[4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4 a salt containing a cationic triphenylphosphanestabilized organostannylene transition metal complex

Article abstract of DOI:10.1515/mgmc-2015-0028

The isolation and molecular structure of bis(di-iso-propoxyphosphonyl)-4-tert-butyl]phenyl}tin triphenylphosphane perchlorate chromium pentacarbonyl, 2, is reported. It is the first example of an ionic compound containing an organostannylene transition metal complex cation stabilized by a phosphane donor. Slow reaction of compound 2 in acetonitrile gave trans-bis-triphenylphosphane chromium tetracarbonyl, trans-(Ph₃P)₂Cr(CO)₄, in a new crystalline modification.

Full text of DOI:10.1515/mgmc-2015-0028

Main Group Met. Chem. 2015; 38(5-6): 169–173
Short Communication
Michael Wagner, Thomas Zöller, Christina Dietz and Klaus Jurkschat*
[4-tBu-2,6-{P(O)(OiPr)2}2C6H Sn(PPh3)Cr(CO) ]ClO4 –
a salt containing a cationic 2triphenylphosp5hane-
stabilized organostannylene transition metal
complex
DOI 10.1515/mgmc-2015-0028
Received September 1, 2015; accepted September 9, 2015; previously
published online October 13, 2015
et al., 2013). Herein, we report the isolation and complete
characterization of the triphenylphosphane-stabilized orga-
nostannylene chromium pentacarbonyl complex 2 (Lꢀ=ꢀPPh3,
Scheme 1). Compound 2 might formally be rationalized as a
push-pull complex (Thimer et al., 2009; Al-Rafia et al., 2011;
Ghadwal et al., 2011; Swarnakar et al., 2014; El Ezzi et al.,
2015). However, as it was demonstrated previously (Wagner
et al., 2013), both the Sn-Cr and Sn-P bonds are highly
covalent.
Compound 2 was obtained as a colorless crystalline
material from a solution of the corresponding perchlorate
salt 1 in acetonitrile to which an equimolar amount of
PPh3 had been added. Compound 2 shows good solubility
Abstract: The isolation and molecular structure of bis(di-iso-
propoxyphosphonyl)-4-tert-butyl]phenyl}tin triphenylphos-
phane perchlorate chromium pentacarbonyl, 2, is reported.
It is the first example of an ionic compound containing an
organostannylene transition metal complex cation stabi-
lized by a phosphane donor. Slow reaction of compound
2 in acetonitrile gave trans-bis-triphenylphosphane chro-
mium tetracarbonyl, trans-(Ph3P)2Cr(CO)4, in a new crystal-
line modification.
Keywords: cation; hypercoordinated tin; pincer-type ligand. in common polar organic solvents such as acetonitrile and
dichloromethane.
The molecular structure of 2, as well as selected inter-
The soft phosphane donor moiety has been used in organo- atomic distances and angles, is shown in Figure 1.
tin chemistry (Izod, 2012; Hupf et al., 2014). Yet, ionogenic
The Sn(1) atom is pentacoordinated and exhibits a trig-
compounds containing tin cations and phosphane Lewis onal-bipyramidalenvironment,whereO(1)andO(2)occupy
bases are scarce (Barney et al., 1999; Objartel et al., 2008; the axial and C(1), Cr(1), and P(3) the equatorial positions,
MacDonald et al., 2011, 2012; Weicker et al., 2013; Burt respectively. The overall geometry is similar to that of the
et al., 2014). Recently, we reported the synthesis of and corresponding DMAP-stabilized derivative (Wagner et al.,
density functional theory (DFT) calculations on the het- 2013). The Cr(1)-Sn(1)-C(1) angle of 138.00(7)° is smaller
eroleptic organostannylene chromium pentacarbonyl com- than in compound 1 (146.31(10)°) (Wagner et al., 2013).
plexes [4-tBu-2,6-{P(O)(OiPr)2}2C6H2(X)SnCr(CO)5] (Xꢀ=ꢀClO4, The Sn(1)-P(3) distance of 2.6665(7) Å in 2 is similar as the
OTf), and [4-tBu-2,6-{P(O)(OiPr)2}2C6H2(L)SnCr(CO)5][ClO4] ones observed in Sn(SCH2CH2)2PPh [2.614(5) Å] (Baumeister
(Lꢀ=ꢀpMe2NC5H4N (DMAP, 4-dimethylaminopyridine), Ph3PO). et al., 1986), [PhB(CH2PPh2)3][SnCl] [2.6746(14) Å] (Barney
Within the scope of these investigations, we also learned et al., 1999) and [(Ph2Ppic)Sn(Cl)][SnCl3] (picꢀ=ꢀ2-picolyl)
about the ability of the soft Lewis base triphenylphos- [2.6962(5) Å] (Objartel et al., 2008). A shorter Sn-P distance
phane, PPh3 to stabilize such complexes but, at that time, wasobservedin[SnCl2(PMe3)2][AlCl4]2 with2.5390(6)Å(Mac-
failed isolating the corresponding representative (Wagner Donald et al., 2012). Similar and longer distances were also
found for phosphane stannylene Lewis pairs [2.6362(6)–
*Corresponding author: Klaus Jurkschat, Lehrstuhl für Anorganische
2.7489(4) Å] (Freitag et al., 2013a,b) and for [PhP(CH2CH2S)2
Chemie II, Technische Universität Dortmund, D-44221 Dortmund,
Sn(C5H5N)Cr(CO)5] [2.756(1) Å] (Jurkschat et al., 1988). For
Germany, e-mail: klaus.jurkschat@tu-dortmund.de
[(oC6H4CH2PPh2)2SnW(CO)5], the Sn-P distances of 2.831(2)
and 3.012(2) Å are much longer, however (Abicht et al.,
1987).
Michael Wagner, Thomas Zöller and Christina Dietz: Lehrstuhl für
Anorganische Chemie II, Technische Universität Dortmund, D-44221
Dortmund, Germany
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ꢀꢀꢀꢁ
170ꢀ ꢀM. Wagner et al.: [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4
OiPr
OiPr
iPrO
iPrO
iPrO
iPrO
P
O
Sn
O
P
O
Sn
O
Cr(CO)5
PPh3
Cr(CO)5
OClO3
PPh3
ClO4
tBu
tBu
P
P
OiPr
OiPr
2
1
Scheme 1:ꢀSynthesis of the ionic compound 2 containing a
triphenylphosphane-stabilized cationic organotin chromium penta-
carbonyl complex.
Figure 2:ꢀMolecular structure (SHELXTL) of trans-[Cr(CO)4(PPh3)2], 3,
showing 30% probability displacement ellipsoids.
The hydrogen atoms are omitted for clarity. Selected interatomic
distances (Å) and angles (°): P(1)-Cr(1) 2.3298(10), P(2)-Cr(1)
2.3370(10), Cr(1)-C(41) 1.902(4), Cr(1)-C(44) 1.876(4), P(1)-Cr(1)-P(2)
177.65(4), C(42)-Cr(1)-C(43) 172.15(15).
A 31P NMR spectrum of the CD3CN solution from which
the crystals of complex 3 had been separated showed two
major resonances at δ 37.3 [J(31P-117/119Sn)ꢀ=ꢀ125/130 Hz] and
30.3 ppm [J(31P-117/119Sn)ꢀ=ꢀ180 Hz], respectively, in an almost
1:1 ratio. The first resonance is assigned to the organotin(II)
perchlorate RSnOClO3, 4 [Rꢀ=ꢀ4-tBu-2,6-{P(O)(OiPr)2}2C6H2].
The chemical shift and magnitude of the coupling con-
stant are close to the values reported for RSnCl [δ 37.8 ppm,
J(31P-117/119Sn)ꢀ=ꢀ113/119 Hz] (Henn et al., 2011). The second
resonance is assigned to compound 1 (Wagner et al., 2013).
A 1H NMR spectrum showed two sets of signals for the aro-
matic protons of the ligand that are assigned to 1 and 4,
respectively. A 1H 13C HMBC spectrum showed cross peaks
Figure 1:ꢀMolecular structure (SHELXTL) of 2 showing 30% prob-
ability displacement ellipsoids.
The hydrogen atoms are omitted for clarity. Selected intera-
tomic distances (Å) and angles (°): Sn(1)-C(1) 2.176(3), Sn(1)-Cr(1)
2.5896(5), Sn(1)-P(3) 2.6665(7), Sn(1)-O(1) 2.3081(19), Sn(1)-O(2)
2.3471(19), Cr(1)-Sn(1)-C(1) 138.00(7), Cr(1)-Sn(1)-P(3) 119.30(2), C(1)-
Sn(1)-P(3) 102.65(7), O(1)-Sn(1)-O(2) 152.18(7).
OiPr
iPrO
During storage of compound 2 in CD3CN solution in a
sealed NMR tube, yellow crystals separated. These were
identified by single crystal X-ray diffraction as trans-
[Cr(CO)4(PPh3)2], 3, which crystallized as a polymorph to
known structures with similar interatomic distances and
angles (Bao et al., 2001; Bennett et al., 2004). Compound
P
O
Sn
O
Cr(CO)5
PPh3
tBu
ClO4
2
P
iPrO
OiPr
2
several weeks
CD3CN
̅
3 crystallized in the space group P1 with two molecules
–CO
in the unit cell. As for structures of trans-[Cr(CO)4(PPh3)2]
OiPr
OiPr
̅
published before, a higher symmetry than P1 is missing
iPrO
iPrO
iPrO
iPrO
P
O
Sn
O
P
O
Sn
O
Cr(CO)5
OClO3
for all structures. The molecular structure of compound 3
is shown in Figure 2. Selected interatomic distances and
angles are given in the figure caption.
+ trans-(Ph3P)2Cr(CO)4
tBu
tBu
+
OClO3
P
P
OiPr
OiPr
A
31P NMR spectrum of compound 3 in C6D6 showed
1
3
4
a signal at δ 75.3 ppm being identical with that reported
previously (Beck et al., 1994).
Scheme 2:ꢀReaction of compound 2 in the CD3CN solution.
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ꢁꢀꢀꢀ
M. Wagner et al.: [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4ꢂ
ꢂ171
110 K (Table 1). The structures were solved with direct methods using
SHELXS-97 (Sheldrick, 2008). Refinements were carried out against
F2 by using SHELXL-97 (Sheldrick, 2008). The C-H hydrogen atoms
were positioned with idealized geometry and refined using a riding
model. All non-hydrogen atoms were refined using anisotropic dis-
placement parameters. CCDC-1047815 (2) and -1047816 (3) contain the
supplementary crystallographic data for this article. These data can
be obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
to the C(1) carbon atoms at δ 170.4, 1, and δ 182.4 ppm, 4.
The low field shift of the C(1) signal, which is assigned
to compound 4, showed the absence of the transition
metal fragment. A similar trend was observed for RSnCl
[Rꢀ=ꢀ4-tBu-2,6-{P(O)(OiPr)2}2C6H2] (δ 186.7 ppm) compared
with RSn(Cl)Cr(CO)5 (δ 171.7 ppm) (Henn et al., 2011).
ThereactionaccordingtoScheme2proceedsvianucle-
ophilic attack of the kinetically labile triphenylphosphane
at the chromium center (Scheme 2). The driving force for
the formation of 3 is its low solubility in acetonitrile.
General
4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(ClO4)Cr(CO)5 (1) was prepared as
described (Wagner et al., 2013). All reactions were performed under
argon. The solvents including NMR solvents were destilled from the
appropriate drying agent and stored over molecular sieve. The NMR
tube was flame sealed. The NMR spectra were run on a Bruker DPX
300/DRX 500 or Varian Mercury spectrometer at room temperature.
Experimental section
Crystallographic details
1
NMR chemical shifs are given in parts per million. The H and 13C
Intensity data for the crystals (2, 3) were collected on an XcaliburS
CCD diffractometer (Oxford Diffraction) using Mo-Kα radiation at
NMR spectra were referenced to SiMe4 using the solvent signal
Table 1:ꢀCrystallographic data.
ꢁ
2
ꢁ
3
Empirical formula
Formula weight (g/mol)
T (K)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C45H54ClCrO15P3Snꢃ
C40H30CrO4P2
688.58
1133.93
173(2)
ꢃ
ꢃ
ꢃ
173(2)
Crystal system
Crystal size (mm)
Space group
a (Å)
monoclinic
triclinic
0.30ꢃ×ꢃ0.14ꢃ×ꢃ0.06 ꢃ
P21/c
0.50ꢃ×ꢃ0.15ꢃ×ꢃ0.08
̅
P1
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
18.2967(7)
13.3670(5)
21.9794(8)
90
104.653(4)
90
10.2390(7)
12.2624(8)
14.7020(10)
97.596(6)
106.237(6)
106.466(6)
1654.17(19)
2
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
5200.7(4)
4
Z
ρcalcd (g/cm3)
μ (mm-1)
F(000)
1.448
1.382
0.895
0.485
2320
712
θ range (°)
(hkl) ranges
2.26–25.50
-22ꢃꢃ≤ꢃꢃhꢃꢃ≤ꢃꢃ22
-16ꢃꢃ≤ꢃꢃkꢃꢃ≤ꢃꢃ16
-26ꢃꢃ≤ꢃꢃlꢃꢃ≤ꢃꢃ26
49117
2.32–25.50
-12ꢃꢃ≤ꢃꢃhꢃꢃ≤ꢃꢃ11
-14ꢃꢃ≤ꢃꢃkꢃꢃ≤ꢃꢃ13
-17ꢃꢃ≤ꢃꢃlꢃꢃ≤ꢃꢃ17
13819
Reflections collected
Completeness to θmax (%)
Independent reflections/Rint
No. of reflections observed with [Iꢃ>ꢃ2σ(I)]ꢃ
Absorption correction
99.9
9672/0.0468
7781
99.9
6167/0.0588
3876
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
Multi-scan
1.0/0.95897
595
Multi-scan
1.0/0.96412
352
T
max/Tmin
Parameter
GoF(F2)
R1(F) [Iꢃ>ꢃ2σ(I)]
1.134
0.984
0.0342
0.0516
wR2(F2) (all data)
Largest difference peak and hole (e/Å3)
CCDC number
0.0926
0.1111
1.160/-1.061
1047815
0.516/-0.441
1047816
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ꢀꢀꢀꢁ
172ꢀ ꢀM. Wagner et al.: [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4
(CD3CN 1H 1.94 ppm, 13C 1.39 ppm). The NMR spectra were referenced
to 85% H3PO4 (31P) and SnMe4 (119Sn). The IR spectra (cm-1) were meas-
ured as solids on an ATR Perkin Elmer Spectrum Two. The melting
point was measured in an open capillary on a Büchi M-560. The elec-
trospray mass spectra were run on a Thermoquest-Finnigan device
using acetonitrile solutions with a concentration of 0.1 mg/mL and
a flow rate of 10 μL/min. The experimental isotopic pattern matched
the theoretical ones.
trans-[Cr(CO)4(PPh3)2], 3:ꢁ31P{1H} NMR (C6D6, 121.49 MHz): δꢀ=ꢀ75.3;
-1
IR (ATR): ꢀ=ꢀ1873 cm (vs, CO), 1940 cm-1 (CO); ESI MS (+, CH3CN):
ꢀ
ν
+
+
+
+ +
m/zꢀ=ꢀ631.1 [M-Ph-+H +H3O ] (100%), 633.2 [M-2CO+H ] .
References
Abicht, H.-P.; Jurkschat, K.; Tzschach, A.; Peters, K.; Peters, E.-M.;
von Schnering, H. G. Synthese und Strukturuntersuchung von
zwei Stannylwolframpentacarbonylen R2SnW(CO)5 (Rꢃ=ꢃo-dimethy
laminomethyl(phenyl) bzw. o-Diphenylphosphinomethyl(phenyl)).
J. Organomet. Chem. 1987, 326, 357–368.
Al-Rafia, S. M. I.; Malcolm, A. C.; Liew, S. K.; Ferguson, M. J.; Rivard, E.
Stabilization of the heavy methylene analogues, GeH2 and SnH2,
within the coordination sphere of a transition metal. J. Am.
Chem. Soc. 2011, 133, 777–779.
Bao, J.; Geib, S. J.; Cooper, N. J. Facile displacement of cyclohexadi-
enide ligand from K[Cr(η5-C6H7)(CO)3] to give crystallographically
characterized trans-[Cr(CO)4(PPh3)2]. J. Organomet. Chem. 2001,
631, 188–192.
Barney, A. A.; Heyduk, A. F.; Nocera, D. G. Synthesis of an anionic
tridentate phosphinoborate and its reaction chemistry with
Sn(II). Chem. Commun. 1999, 2379–2380.
Baumeister, U.; Hartung, H.; Jurkschat, K.; Tzschach, A. Reactivity
and crystal and molecular structure of 5-phenyl-5-phospha-2,8-
dithia-1-stanna(II)bicyclo[3.3.01,5]octane. J. Organomet. Chem.
1986, 304, 107–114.
Beck, G.; Lappert, M. F.; Hitchcock, P. B. Synthesis of the sterically
hindered complexes [M(CO)5(CNBR2)] [Rꢃ=ꢃCH(SiMe3)2; Mꢃ=ꢃCr, Mo,
or W]. Crystal structure of [Cr(CO)5(CNBR2)]. J. Organomet. Chem.
1994, 468, 143–148.
Bennett, D. W.; Siddiquee, T. A.; Haworth, D. T.; Kabir, S. E.;
Camellia, F. K. The crystal and molecular structure of trans-
tetracarbonylbis(triphenyl-phosphine)chromium(0) in a new
unit cell: Is the trans conformer more stable than the cis?
J. Chem. Cryst. 2004, 34, 353–359.
Burt, J.; Levason, W.; Reid, G. Coordination chemistry of the main
group elements with phosphine, arsine and stibine ligands.
Coord. Chem. Rev. 2014, 260, 65–115.
[2,6-Bis(di-iso-propoxyphosphonyl)-4-tert-butyl]
phenyl}tin triphenylphosphane perchlorate chromium
pentacarbonyl, [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)
Cr(CO)5]ClO4 (2)
Triphenylphosphane (51 mg, 0.19 mmol) was added to a solution of
[4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(ClO4)Cr(CO)5] (170 mg, 0.19 mmol) in
CH3CN (3 mL). Afer addition of toluene, colorless crystals were grown
at 4°C, which were washed with toluene and dried in vacuo. Yield
1
(86 mg, 39%); mp 138°C (decomp); H NMR (CD3CN, 300.13 MHz):
3
1
3
1
δꢀ=ꢀ1.11 [d, J(1H- H)ꢀ=ꢀ6.2 Hz, 12H, CH(CH3)2], 1.29 [d, J(1H- H)ꢀ=ꢀ6.2 Hz,
12H, CH(CH3)2], 1.41 [s, 9H, C(CH3)3], 4.36–4.55 [not resolved, ν1/2ꢀ=ꢀ26 Hz,
4H, CH(CH3)2], 7.28 (br t, Jꢀ=ꢀ7.5 Hz, 6H, Ph3P), 7.42 (br t, Jꢀ=ꢀ7.6 Hz, 6H,
Ph3P), 7.54 [br t, J(1H- H)ꢀ=ꢀ7.6 Hz, 3H, para-Ph3P], 8.10 [pseudo-d,
3
1
3J(31P- H)ꢀ=ꢀ14.6 Hz, 2H, CHaryl]; 13C{1H} NMR (CD3CN, 75.47 MHz): δꢀ=ꢀ23.8–
1
23.9 [not resolved, CH(CH3)2], 23.9–24.1 [not resolved, CH(CH3)2], 31.2
[s, C(CH3)3], 36.1 [s, C(CH3)3], 76.2 [complex pattern, CH(CH3)2], 130.4
31
1
31
3
31
[d, J(13C- P)ꢀ=ꢀ9.4 Hz, CPPh ], 132.4 [dd, J(13C- P)ꢀ=ꢀ188 Hz, J(13C- P)ꢀ=ꢀ
3
18.9 Hz, C2,6aryl], 132.7 (br s, para-CPPh ), 134.0 (dd, 2J(13C- P)ꢀ=ꢀ13.8
31
3
4
31
31
Hz, J(13C- P)ꢀ=ꢀ4.4 Hz, C3,5aryl], 134.8 [d, J(13C- P)ꢀ=ꢀ13.8 Hz, CPPh ], 157.0
3
3
31
[t, J(13C- P)ꢀ=ꢀ12.0 Hz, C4aryl], 168.4 (complex pattern, C1aryl), 219.0 [s,
2J(13C-117/119Sn)ꢀ=ꢀ116 Hz, COcis], 225.2 (s, COtrans), ipso-CPPh not found;
3
31P{1H} NMR (CD3CN, 121.49 MHz): δꢀ=ꢀ28.5 [s, J(31P-117/119Sn)ꢀ=ꢀ168 Hz], 1.4
ꢀ
ν
(s, ν1/2ꢀ=ꢀ95 Hz); IR (ATR): ꢀ=ꢀ2981 (CH), 2052 (CO), 1974 (CO), 1946
(CO), 1921 (CO), 1230, 1174, 1148, 1129, 1084, 983. Although single crys-
talline material was used for elemental analysis (under aerobic con-
ditions), the values obtained differed by approximately 2%–6% from
the calculated values.
El Ezzi, M.; Kocsor, T.-G.; D’Accriscio, F.; Madec, D.; Mallet-Ladeira, S.;
Castel, A. Iron complexes with stabilized germylenes: syntheses
and characterizations. Organometallics 2015, 34, 571–576.
Freitag, S.; Henning, J.; Schubert, H.; Wesemann, L. Phosphastan-
nirane: a phosphorus/tin(II) Lewis pair that undergoes alkyne and
alkene addition. Angew. Chem. Int. Ed. 2013a, 52, 5640–5643.
Freitag, S.; Krebs, K. M.; Henning, J.; Hirdler, J.; Schubert, H.;
Wesemann, L. Stannylene-based Lewis pairs. Organometallics
2013b, 32, 6785–6791.
Storage of [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]
ClO4 (2)
A
sample of [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4 in
CD3CN was stored in a sealed NMR tube for 10 weeks during which a
few yellow crystals precipitated. The solution was checked NMR spec-
troscopically and the crystals were identified as trans-[Cr(CO)4(PPh3)2]
via single crystal X-ray diffraction analysis.
Ghadwal, R. S.; Azhakar, R.; Pröpper, K.; Holstein, J. J.; Dittrich, B.;
Roesky, H. W. N-heterocyclic carbene stabilized dichlorosilylene
transition-metal complexes of V(I), Co(I), and Fe(0). Inorg. Chem.
2011, 50, 8502–8508.
31P{1H} NMR (CD3CN, 81.02 MHz):ꢁδꢀ=ꢀ55.7 (s, not assigned, inte-
gral 12), 37.3 [s, J(31P-117/119Sn)ꢀ=ꢀ125/130 Hz, 4, integral 41], 30.3 [bs,
J(31P-117/119Sn)ꢀ=ꢀ180 Hz, 1, integral 38], 2.0 (bs, PPh3, integral 9); 13C NMR Henn, M.; Deáky, V.; Krabbe, S.; Schürmann, M.; Prosenc, M. H.;
(CD3CN, gHMBC 125.67/499.78 MHz): δꢀ=ꢀ182.4 (C1aryl, 4), 170.4 (C1aryl, 1),
134.3 (C2,6aryl, 4), 133.5 (C2,6aryl, 4); 1H NMR (CD3CN, 499.79 MHz, signals
that are not superimposed): δꢀ=ꢀ8.13 (br pseudo-d, CHaryl, 1, integral
0.92), 7.97 (pseudo-d, CHaryl, 4, integral 1.08); 119Sn{1H} NMR (CD3CN,
111.92 MHz): δꢀ=ꢀ-263 (bs, not assigned).
Herres-Pawlis, S.; Mahieu, B.; Jurkschat, K. Heteroleptic orga-
nostannylenes and an organoplumbylene bearing phosphorus-
containing pincer-type ligands – structural variations and
insights into the configurational stability. Z. Anorg. Allg. Chem.
2011, 637, 211–223.
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M. Wagner et al.: [4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4ꢂ
ꢂ173
Hupf, E.; Lork, E.; Mebs, S.; Beckmann, J. Intramolecularly coordi-
nated (6-(diphenylphosphino)acenaphth-5-yl)stannanes. Repul-
sion vs attraction of P- and Sn-containing substituents in the
peri positions. Organometallics 2014, 33, 2409–2423.
Izod, K. Heavier group 14 complexes with anionic P-donor ligands.
Coord. Chem. Rev. 2012, 256, 2972–2993.
Jurkschat, K.; Tzschach, A.; Meunier-Piret, J.; van Meerssche, M.
Crystal structure of pentacarbonyl-5-phenyl-5-phospha-
2,8-dithia-1-stannabi-cyclo[3.3.01,5]octanechromium(0)pyri-
dine. J. Organomet. Chem. 1988, 349, 143–147.
Sheldrick, G. M. A short history of SHELX. Acta Cryst. 2008, A64,
112–122.
Swarnakar, A. K.; McDonald, S. M.; Deutsch, K. C.; Choi, P.;
Ferguson, M. J.; McDonald, R.; Rivard, E. Application of the
donor-acceptor concept to intercept low oxidation state group
14 element hydrides using a Wittig reagent as a Lewis base.
Inorg. Chem. 2014, 53, 8662–8671.
Thimer, K. C.; Al-Rafia, S. M. I.; Ferguson, M. J.; McDonald, R.;
Rivard, E. Donor/acceptor stabilization of Ge(II) dihydride.
Chem. Commun. 2009, 7119–7121.
MacDonald, E.; Doyle, L.; Burford, N.; Werner-Zwanziger, U.;
Decken, A. Stannylphosphonium cations. Angew. Chem. Int. Ed.
2011, 50, 11474–11477.
Wagner, M.; Henn, M.; Dietz, C.; Schürmann, M.; Prosenc, M. H.;
Jurkschat, K. Chromium pentacarbonyl-substituted
organotin(II) cation stabilized by p-dimethylaminopyridine
or triphenylphosphane oxide. Organometallics 2013, 32,
2406–2415.
MacDonald, E.; Doyle, E.; Chitnis, S. S.; Werner-Zwanziger, U.;
Burford, N.; Decken, A. Me3P complexes of p-block Lewis acids
+
2+
SnCl4, SnCl3 and SnCl2 . Chem. Commun. 2012, 48, 7922–7924. Weicker, S. A.; Dube, J. W.; Ragogna, P. J. Synthesis of zwitteri-
Objartel, I.; Ott, H.; Stalke, D. Low-temperature NMR and crystal
structure analyses of a hemilabile tin complex. Z. Anorg. Allg.
Chem. 2008, 634, 2373–2379.
onic group 14 centered complexes: traditional coordination
and unusual insertion chemistry. Organometallics 2013, 32,
6681–6689.
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