796 Organometallics, Vol. 28, No. 3, 2009
Partyka et al.
) 2.3 Hz), 129.92 (J ) 7.6 Hz), 128.53 (s), 127.11 (d, J ) 7.7
Hz), 125.89 (s), 125.38 (s), 124.88 (s), 37.67 (d, J ) 32.8 Hz),
34.84 (d, J ) 35.1 Hz), 30.74 (d, J ) 2.3 Hz), 30.54 (d, J ) 5.4
Hz), 29.56 (s), 28.71 (d, J ) 2.3 Hz), 26.90 (s), 26.75 (d, J ) 6.9
Hz), 26.38 (s), 26.24 (s), 25.69 (d, J ) 15.3 Hz), 20.99 (s) ppm.
31P NMR (C6D6): δ 35.1 (s) ppm. IR (KBr, cm-1): 2058 (νas: NdNdN,
vs), 1288 (νs: NdNdN, w) cm-1. Anal. Calcd for C25H33AuN3P: C, 49.76;
H, 5.51; N, 6.96. Found: C, 49.79; H, 5.33; N, 6.68.
Experimental
Abbreviations: SIPr: 1,3-bis(2,6-diisopropylphenyl)-4,5-dihy-
droimidazolin-2-ylidene; XPhos: 2′,4′,6′-triisopropyl-2-biphenyl)-
dicyclohexylphosphine.
(SIPr)AgCl17 and (SIPr)AuCl18 were synthesized according to
literature methods. The phosphine-ligated gold(I) chlorides used
to synthesize 1-3 were prepared according to the literature
procedure.19 All solvents and reagents were used as received.
Microanalyses (C, H, and N) were performed by Quantitative
Technologies, Inc. NMR spectra (1H, 13C{1H}, and 31P{1H}) were
recorded on a Varian AS-400 spectrometer operating at 399.7,
161.8, and 100.5 MHz, respectively.
[(Xphos)AuN3](3).In8mLoftoluenewassuspended[(PCy2(2′,4′,6′-
triisopropylbiphenyl))AuCl] (51 mg, 0.072 mmol), and to this
suspension was added thallium(I) acetylacetonate (36 mg, 0.12
mmol). The resultant suspension was stirred under nitrogen for 48 h.
The suspension was then filtered though celite yielding a clear
filtrate. To the filtrate was added 30 µL (0.23 mmol) of trimeth-
ylsilyl azide and 2 mL of methanol, which, upon addition, formed
a white precipitate. The suspension was then stirred for 16 h. The
suspension was filtered through celite, resulting in a clear filtrate,
which was rotary evaporated to near dryness and triturated with
pentane. This resulted in the formation of a white crystalline
precipitate. The white solid was collected, washed three times with
50 mL portions of pentane, and vacuum-dried. Yield: 40 mg (77%).
1H NMR (C6D6): δ 7.51 (s, 2H, 2′,4′,6′-triisopropylbiphenyl),
7.14-7.18 (m, 1H, 2′,4′,6′-triisopropylbiphenyl), 6.94-7.05 (m, 3H,
2′,4′,6′-triisopropylbiphenyl), 3.32 (sep, 1H, CH(CH3)2, J ) 6.8
Hz), 2.38 (sep, 2H, CH(CH3)2, J ) 6.8 Hz), 1.61 (d, 6H, CH(CH3)2,
J ) 6.8 Hz), 1.50 (d, 6H, CH(CH3)2, J ) 6.8 Hz), 1.04 (d, 6H,
CH(CH3)2, J ) 6.4 Hz), 0.79-1.80 (m, 22H, C6H11) ppm. 13C NMR
(C6D6): δ 150.78 (s), 147.86 (d, J ) 14.5 Hz), 146.01 (s), 135.56
(d, J ) 6.1 Hz), 133.72, (d, J ) 7.6 Hz), 131.94 (d, J ) 3.1 Hz),
130.32 (d, J ) 2.3 Hz), 128.44 (s), 127.03 (d, J ) 6.8 Hz), 121.88
(s), 37.04 (s), 36.70 (s), 34.88 (s), 31.38 (s), 31.05 (d, J ) 2.3 Hz),
29.94 (s), 26.97 (d, J ) 13.7 Hz), 26.59 (d, J ) 30.0 Hz), 25.91
(s), 25.64 (s), 24.24 (s), 22.97 (s) ppm. 31P NMR (C6D6): δ 34.1
(s) ppm. IR (KBr, cm-1): 2056 (νas: NdNdN, vs), 1265 (νs: NdNdN, w)
cm-1. Anal. Calcd for C33H49AuN3P: C, 55.38; H, 6.90; N, 5.87.
Found: C, 55.60; H, 7.14; N, 5.61.
[(SIPr)AuN3] (4) (Method A). In 5 mL of degassed CH2Cl2
was dissolved recrystallized (SIPr)AuCl (170 mg, 0.27 mmol), and
to this was added 1.1 equiv of thallium(I) acetylacetonate (91 mg,
0.30 mmol). A white material immediately precipitated. The
suspension was stirred for 1 h and filtered through Celite. To the
filtrate via syringe was added trimethylsilyl azide (0.04 mL), and
a milky white solid precipitated. This suspension was stirred for 2
min, and 0.05 mL methanol was added by syringe. This suspension
was stirred for 6 h, filtered, the solvent removed by rotary
evaporation, and the solid triturated with pentane, collected, and
dried. Yield: 147 mg (86%). 1H NMR (CDCl3): δ 7.43 (t, 2H, J )
7.6 Hz), 7.24 (d, 4H, J ) 7.6 Hz), 4.05 (s, 4H), 3.02 (sep, 4H, J )
6.8 Hz), 1.39 (d, 12H, J ) 7.2 Hz), 1.33 (d, 12H, J ) 7.2 Hz)
ppm. 13C NMR (C6D6): δ 194.66 (s, C carbene), 146.46 (s, CH
aromatic), 133.87 (s, CH aromatic), 130.10 (s, CH aromatic), 124.65
(s, CH aromatic), 53.45 (s, CH imidazole), 28.96 (s, CH(CH3)2),
25.06 (s, CH(CH3)2), 24.10 (s, CH(CH3)2) ppm. IR (KBr, cm-1):
2048 (νas: NdNdN, vs), 1274 (νs: NdNdN, m) cm-1. Anal. Calcd. for
C27H38AuN5: C, 51.51; H, 6.08; N, 11.12. Found: C, 52.06; H, 6.22;
N, 10.59.
Caution! Metal azide complexes are potentially explosiVe, and
appropriate precautions should be taken. Although we haVe not
experienced incidents with the present compounds, metal azides
should be protected from heat and percussion. Reaction with acids
may release toxic hydrazoic acid. ProtectiVe eyewear and protectiVe
clothing are essential.
[(PCy2(2-biphenyl))AuN3] (1). In 20 mL of toluene was
suspended [(PCy2(o-biphenyl))AuCl] (151 mg, 0.26 mmol), and
to this suspension was added thallium(I) acetylacetonate (97 mg,
0.32 mmol). The resultant suspension was stirred under nitrogen
for 24 h. The suspension was then filtered though celite, yielding
a clear filtrate. To the filtrate was added 70 µL (0.53 mmol) of
trimethylsilyl azide and 4 mL of methanol, which, upon addition,
formed a white precipitate. The suspension was then stirred for
16 h. The suspension was filtered through celite, resulting in a clear
filtrate, which was evaporated to near dryness and then triturated
with pentane. This resulted in the formation of a white crystalline
precipitate. The white solid was collected, washed three times with
50-mL portions of pentane, and vacuum-dried. Yield: 133 mg
1
(87%). H NMR (C6D6): δ 7.66 (td, 1H, 2′-biphenyl, J ) 1.6, 7.2
Hz), 7.52 (t, 2H, 2′-biphenyl, J ) 7.6 Hz), 7.13 (dd, 2H, 2′-biphenyl,
J ) 1.2, 8.0 Hz,), 6.95-7.08 (m, 4H, 2′-biphenyl), 0.71-1.72 (m,
22H, C6H11) ppm. 13C NMR (C6D6): δ 132.36-132.57 (m), 130.38
(d, J ) 2.1 Hz), 129.41 (s), 127.39 (d, J ) 6.4 Hz), 127.14 (d, J
) 7.8 Hz), 36.23 (d, J ) 33.6 Hz), 30.73 (s), 29.12 (s), 26.58 (s),
26.44 (d, J ) 5.1 Hz), 26.26 (s), 25.34 (s) ppm. 31P NMR (C6D6):
δ 37.8 (s) ppm. IR (KBr, cm-1): 2055 (νas: NdNdN, vs), 1286
(νs:
w) cm-1. Anal. Calcd for C24H31AuN3P: C, 48.90; H,
5.30; N, 7.13. Found: C, 49.17; H, 5.53; N, 6.78.
NdNdN,
[(PCy2(2′-methyl-2-biphenyl))AuN3] (2). In 8 mL of toluene
was suspended [(PCy2(2′-methylbiphenyl))AuCl] (87 mg, 0.15
mmol), and to this suspension was added thallium(I) acetylacetonate
(63 mg, 0.21 mmol). The resultant suspension was stirred under
nitrogen for 48 h. The suspension was then filtered though celite,
yielding a clear filtrate. To the filtrate was added 40 µL (0.30 mmol)
of trimethylsilyl azide and 2 mL of methanol, which, upon addition,
formed a white precipitate. The suspension was then stirred for
16 h. The suspension was filtered through celite, resulting in a clear
filtrate, which was rotary evaporated to near dryness and triturated
with pentane. This resulted in the formation of a white crystalline
precipitate. The white solid was collected, washed three times with
50-mL portions of pentane, and vacuum-dried. Yield: 73 mg (82%).
1H NMR (C6D6): δ 7.62-7.71 (m, 2H, 2′-methylbiphenyl), 7.31
(td, 1H, 2′-methylbiphenyl, J ) 1.6, 7.2 Hz,), 6.94-7.22 (m, 4H,
2′-methylbiphenyl), 6.87-6.92 (m, 1H, 2′-methylbiphenyl), 1.98
(s, 3H, CH3), 0.68-1.82 (m, 22H, C6H11) ppm. 13C NMR (C6D6):
149.70 (d, J ) 13.0 Hz), 140.59 (d, J ) 5.2 Hz), 135.77 (s), 132.45
(d, J ) 7.6 Hz), 132.23 (d, J ) 3.8 Hz), 131.28 (s), 130.83 (d, J
[(SIPr)AuN3] (4) (Method B). SIPrAuCl (142 mg, 0.23 mmol)
was suspended in benzene (10 mL), and to this suspension was
added 1.05 equiv (40 mg, 0.24 mmol) of silver(I) acetate. The
mixture was stirred for 2 h, and azidotrimethylsilane (3 equiv, 0.09
mL, 0.67 mmol) was added directly by syringe. The resultant
mixture was stirred 12 h, and filtered, and the solvent was removed
by rotary evaporation. This yielded only a small amount of product.
The insoluble material (the material initially filtered out of the
product suspension in benzene) was further extracted with dichlo-
romethane and filtered. After the dichloromethane was removed
by rotary evaporation, the residue was triturated with pentane. The
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