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A. Alsalme et al. / Polyhedron 88 (2015) 1–5
Labs. Ltd. grade). Hexane, acetone and methanol were used as com-
mercially available (BDH-Analar grade) and kept over molecular
sieves. The compounds [AuAC„CAPh]n and [AuAC„CABut]n were
made as described by Coates and Parkin [18] and detailed below.
revealed the composition {PPN+[(N„CAAuAC„CABut)]ꢁꢀH2O}
(C43H41AuN2OP2), m.p. 135 °C. Compound 2 is isolated containing
one molecule of water per formula unit. Elemental analysis: Found
(calc.): %C: 59.84 (60.00),%H: 4.58 (4.76),%N: 3.26 (3.26), FTIR:
m
(max) cmꢁ1 (KBr disk) 1283, 1261 (s, P2@N), 1114 (s, PAC),
2137 (m, C„N), 1983 (vw, C„C) cmꢁ1
.
Syntheses of [Au(C„CAPh)]n and [Au(C„CABut)]n. An aqueous
solution of KBr (4.5 g, 3.78 mmol) was added to an aqueous-
acetone solution (1:1 ratio) of HAuCl4 (3.0 g of HAuCl4ꢀxH2O, 51%
Au, 7.77 mmol). A clear deep red solution was obtained. The
mixture was cooled at 10 °C with water/ice and then the resulting
solution was treated dropwise with a fresh aqueous solution of SO2
until the color of the solution became light red, and was left
stirring for 5 min without further addition. Next, an aqueous
solution of SO2 was added dropwise followed by a color change to
pale-yellow. Subsequent addition of acetylene (7.77 mmol,
HC„CAPh: 0.850 mL, HC„CABut: 0.955 mL) and sodium acetate
(6.37 g, 7.77 mmol) led to the formation of an off-white precipitate
within 1 h. The precipitate was separated by filtration and washed
several times with water, ethanol and cold acetone, yielding
[Au(C„CAPh)]n (2.20 g, 95%), m.p. 150 °C (decomp.), IR as KBr
The overall equation of formation for compound 2 is as follows:
PPNClþKCBNþ1=n½AuACBCAButꢂn!KClþPPNþ½NBCAAuACBCAButꢂꢁ
The elemental analyses were performed by using a Perkin Elmer
Series II-2400 analyzer and the FT-IR spectrum was recorded on a
Thermo Scientific Nicolet iS10.
The excitation and emission spectra were recorded at room
temperature using a Shimadzu RF-5301PC spectrofluoriphotome-
ter equipped with a solid-state sample holder. The excitation spec-
trum was recorded by constantly monitoring the emission
spectrum at the wavelength of most intense luminescence while
scanning the excitation wavelength from 220 to 400 nm. The exci-
tation spectrum has been corrected for the response of the detector
and light source.
Single crystals of C48H43AuN2O2P2 (compound 1) and C43H41-
AuN2OP2 (compound 2) were collected from the synthetic batches.
A suitable crystal was selected and measured on a Bruker APEX-II
CCD diffractometer. Each crystal was kept at 153.2 K during data
collection. Using Olex2 [19] the structures were solved with the
Superflip [20–22] structure solution program by Charge Flipping
and refined with the SHELXL [23] refinement package, using Least
Squares minimization (see Tables 1 and 2).
disc:
m(
C„C) 1962 cmꢁ1, or [Au(C„CABut)]n (2.00 g, 92%), m.p.
C„C) 1960 cmꢁ1
170 °C (decomp.), IR as KBr disc:
m
(
.
The new compound PPN+[N„CAAuAC„CAPh]ꢁ (compound 1)
has been synthesized as follows: Gold(I) phenylacetylide,
[AuAC„CAPh]n (0.298 g, 1 mmol) was added to a clear solution
of bis(triphenylphosphane)iminium chloride, [N(PPh3)2]+Clꢁ
(0.574 g, 1 mmol) in methanol (30 mL). While stirring for 30 min
a clear solution was formed, and subsequently potassium cyanide
(0.065 g, 1 mmol) was added which dissolved within 10 min. After
20 min a yellow solid precipitated. The suspension was evaporated
to dryness and the residue was extracted with acetone (20 mL). A
grey precipitate was formed which was filtered off (KCl, 0.073 g,
97%). To the remaining clear solution hexane (35 mL) was added,
and a crystalline material was collected in high yield (95%,
0.890 g). A single-crystal X-ray diffraction analysis revealed the
composition {PPN+[(N„CAAuAC„CAPh)]ꢁꢀH2O(acetone)} (C48-
H43AuN2O2P2), m.p. 120 °C. Elemental analysis: Calc. for C48H43-
AuN2P2O2: C, 61.41; H, 4.62; N, 2.98. Found: C, 63.15; H, 4.60; N,
3.15%. The found%C is 1.7% higher than calculated; this is not
understood and is tentatively ascribed to an experimental aberra-
tion, as the crystal batch appears homogeneous, and the XRD anal-
ysis (vide infra), clearly shows one acetone in the lattice. Part of the
recrystallized precipitate, when dried at 100 °C for 1 h, gave a
white solid without solvent molecules in the crystal lattice analyz-
ing for [(N„CAAuAC„CAPh)]ꢁPPN+ (C45H35AuN2P2), m.p. 132 °C,
Found (Calc.): C, 62.31 (62.65); H, 4.18 (4.06); N, 3.00(2.25)%. FTIR:
3. Results and discussion
3.1. Synthesis and characterization
The two new compounds appeared to crystallize with lattice
solvents, i.e. water and acetone for compound 1, and only water
Table 1
Crystal data and structure refinement for compound 1.
CCDC number
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
1030371
48H43AuN2O2P2
938.75
153(1)
monoclinic
P21/c
9.8763(3)
18.6454(6)
22.8316(7)
90
C
b (Å)
c (Å)
m
(max) cmꢁ1 (as KBr disk) 1282, 1262 (s, P2@N), 1114 (s, P–C),
a
(°)
2139 (m, C„N), 2113 (w, C„C) cmꢁ1. The schematic equation of
b (°)
97.3149(17)
90
4170.2(2)
4
1.495
3.645
formation reads:
PPNClþKCBNþ1=n½AuACBCAPhꢂn!KClþPPNþ½NBCAAuACBCAPhꢂꢁ
c
(°)
Volume (Å3)
Z
Calculated density (mg mmꢁ3
)
)
The new compound PPN+[N„CAAuAC„CABut]ꢁ (compound 2)
has been synthesized as follows: Gold t-butylacetylide (3,3-dim-
ethylbutynylgold) [AuC„CABut]n (0.278 g, 1 mmol) was added to
Absorption coefficient (mmꢁ1
F(000)
1880.0
Crystal size (mm3)
Radiation
0.411 ꢃ 0.243 ꢃ 0.01
Mo Ka (k = 0.71073)
a
clear solution of bis(triphenylphosphane)iminium chloride,
2H
range for data collection (°)
4.698–52.77
[N(PPh3)2]+Clꢁ (0.574 g, 1 mmol) in methanol (30 mL). While stir-
ring for 30 min a clear solution was formed, and subsequently
potassium cyanide (0.065 g, 1 mmol) was added which dissolved
within 10 min. After 20 min a white solid precipitated. The suspen-
sion was evaporated to dryness and the residue was extracted with
acetone (25 mL). A grey precipitate was formed which was filtered
off (KCl, 0.070 g, 93%). To the remaining clear solution n-hexane
(40 mL) was added, and a crystalline material was collected in high
yield (90%, 0.774 g). A single-crystal X-ray diffraction analysis
Index ranges
ꢁ11 6 h 6 12, ꢁ23 6 k 6 23,
ꢁ24 6 l 6 28
Reflections collected
30964
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
8499 [Rint = 0.0382, Rsigma = 0.0393]
8499/0/501
1.161
R1 = 0.0420, wR2 = 0.0818
R1 = 0.0531, wR2 = 0.0850
1.43/ꢁ1.51
Final R indexes [I P 2
Final R indexes (all data)
Largest difference in peak/hole
(e Åꢁ3
r(I)]
)