Article
Inorganic Chemistry, Vol. 50, No. 4, 2011 1267
(0.055 g, 0.12 mmol) was added to a 2 mL aqueous solution of
KAu(CN)4 (0.036 g, 0.11 mmol). Slow evaporation of the
solution yielded colorless, X-ray quality crystals of [AsPh4]-
[Au(CN)4] after 10 days, which were vacuum-filtered and air-
dried. Yield: 0.044 g, 92%. Anal. Calcd. for C28H20N4AsAu:
C 49.14%, H 2.95%, N 8.19%. Found: C 49.13%, H 2.88%, N
8.29%. IR (ATR): 3160(w), 3085(w), 3060(w), 3026(w), 2658(w),
2998(w), ν(CN): 2192(vw), 2180(vw), 1558(w), 1484(m), 1439(st),
1341(mw), 1310(mw), 1189(mw), 1162(w), 1081(st), 1023(mw),
Synthesis of [Ni(en)3][Au(CN)4]2 (7). To an 2 mL aqueous
solution of nickel(II) perchlorate, Ni(ClO4)2 6H2O, (0.035 g,
3
0.096 mmol) 3 mL of an aqueous ethylenediamine (en) stock
solution (0.1 M, 0.3 mmol) was added, resulting in a purple
solution. A 2 mL aqueous solution of KAu(CN)4 (0.066 g,
0.19 mmol) was added to this solution, which did not cause a
change in color or formation of a precipitate; the resultant
solution was covered with parafilm. After four days, large,
purple, X-ray quality crystals of [Ni(en)3][Au(CN)4]2 were re-
covered by vacuum-filtration and subsequently air-dried. Yield:
0.047 g, 58%. Anal. Calcd. for C14H24N14Au2Ni: C 19.99%,
H 2.88%, N 23.32%. Found: C 20.30%, H 2.69%, N 23.57%.
IR (ATR): 3341(m), 3291(m), 2960(w), 2895(w) ν(CN): 2185(w),
2176(w), 1604(m), 1579(m), 1467(w), 1327(w), 1286(w), 1098(m),
997(st), 922(w), 843(w) cm-1
.
Synthesis of [N(PPh3)2][Au(CN)4] (3). Dropwise addition
of bis(triphenylphosphine)iminium chloride, [N(PPh3)2]Cl,
(0.063 g, 0.11 mmol) in a 6 mL 67% v/v methanol/water solution
to a 2 mL aqueous solution of KAu(CN)4 (0.036 g, 0.11 mmol)
resulted in a white precipitate, which was dissolved upon further
addition of 20 mL methanol. X-ray quality colorless crystals of
[N(PPh3)2][Au(CN)4] formed during slow evaporation of the
solution (for about two weeks); they were then vacuum-filtered
and air-dried. Yield: 0.034 g, 54%. Anal. Calcd. for C40H30-
N5AuP2: C 57.22%, H 3.60%, N 8.34%. Found: C 57.22%, H
3.46%, N 8.20%. IR (ATR): 3060(w), 3017(w), 2995(w), ν(CN):
2179(vw), 1588(mw), 1480(mw), 1438(m), 1334(m), 1302(m),
1181(mw), 1159(w), 1114(st), 998(m), 968(w), 928(w), 854(w),
1023(st), 967(st) cm-1
.
Synthesis of [Co(NH3)6][Au(CN)4]3 4H2O (8). A 3 mL aque-
3
ous solution of hexaamminecobalt(III) chloride, [Co(NH3)6]Cl3,
(0.026 g, 0.14 mmol) was added to a 4 mL aqueous solution of
KAu(CN)4 (0.102 g, 0.300 mmol), which did not alter the color of
the initial orange solution. The solution was covered with para-
film and yielded orange, X-ray quality crystals of [Co(NH3)6]-
[Au(CN)4]3 4H2O after five weeks, which were then vacuum-
3
filtered and air-dried. Yield: 0.065 g, 57%. Anal. Calcd. for
C12H26N18Au3CoO4: C 12.68%, H 2.31%, N 22.19%. Found:
C 12.87%, H 2.06%, N 21.91%. IR (KBr): 3653(m), 3644(m),
3229(s,br), 3174(s,br), ν(CN): 2191(m), 2189(m), 1600(st), 1349(m),
753(m), 721(st), 691(st) cm-1
.
Synthesis of [Co(phen)3][Au(CN)4]2 (4). A 2 mL 50% v/v
methanol/water solution of 1,10-phenanthroline (phen) (0.036
g, 0.18 mmol) was added to a 3 mL 50% v/v methanol/water
1325(st), 1259(w), 987(w), 822(st), 473(m), 458(m) cm-1
.
Synthesis of [Hdabco][Au(CN)4] (9). Adding a 3 mL aqueous
solution of [Hdabco]Cl (0.032 g, 0.22 mmol) to a 5 mL aqueous
solution KAu(CN)4 (0.068 g, 0.20 mmol) resulted in a colorless
solution. The solution was covered with parafilm and colorless
X-ray quality crystals of [Hdabco][Au(CN)4] were deposited,
which were filtered and air-dried. Retention of the filtrate
and further slow evaporation yielded additional crystals of
[Hdabco][Au(CN)4]. Yield: 0.049 g, 59%. Anal. Calcd. for
C10H13N6Au: C 29.00%, H 3.16%, N 20.29%. Found: C
29.14%, H 3.00%, N 19.83%. IR (KBr): 3054(w), 2958(w),
2890(w), 2678(w), ν(CN): 2196(w), 2184(w), 2175(w), 1461(m),
1326(st), 1175(st), 1088(st), 1057(st), 1014(st), 941(m), 837(m),
solution of cobalt(II) perchlorate, Co(ClO4)2 6H2O, (0.023 g,
3
0.063 mmol) resulting in an orange solution. A 10 mL 50% v/v
methanol/water solution of KAu(CN)4 (0.068 g, 0.20 mmol)
was then added to the solution, which resulted in forma-
tion of orange crystals of [Co(phen)3][Au(CN)4]2 after 1 day,
which were then vacuum-filtered and air-dried. Yield:
0.055 g, 73%. Anal. Calcd. for C34H24N14Au2Co: C 43.98%,
H 2.01%, N 16.32%. Found: C 43.88%, H 1.78%, N 15.96%.
IR (KBr): 3436(m), 3128(w), 3067(m), 3020(w), 2943(w),
2836(w), ν(CN): 2199(w), 2190(w), 2185(w), 2180(w), 1626(m),
1587(m), 1519(st), 1426(st), 1343(m), 1225(m), 1144(m), 1104(m),
1024(w), 847(st), 786(m), 725(st), 644(m), 473(m), 458(st),
798(st), 772(m), 626(st), 602(st), 458(m) cm-1
.
419(st) cm-1
.
X-ray Crystallographic Analysis. Crystallographic data for all
compounds are collected in Table 1. X-ray crystallographic
analysis was performed by mounting crystals onto glass fibers
using epoxy adhesive and then placing them into a cold nitrogen
stream. The diffraction data was collected using a Bruker
SMART APEX II CCD area detector diffractometer positioned
6.0 cm from the crystal. The X-ray source was a monochro-
Synthesis of [Mn(terpy)2][Au(CN)4]2 (5). A 3 mL 50% v/v
methanol/water solution of 2,20;60,200-terpyridine (terpy) (0.024
g, 0.10 mmol) was added to a 2 mL 50% v/v methanol/water
solution of manganese(II) chloride, MnCl2 6H2O, (0.019 g,
3
0.052 mmol) resulting in a yellow solution. A 2 mL aqueous
solution of KAu(CN)4 (0.069 g, 0.20 mmol) was then added to
the solution without any color change. The yellow solution was
allowed to slowly evaporate and yellow, X-ray quality crystals
of [Mn(terpy)2][Au(CN)4]2 were deposited after six days, which
were then vacuum-filtered and air-dried. Yield: 0.024 g, 43%.
Anal. Calcd. for C38H22N14Au2Mn: C 40.62%, H 1.97%, N
17.45%. Found: C 40.62%, H 1.86%, N 17.07%. IR (KBr):
3113(w), 3062(w), 3054(w), 3031(w), 3021(w), ν(CN): 2188(w),
1572(m), 1595(st), 1475(m), 1450(st), 1318(m), 1248(m), 1162(m),
1115(m), 1108(m), 1099(st), 1086(st), 1014(m), 775(st), 651(m),
˚
mated Mo KR radiation (λ = 0.71073 A) from a rotating anode
with a mirror focusing apparatus operated at 1.2 kW (50 kV,
24 mA). The frames were collected with a scan width of 0.5° in ω
and were integrated with the Bruker SAINT software. Correc-
tions for absorption were made by SADABS.
The structure of each compound was solved using the Sir 92
routine and expanded using Fourier techniques within the
CRYSTALS38 software package. Hydrogen atoms were placed
geometrically, oriented with probable hydrogen bonds, and
refined with a riding model to link the shifts of the respective
carbon and nitrogen atoms. The crystal of 6 was of poor quality
and twinned and was therefore analyzed using twinning decon-
volution software. Diagrams were made using Ortep-3 (version
2.02)39 and POV-Ray (version 3.6.0).40
624(m), 458(st) cm-1
.
Synthesis of trans-[Co(en)2Cl2][Au(CN)4] (6). A 5 mL 80% v/v
methanol/water solution of trans-(bis-ethylenediamine) cobalt-
(III) chloride, trans-[Co(en)2Cl2]Cl, (0.030 g, 0.11 mmol) was
added to a 5 mL 80% v/v methanol/water solution of KAu-
(CN)4 (0.035 g, 0.10 mmol). The solution was covered with
parafilm. After four days, X-ray quality, green crystals of
trans-[Co(en)2Cl2][Au(CN)4] had formed, and were vacuum-
filtered and air-dried. Yield: 0.030 g, 53%. Anal. Calcd. for
C8H16N8AuCl2Co: C 17.44%, H 2.93%, N 20.33%. Found: C
17.65%, H 2.58%, N 20.17%. IR (KBr): 3443(m), 3301(st),
3281(st), 3237(st), 3135(m), 3126(m), 3001(w), 2986(w), 2959-
(mw), ν(CN): 2186(mw), 1584(st), 1450(w), 1282(m), 1218(st),
Nitrogen-15 CP MAS NMR. 15N {1H} cross-polarization
(CP) magic-angle spinning (MAS) NMR was acquired on a
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(40) Fenn, T. D.; Ringe, D.; Petsko, G. A. J. Appl. Crystallogr. 2003, 36,
944–947.
1124(st), 1054(st), 1003(m), 794(w), 589(m) cm-1
.