34
C. Hollatz et al. ■Diphenyl(2-hydroxy-phenyl)phosphine
153 mg. 92% ; white solid, m.p. 226°C. stable to air
and moisture, sparingly soluble in dichloromethane, chlo-
roform and methanol, and insoluble in diethylether and
pentane. - 'H NMR: b = 7.36-7.71 [m. Ph]; 6.77-7.00
[m. C6H4], - i3C{'H} NMR: b = 157.9 [d, 2j(P,C) = 5.37
Hz, C2-C6H4]; 134.2 [d. 2/(P.C) = 13.81 Hz, C2/6-Ph];
134.1 [s, C6-C6H4]; 133.8 [s, C4-C6H4]; 131.8 [s, C4-
Ph]; 129.1 [d. 3/(P,C) = 12.28 Hz. C3/5-Ph]: 128.3 [d.
'/(P.C) = 62.93 Hz, Cl-Ph]; 121.0 [d. V(P,C) = 10.74
Hz, C5-C6H4]; 116.8 [d. 3/(P.C) = 5.37 Hz, C3-C6H4];
CI-C6H4 was not detected. - ' 1P{ 1H} NMR: b = 25.9 [s],
- MS (FAB): m/z = 1029 [2M - Br]+, 556 [M +1]+, 554
[M - 1]+, 475 [M - Br]+.
isom ers [L2A u]+and [A uX t]- have been observed
by NM R spectroscopy in solution, although mass
spectrom etric studies have indicated that cations
[L tA u]+ are form ed in the vaporization and ion-
ization process. Thus inter-ligand hydrogen bond-
ing (-O H /-O H ) in hom oleptic cations [L2Äu]+ is
also not com peting effectively with the O-H - Cl hy-
drogen bonding observed for the heteroleptic com -
pound 1 as the sole binding contacts between the
m olecules. Sim ilar results have been obtained for
analogous phosphinous acid com plexes [15].
Experimental Section
C i8H,5AuBrOP (555.16)
General: All experiments were routinely carried out in
an atmosphere of dry nitrogen. Solvents were dried and
saturated with nitrogen; glassware was oven-dried and
filled with nitrogen. Standard analytical and spectroscopic
equipment was used throughout. Starting materials were
commercially available or prepared and purified follow-
ing published procedures. All NMR data were recorded
in CDCb at 23°C unless otherwise stated.
Calcd C 38.94 H 2.72 %,
Found C 38.69 H 2.93 %.
Pentafluorophenyl[diphenyI-(2-hydroxy-phenyl)phos-
phine]gold(I) (3): Pentafiuorophenyl(tetrahydrothiophe-
ne)gold(I) (136 mg. 0.3 mmol) and Ph2P(C6H40H) (84
mg, 0.3 mmol) were dissolved in CH2CI2 (20 ml) and the
reaction mixture stirred for 1 h at room temperature. The
solvent was evaporated in a vacuum to leave a volume of
3 ml. Pentane (30 ml) was added to precipitate a white
solid, that contained small amounts of the phosphine ox-
ide Ph2P(0 )(C6H40 H), which could not be separated. -
'H NMR: b = 7.21-7.74 [m. Ph]: 6.76-7.05 [m, C6H4].
- 13C{'H} NMR: b = 157.9 [d, 2/(P,C) = 6.91 Hz, C2-
C6H4]; 148.7 [d, '/(F.C) = 258.60 Hz, C2/6-C6F5]; 141.3
[s br, C4-C6F5]; 137.2 [d, '/(E C ) = 271.67 Hz, C3/5-
C6F5]; 134.4 [s, C6-C6H4]; 134.3 [d, 27(P,C) = 13.82 Hz,
C2/6-Ph]; 134.3 [s, C4-C6H4]; 131.7 [d, 4/(P,C) = 3.07
Hz, C4-Ph]; 129.3 [d,3/(P ,C )= l1.52 Hz, C3/5-Ph]; 128.8
[d, '/(P,C) = 56.79 Hz, Cl-Ph]; 121.4 [d, 3/(P,C) = 8.44
Hz, C5-C6H4]; 117.2 [d, 3/(P,C) = 4.61 Hz, C3-C6H4];
115.0 [d, '/(P.C) = 55.25 Hz. C 1-C6H4). - 31P{1H} NMR:
6 =41.0 [s. Ph2P(0)(C6H40H )]; 31.9 [t,4/(F.P) = 7.40 Hz,
Ph2P(C6H4OH)AuC6F5 3], - l9F{'H} NMR (CF3COOH
as reference): b = -85.8 [t, ’/( F,F) = 20.60 Hz, meta-F];
-83.3 [t, 3/(F,F) = 19.72 Hz, para-F]; -43.1 [d, 3/(F,F) =
14.85 Hz, ortho-F]. - C24H,?AuF5OP (642.31).
/Diphenyl-(2-hydroxy-phenyl)phosphine]gold(I) chlo-
ride (1): (Dimethylsulfide)gold(I) chloride (88 mg, 0.3
mmol) and PhbPtCa^O H) (84 mg. 0.3 mmol) were dis-
solved in CH2CI2 (20 ml) and the reaction mixture stirred
at room temperature. The product precipitated as a white
solid, which was collected by filtration after a reaction
time of 1 h. The solvent of the filtrate was evaporated
in a vacuum to leave a volume of 3 ml. Pentane (30 ml)
was added to precipitate the remainder of the product.
Colourless crystals were obtained by slow evaporation of
a saturated CH2CI2 solution: 150 mg, 98% yield; m.p.
251°C (dec.), stable to air and moisture, sparingly sol-
uble in dichloromethane, chloroform and methanol, and
insoluble in diethylether and pentane. - 'H NMR: b =
7.29-7.68 [m. Ph]; 6.82-7.23 [m, C6H4]; 5.80 [s br, OH],
- 13C {1H} NMR: b = 134.2 [d, 2/(P,C) = 13.82 Hz. C2/6-
Ph]; 134.0 [s, C6-C6H4]; 131.9 [d. V(P,C) = 3.07 Hz,C4-
Ph]; 130.7 [s, C4-C6H4]; 129.2 [d, 3/(P.C) = 12.28 Hz,
C3/5-Ph]; 127.9 [d, ‘/(P,C) = 63.72 Hz, Cl-Ph]; 121.4 [d,
3/(P,C) = 10.75 Hz, C5-Cf,H4]; 117.0 [d, iJ(P,C) = 5.37
Hz, C3-C(,H4]; C I-C 6H4 and C2-C6H4 were not detected.
- 3IP{'H} NMR: b = 22.4 [s], - MS (FAB): ni/z = 753
[{Ph2P(C6H4OH)}2Au]+. 475 [M - Cl]+.
Triethylamine-[diphenyl-(2-hydroxy-phenyl)phosphi-
ne]gold(I) chloride (4): [Diphenyl-(2-hydroxy-phenyl)-
phosphine]gold(I) chloride (1) (51 mg, 0.1 mmol) was
dissolved in toluene (50 ml) and the clear colourless so-
lution was treated with an excess of NEt3 (1 ml). Af-
ter stirring for 1 h at room temperature the solvent was
evaporated in a vacuum to leave a volume of 3 ml. Pen-
tane (40 ml) was added to precipitate a white solid,
that contained small amounts of the phosphine oxide
Ph2P(0 )(C6H40 H). Attempted purification by crystal-
lization led to the formation of compound 1 with the free
hydroxy function. - 'H NMR: b = 7.17-7.67 [m, 10H.
C I8H ,5AuC10P(510.69)
Calcd C 42.33 H 2.96 %,
Found C 42.25 H 3.03 %.
[Diphenyl-(2-hydroxy-phenyl)phosphine]gold(I) bro-
mide (2): The procedure was the same as described for
1. using 102 mg of (dimethylsulfide)gold(I) bromide (0.3
mmol) and 84 mg of Ph2P(C6H4OH) (0.3 mmol); yield
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