure 4. RSBI analysis of 7. Top left: AIM bond paths motif with bond critical points (bcps, red spheres). Top right: NCI iso-surface at s(r) =
0.5 color coded with sign(λ2)ρ in a.u. Blue surfaces refer to attractive forces and red to repulsive forces. Green indicates weak interactions.
Bottom left: ELI-D localization domain representation at iso-value of 1.4. Basins are color coded from blue (small) to red (large) with H-Basins
given in transparent mode.
pounds, a cage like distribution of the d-orbital lone pairs
of the transition metals can be found in the ELI-D analysis.
Particularly, this can be seen for 5–8 as the non-bonding d-
orbitals are distributed in a key-lock fashion pointing to the
corners of a cube in regard to the other six bonds (see Figure 2,
Figure 3, Figure 4, and Figure 5, bottom insets). A structural
feature in the gas-phase structure of the palladium complex 9
is the formation of a weak Pd···Pd palladophilic interaction
Conclusions
The synthesis of three transition metal containing
acenaphthyl
compounds
is
presented,
namely
(6-Ph2P-Ace-5-)2Rh(CO)Cl (7), (6-Ph2P-Ace-5-)2PtCl2 (8),
and [(6-Ph2P-Ace-5-)PdCl]2 (9). The relatively large electrone-
gativity of these transition metals leads to M–C bonds with
substantial covalent contributions and are comparable to the
Au–C bonds in the gold cations of 5 and 6. While the solid-
state structure of the palladium compound 9 shows a planar
Pd2Cl2 core with a long Pd···Pd separation, the optimized gas-
phase structure give rise to a bend Pd2Cl2 with a short Pd···Pd
distance and is characterized as a palladophilic interaction. The
latter case also illustrates the flexibility of the palladium com-
plex in different aggregates.
revealing a small electron density at the bcp of ρ(r)bcp
0.21 e·Å–3 a positive Laplacian of ٌ2ρ(r)bcp = 2.1 e·Å–5,
a positive kinetic energy density over ρ(r)bcp [G/ρ(r)bcp
=
=
0.80 h·e–1] and a negative, but close to zero total energy den-
sity over ρ(r)bcp of H/ρ(r)bcp = –0.11 h·e–1, which are similar
values compared to Au···Au and Hg···M (M = Hg, Cu, Ag,
Au) metallophilic interactions in other acenaphthyl based sys-
tems.[15,16,29] The palladophilic interaction is further validated
in the formation of a blue colored disk shaped area along the
Pd-Pd axis in the NCI analysis (Figure 6, top right) and the
observation of increased electron localizability on a Pd ELI-D
basin pointing towards the neighboring Pd atom as indicated
by the red area (Figure 6, bottom right).
Experimental Section
General: All reagents were obtained commercially (Sigma–Aldrich,
Germany) and were used as received. Dry solvents were collected from
a
SPS800 mBraun solvent system. The starting materials
bis(6-diphenylphosphinoacenapht-5yl)mercury[15] and 6-(diphenyl-
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Figure 5. RSBI analysis of 8. Top left: AIM bond paths motif with bond critical points (bcps, red spheres). Top right: NCI iso-surface at s(r) =
0.5 color coded with sign(λ2)ρ in a.u. Blue surfaces refer to attractive forces and red to repulsive forces. Green indicates weak interactions.
Bottom left: ELI-D localization domain representation at iso-value of 1.4. Basins are color coded from blue (small) to red (large) with H-Basins
given in transparent mode.
phosphanyl)acenaphth-5-yl)-tributyltin[18] were prepared according to
literature procedures. 1H-, 13C- and 31P-NMR spectra were recorded
at room temperature (unless otherwise stated) using Bruker Avance
360 and Bruker Avance Neo 600 spectrometer and are referenced to
tetramethylsilane (1H, 13C) and phosphoric acid (85% in water) (31P).
Chemical shifts are reported in parts per million (ppm) and coupling
constants (J) are given in Hertz (Hz). Electrospray ionization mass
spectrometry (ESI-MS) was carried out using a Bruker Impact II. The
solutions 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 4 L·min–1 and a pressure of
0.4 bar. The spectra were collected for 30 s and averaged. The IR
spectrum was recorded on a Hyperion 3000 spectrometer as thin coat-
ing on a gold surface. Wavenumbers are reported in cm–1.
slow diffusion of n-hexane into the obtained red solution at room tem-
perature which led to 7 as yellow solid [30.0 mg, 0.036 mmol, 60%,
m.p. 220 °C (dec.)]. Single crystals suitable for X-ray diffraction were
obtained in the same way. 1H NMR (600.5 MHz, [D8]THF): δ = 8.17–
8.14 (m, 2 H), 8.08–8.02 (m, 2 H), 7.81–7.78 (m, 2 H), 7.71–7.68 (m,
3
2 H), 7.33–7.30 (m, 5 H), 7.27–7.22 (m, 2 H), 7.15 (d, J (1H-1H) =
3
6.9 Hz, 1 H), 7.08–6.99 (m, 5 H), 6.73 (t, J (1H-1H) = 7.3 Hz, 1 H),
6.48 (d, 3J (1H-1H) = 7.2 Hz, 1 H), 6.38–6.35 (m, 2 H), 6.27 (d, 3J
(1H-1H) = 7.2 Hz, 1 H), 6.14–6.11 (m, 2 H), 3.52–3.38 (m, 4 H, H1 or
H2), 3.28–3.18 (m, 2 H, H1 or H2), 3.13–3.05 (m, 2 H, H1 or H2).
13C{1H} NMR (150.1 MHz, [D8]THF): δ = 188.8 (ddd, 1J (103Rh-13C)
= 146.7, 2J (31P-13C) = 11.4 Hz, CO), 163.6 (dd, J (103Rh-13C) = 107.3,
J (31P-13C) = 28.9 Hz), 151.9 (s), 150.8 (s), 149.5 (d, J (31P-13C) =
38.6 Hz), 146.6 (d, J (31P-13C) = 36.3 Hz), 142.0 (s), 141.0 (dd, J =
19.3, 4.7 Hz), 140.5 (d, J = 17.5), 139.9 (dd, J = 28.0, 12.3 Hz), 139.1
(d, J = 38.8 Hz), 138.4 (d, J = 23.9 Hz), 134.8 (dd, J = 38.8, 10.0 Hz),
134.4 (s), 133.9–133.2 (m), 133.0 (dd, J = 48.2, 10.2 Hz), 132.3 (dd,
J = 20.7, 9.4 Hz), 130.8 (s), 130.2 (d, J = 26.6 Hz), 128.7 (dd, J =
Synthesis of (6-Ph2P-Ace-5-)2Rh(CO)Cl (7): Bis(6-(diphenylphos-
phanyl)acenaphth-5-yl)mercury (50.0 mg, 0.06 mmol) and di-μ-chloro
tetracarbonyldirhodium(I) (11.1 mg, 0.03 mmol) were dissolved in
tetrahydrofuran (3 mL) and stirred at room temperature overnight. The
gray residue was filtered and the raw product was recrystallized via 15.3, 9.6 Hz), 128.2 (d, J = 10.2 Hz), 127.9 (d, J = 51.2 Hz), 126.4 (d,
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Figure 6. RSBI analysis of 9. Top left: AIM bond paths motif with bond critical points (bcps, red spheres). Top right: NCI iso-surface at s(r) =
0.5 color coded with sign(λ2)ρ in a.u. Blue surfaces refer to attractive forces and red to repulsive forces. Green indicates weak interactions.
Bottom left: ELI-D localization domain representation at iso-value of 1.4. Basins are color coded from blue (small) to red (large) with H-Basins
given in transparent mode. Bottom right: ELI-D distribution (unitless) color-coded onto one of the Pd ELI-D basin.
3
J = 9.8 Hz), 125.6 (d, J = 42.0 Hz), 122.3 (d, J = 80.7 Hz), 121.5 (s), δ = 152.7 (s, Cc or Cd), 146.7 (t, J(31P-13C) = 18.6 Hz, Cb), 142.1 (s,
2
119.7 (d, J = 8.6 Hz), 119.3 (d, J = 6.8 Hz), 31.5 (s, C1 or C2), 31.1
(s, C1 or C2), 30.6 (s, C1 or C2), 29.8 (s, C1 or C2). 31P{1H} NMR
Cc or Cd), 140.9 (t, J(31P-13C) = 9.0 Hz, Ca), 135.8–135.6 (m), 135.0
(t, J(195Pt-13C) = 30.8, J(31P-13C) = 3.1 Hz, C4), 134.4 (t, J(31P-13C)
2
4
(242.3 MHz, [D8]THF): δ = 46.2 (dd, J (103Rh-31P) = 110.7, J (31P- = 4.9 Hz), 131.0 (d, J(31P-13C) = 29.6 Hz), 130.1 (s), 128.5 (t, J(195Pt-
1
2
31P) = 34.8 Hz), 22.2 (dd, 1J (31P-103Rh) = 74.5, 2J (31P-31P) =
34.8 Hz). HR-ESI MS: (CH2Cl2/MeCN 1:100, positive mode): calcd.
for C49H36OP2Rh [M–Cl]+, 805.12909; found, 805.12860. IR: ν˜ =
3050 (CH), 2922 (CH), 2071 (CO) cm–1.
13C) = 28.2, J(31P-13C) = 5.2 Hz,), 124.3 (t, J(31P-13C) = 5.4 Hz), 122.6
(t, 3J(31P-13C) = 28.0 Hz, C5), 120.3 (t, 3J(195P-13C) = 58.9 Hz, C3),
119.6 (t, J(31P-13C) = 4.4 Hz, C8), 31.3 (s, C1 or C2), 29.9 (s, C1 or
2
C2). 31P{1H} NMR (145.9 MHz, CDCl3): δ = 37.2 (t, J (195Pt-31P) =
1
2133.2 Hz). HR-ESI MS: (CH2Cl2/MeOH 1:10, positive mode): calcd.
for C48H35P2Pt [M–HCl–Cl]+, 868.18607; found, 868.18536, ESI MS:
(MeCN, positive mode): m/z = 870.5 (C48H37Cl2P2Pt) for [M + H]+.
Synthesis of (6-Ph2P-Ace-5-)2PtCl2 (8): Pt(CH3CN)Cl2 was prepared
by refluxing PtCl2 (15.2 mg, 0.06 mmol) in acetonitrile (3 mL) for 1
h until the formation of a transparent brown solution without any resi-
due of PtCl2 took place. After addition of bis(6-(diphenylphosphanyl)-
Synthesis of [6-Ph2P-Ace-5-PdCl]2 (9): Pd(CH3CN)Cl2 was prepared
acenaphth-5-yl)mercury (50.0 mg, 0.06 mmol) the reaction mixture by refluxing PdCl2 (14.2 mg, 0.08 mmol) in acetonitrile (5 mL) for
was further stirred for 4 h at 70 °C and 12 h at room temperature. The 1 h until the formation of a transparent brown solution without any
solvent was evaporated, and dichloromethane (10 mL) was added to
the crude product. Aqueous workup and removal of the solvent by
rotary evaporation led to 2 as yellow solid (26.0 mg, 0.03 mmol, 48%,
residue of PtCl2 took place. After addition of 6-(diphenylphosphanyl)-
acenaphth-5-yl)-tributyltin (50.0 mg, 0.08 mmol) the reaction mixture
was further stirred for 1 h at 70 °C and 12 h at room temperature. The
m.p. 133 °C (dec.)). Single crystals suitable for X-ray diffraction were precipitate was filtered off, washed with acetonitrile and hexane to
obtained by letting an acetonitrile solution of 8 stand at room tempera- obtain 9 as a yellow solid [21.0 mg, 0.04 mmol, 54%, 217 °C (dec.)].
1
ture for several weeks. H NMR (360.3 MHz, CDCl3): δ = 8.36–8.31 Single crystals suitable for X-ray diffraction were obtained via slow
(m, 4 H), 8.07–8.02 (m, 2 H), 7.96–7.91 (m, 4 H), 7.52 (d, 3J (1H-1H)
= 7.1 Hz, 2 H, H–7), 7.48–7.43 (m, 2 H), 7.37–7.30 (m, 10 H), 6.16
evaporation of a dichloromethane solution of 9 at room temperature.
3
1H NMR (600.5 MHz, CD2Cl2): δ = 8.47 (d, J (1H-1H) = 8.2 Hz, 1
3
3
4
(d, J (1H-1H) = 7.4 Hz, 2 H), 5.91 (dt, J (1H-1H) = 7.4, J (1H-1H) H), 7.67–7.64 (m, 3 H), 7.50–7.47 (m, 1 H), 7.44–7.41 (m, 3 H), 7.31
= 1.6, J (195Pt– H) = 50.8 Hz, 2 H, H–4), 3.52–3.36 (m, 4 H, H1 or
H2), 3.29–3.13 (m, 4 H, H1 or H2). 13C{1H} NMR (90.6 MHz, CDCl3):
(t, J (1H-1H) = 7.7 Hz, 4 H), 7.28–7.25 (m, 1 H), 7.18 (d, J (1H-1H)
3
1
3
3
= 7.2 Hz, 1 H), 3.48–3.46 (m, 2 H, H1 or H2), 3.42–3.40 (m, 2 H, H1
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Table 3. Crystal data and structure refinement of 7–9.
7·THF
8·NCMe
9·2 CHCl3
Formula
C53H44ClOP2Rh
913.18
C50H39Cl2NP2Pt
981.75
C50H38Cl8P2P2
1197.14
Formula weight /g·mol–1
Crystal system
Crystal size /mm
Space group
a /Å
b /Å
c /Å
monoclinic
0.40ϫ0.20ϫ0.08
P21/c
11.0057(5)
16.8947(9)
22.118(1)
90
91.345(1)
90
4111.4(3)
4
triclinic
0.10ϫ0.10ϫ0.07
¯
P1
triclinic
0.20ϫ0.06ϫ0.05
¯
P1
11.772(5)
13.186(6)
13.600(7)
93.86(2)
97.19(2)
96.69(2)
2073(2)
2
9.2489(2)
11.5531(3)
12.5609(3)
101.584(1)
108.241(1)
106.764(1)
1156.34(5)
1
α /°
β /°
γ /°
V /Å3
Z
ρcalcd /Mg·m–3
μ (Mo-Kα) /mm–1
F(000)
1.475
0.602
1880
1.573
3.627
976
1.719
1.346
596
θ range, deg
Index ranges
2.38 to 28.35
–14 Յ h Յ 14
–22 Յ k Յ 22
–29 Յ l Յ 29
82508
2.48 to 29.96
–16 Յ h Յ 16
–18 Յ k Յ 18
–19 Յ l Յ 19
233055
2.48 to 29.96
–13 Յ h Յ 13
–16 Յ k Յ 16
–17 Յ l Յ 17
91725
No. of reflns collected
Completeness to θ max
No. indep. reflns
99.9%
10247
99.9%
12069
99.9%
6785
No. obsd reflns with [I Ͼ 2σ(I))
No. refined parameters
GooF (F2)
8540
532
1.014
11109
506
1.038
6289
280
1.034
R1 (F) [I Ͼ 2σ(I)]
0.0284
0.0664
0.528 / –0.556
0.0201
0.0499
1.138 / –0.892
0.0290
0.0648
1.234 / –1.820
wR2 (F2) (all data)
Largest diff peak/hole /e·Å–3
or H2). 13C{1H} NMR (150.1 MHz, CD2Cl2): δ = 152.3 (s, Cc or Cd), potentials (Pt, Au: ECP60MDF, Rh, Pd: ECP28MDF)[22] and corre-
sponding cc-pVTZ[22] basis sets were utilized. The basis sets as well
as the effective core potential (ECP) were obtained from the Basis
Set Exchange Library.[33] Dispersion effects have been modelled using
Grimme's GD3BJ parameters.[23] All computations were performed
with the Gaussian09 software.[34] The wavefunction files were used
for a topological analysis of the electron density according to the
Atoms-In-Molecules space-partitioning scheme[25] usingAIM2000,[35]
whereas DGRID[36] was used to generate and analyze the Electron-
Localizability-Indicator (ELI-D) related real-space bonding descrip-
tors[26] applying a grid step size of 0.05 a.u. The NCI grids were com-
puted with NCIplot.[37] Bond paths are displayed with AIM2000,[35]
while ELI-D and NCI figures are displayed with VMD.[38]
148.4 (s, Cc or Cd), 140.7 (s, Cb) 137.3–137.2 (m, Co), 136.4 (s),
134.1–134.0 (m), 131.9 (s, Cp), 131.0–130.7 (m), 130.0 (s), 129.3–
129.2 (m, Cm), 124.7–124.6 (m), 123.6–123.2 (m,), 121.4 (s, C3),
120.0–119.9 (m, C8), 31.9 (s, C1 or C2), 31.7 (s, C1 or C2). 31P{1H}
NMR (242.3 MHz, CD2Cl2): δ = 17.0 (s). HR-ESI MS (CH2Cl2/
MeCN 1:10, positive mode): calcd. for C24H18PPd [M–Cl]+,
443.01850; found, 443.01782.
X-ray Crystallography: Intensity data of 7–9 were collected at 100 K
with a Bruker Venture D8 diffractometer with graphite-monochro-
mated Mo-Kα (0.7107 Å) radiation. All structures were solved by di-
rect methods and refined based on F2 by use of the SHELX program
package as implemented in OLEX.[30] Strongly disordered solvent
molecules were accounted using the SQUEEZE routine for 8.[31] All
non-hydrogen atoms were refined using anisotropic displacement pa-
rameters. Hydrogen atoms attached to carbon atoms were included in
geometrically calculated positions using a riding model. Crystal and
refinement data are collected in Table 3. Figures were created using
DIAMOND.[32]
Supporting Information (see footnote on the first page of this article):
Figures of NMR and IR spectra and additional results from DFT
calculations.
Acknowledgements
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-1987351 (7·THF), CCDC-1987352 (8·NCMe), and
CCDC-1987353 (9·2CHCl3) (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
The Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowl-
edged for financial support. We are grateful to Umicore (Hanau, Ger-
many) for a donation of precious metals. Open access funding enabled
and organized by Projekt DEAL.
Computational Methodology: Geometry optimizations of the gas-
phase structure were performed using density functional theory (DFT) Keywords: Peri-interactions; Transmetallation; Rhodium;
with the B3PW91[20] functional and the 6-311+G(2df,p) (for H, C, O,
Palladium; Platinum
P and Cl)[21] basis-set. For the Rh, Pd, Pt and Au atoms, effective core
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