Notes
Organometallics, Vol. 18, No. 3, 1999 453
2
apparently similar to that of H+. However, for reasons
that are not understood at this time, the formation of
benzidine, the favored product with H+, is not observed
with [Ph3PAu]+. Additionally, the gold semidine prod-
ucts are both rather stable (no change in THF at 70 °C
over 24 h) and do not react further with 1,2-diphenyl-
hydrazine; therefore, the [Ph3PAu]+- induced rearrange-
ment is stoichiometric rather than catalytic. Our work
on elucidating the details of [LAu]+- induced rearrange-
ments of hydrazines will be published in a future paper.
Ph), 137.2 (Cpara of C6H4), 134.2 (d, J CP ) 13.5 Hz, Cortho of
PPh3), 132.3 (br s, Cpara of PPh3), 129.6 (d, 3J CP ) 11.7 Hz, Cmeta
of PPh3), 129.5 (d, J CP ) 60.0 Hz, Cipso of PPh3), 125.7 (Cortho
of C6H4), 120.3 (Cmeta of Ph), 119.8 (Cpara of Ph), 116.0 (Cortho of
Ph). Assignments are tentative. 31P{1H} NMR (CH2Cl2, 101
MHz, 25 °C, ppm): 28.9. UV-vis (CH2Cl2, λmax, nm (ꢀ, M-1
cm-1)): 300 (16 574). IR (KBr, cm-1): 3370 (s, NH).
1
P r ep a r a t ion of [(P h 3P Au )3(µ-N-1,2-C6H 4-NH P h )]BF 4
(2). o-Semidine (0.009 g, 0.050 mmol) was dissolved in CH2-
Cl2 (2 mL), followed by addition of a solution of [(Ph3PAu)3(µ-
O)]BF4 (0.030 g, 0.020 mmol) in CH2Cl2 (2 mL). After the
solution was stirred at ambient temperature for 4 h, Et2O (20
mL) was added. The precipitate was collected through filtra-
tion and washed twice with Et2O (3 mL) to obtain a light yellow
solid (0.030 g, 91.0%). Mp: 153-156 °C. 1H NMR (CD2Cl2, 250
MHz, 25 °C, ppm): 6.29 (NH). 13C{1H} NMR (CD2Cl2, 63 MHz,
25 °C, ppm): 151.7 (C1 of C6H4), 144.6 (Cipso of Ph), 136.0 (C2
of C6H4), 134.2 (d, J CP ) 13.4 Hz, Cortho of PPh3), 132.3 (br s,
Cpara of PPh3), 129.9 (C6 of C6H4), 129.6 (d, J CP ) 11.7 Hz,
Cmeta of PPh3), 129.2 (d, J CP ) 60.4 Hz, Cipso of PPh3), 127.9
(C3 of C6H4), 122.6, 122.5 (C4/C5 of C6H4), 121.4 (Cpara of Ph),
120.7 (Cortho of Ph), 117.6 (Cmeta of Ph). Assignments are
tentative. 31P{1H} NMR (CH2Cl2, 101 MHz, 25 °C, ppm): 28.6.
UV-vis (CH2Cl2, λmax, nm (ꢀ, M-1 cm-1)): 300 (14 745). IR
(KBr, cm-1): 3327 (s, NH).
Exp er im en ta l Section
Gen er a l P r oced u r es. Experiments were performed under
a
nitrogen atmosphere in a Vacuum Atmospheres Corp.
drybox. Solvents were dried by standard techniques and stored
under nitrogen over 4 Å molecular sieves. NMR spectra were
recorded on a Bruker AMX-250 spectrometer. The semidines
and 1,2-diphenylhydrazine were used as received (Aldrich).
[(Ph3PAu)3(µ-O)]BF4 and 1,2-diphenylhydrazine-d10 were pre-
pared by literature procedures.12,13
Rea ction of 1,2-d ip h en ylh yd r a zin e w ith [(P h 3P Au )3-
(µ-O)]BF 4. 1,2-Diphenylhydrazine (0.009 g, 0.05 mmol) was
dissolved in CH2Cl2 (2 mL), followed by addition of a solution
of [(PPh3Au)3(µ-O)]BF4 (0.030 g, 0.020 mmol) in CH2Cl2 (2 mL).
After the solution was stirred at ambient temperature for 4
h, Et2O (20 mL) was added. The precipitate was collected
through filtration and washed twice with Et2O (3 mL) to obtain
a light yellow solid (0.030 g, 91.0%). The 31P NMR spectrum
of the product mixture consists of two singlets at 28.9 and 28.6
ppm at a ratio of 82:18.
P r ep a r a t ion of [(P h 3P Au )3(µ-N-1,4-C6H 4-NH P h )]BF 4
(1). p-Semidine (0.009 g, 0.050 mmol) was dissolved in CH2-
Cl2 (2 mL), followed by addition of a solution of [(Ph3PAu)3(µ-
O)]BF4 (0.030 g, 0.020 mmol) in CH2Cl2 (2 mL). After the
solution was stirred at ambient temperature for 4 h, Et2O (20
mL) was added. The precipitate was collected through filtra-
tion and washed twice with Et2O (3 mL) to obtain a light yellow
solid (0.030 g, 91.0%). Anal. Calcd (found): C, 48.09 (48.09);
H, 3.34 (2.94); N, 1.70 (1.94). Mp: 170-172 °C. 1H NMR (CD2-
Cl2, 250 MHz, 25 °C, ppm): 5.66 (NH). 13C{1H} NMR (CD2-
Cl2, 63 MHz, 25 °C, ppm): 153.7 (Cipso of C6H4), 145.3 (Cipso of
2
3
1
X-r a y Cr ysta llogr a p h y. Yellow prismatic crystals of 1
were grown from CH2Cl2/Et2O at -30 °C. A crystal of dimen-
sions 0.5 × 0.2 × 0.1 mm was selected and mounted with
grease on the end of a glass fiber. The crystal was placed in
the cold nitrogen stream of the diffractometer for data collec-
tion. This followed routine procedures with a Siemens SMART
CCD system as outlined in Table 1. Data were corrected for
absorption with the SADABS program. The structure was
solved using direct methods, completed by subsequent Fourier
difference syntheses, and refined by full-matrix least-squares
methods. All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included in idealized “riding” positions.
Software for data collection and processing were contained in
the Siemens SMART software package. SHELXTL version 5
(Sheldrick, 1994), RES2INS (Len Barbour, 1996), and ORTEP
III were used for solution, refinement, and structure drawing.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, anisotropic thermal parameters, and bond dis-
tances and angles. This material is available free of charge
(12) Nesmeyanov, A. N.; Perevalova, E. G.; Struchkov, Y. T.; Antipin,
M. Y.; Grandberg, K. I.; Dyadchenko, V. P. J . Organomet. Chem. 1980,
201, 243.
(13) Vogel, A. I.; Smith, B. V.; Waldron, N. M. Vogel’s Elementary
Practical Organic Chemistry, 3rd ed.; Longman: New York, 1980; Vol.
1 (Preparations), p 308.
OM980763J
Xia, Aibing
