Dithiolate diphosphine polynuclear gold complexes. X-ray structure of [Au2 (μ-dppm) (C6F5) 2 (S2C6H4) ]

Article abstract of DOI:10.1016/S0277-5387(98)00066-7

The gold (I) complexes [Au₂ (S-S) (AsPh₃) ] n (S-S = S₂C₆H₄, S₂C₆H₃CH₃) react with (Ph₂P (CH₂) nPPh₂) (n = 1, dppm; 2, dppe) affording [Au₂ (S-S) (dppe) ] (1-2) or [Au₄ (S-S)₂ (dppm)₂] (3, 4) . The gold (III) derivative [Au (C₆F₅) (S-S) (AsPh₃) ] reacts with dppe giving rise to [{Au (C₆F₅) (S-S) }₂ (μ-dppe) ] (5, 6) or with dppm affording [Au (C₆F₅) (S-S) dppm] (7, 8) . Complexes 7, 8 further react with the gold (I) compounds [AuX (tht) ] (X = Cl, C₆F₅) giving after substitution of the tetrahydrothiophene group, [Au₂ (μ-dppm) (C₆F₅) X (S-S) ] (9, 10) . The crystal structure of [Au₂ (μ-dppm) (C₆F₅)₂(S₂C₆H ₄) ] (10) has been established by X-ray diffraction and shows a linear Au (I) atom, bonded to a C₆F₅ group and a phosphorus of the dppm, which then bridges via the other phosphorus to a square planar Au (III) atom, which also carries a C₆F₅ group and a chelating dithiolate.

Full text of DOI:10.1016/S0277-5387(98)00066-7

Polyhedron Vol[ 06\ No[ 04\ pp[ 1322Ð1328\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] S9166Ð4276"87#99955Ð6
Dithiolate diphosphine polynuclear gold
complexes[ X!ray structure of
ðAu1"m!dppm#"C5F4#1"S1C5H3#Ł
Raquel Terrobaab\ Eduardo J[ Fernandeza\ Michael B[ Hursthouseb\
ꢀ
Mariano Lagunacꢁ
aDepartamento de Qu(mica\ Universidad de la Rioja\ 15990 Logrono\ Spain
ꢀ
½
bDepartment of Chemistry\ University of Wales Cardi}\ P[O[ Box 801\ Cardi} CF0 2TB\ U[K[
cDepartamento de Qu(mica Inorganica\ Instituto de Ciencia de Materiales de Aragon\ Universidad de
ꢀ
ꢀ
ꢀ
Zaragoza\ C[S[I[C[\ 49998 Zaragoza\ Spain
"Received 10 November 0886^ accepted 3 February 0887#
Abstract*The gold"I# complexes ðAu1"SÐS#"AsPh2#Łn "SÐS ꢂ S1C5H3\ S1C5H2CH2# react with
"Ph1P"CH1#nPPh1# "n ꢂ 0\ dppm^ 1\ dppe# a}ording ðAu1"SÐS#"dppe#Ł "0Ð1# or ðAu3"SÐS#1"dppm#1Ł "2\ 3#[ The
gold"III# derivative ðAu"C5F4#"SÐS#"AsPh2#Ł reacts with dppe giving rise to ð"Au"C5F4#"SÐS##1"m!dppe#Ł "4\ 5#
or with dppm a}ording ðAu"C5F4#"SÐS#dppmŁ "6\ 7#[ Complexes 6\ 7 further react with the gold"I# compounds
ðAuX"tht#Ł "X ꢂ Cl\ C5F4# giving after substitution of the tetrahydrothiophene group\ ðAu1"m!dppm#"C5F4#
X"SÐS#Ł "8\ 09#[ The crystal structure of ðAu1"m!dppm#"C5F4#1"S1C5H3#Ł "09# has been established by X!ray
di}raction and shows a linear Au"I# atom\ bonded to a C5F4 group and a phosphorus of the dppm\ which then
bridges via the other phosphorus to a square planar Au"III# atom\ which also carries a C5F4 group and a
chelating dithiolate[ Þ 0887 Elsevier Science Ltd[ All rights reserved
Keywords] gold^ dithiolate^ diphosphine^ penta~uorophenyl^ X!ray structure
———————————————————————————————————————————————
0[ INTRODUCTION
aneS2#1Ł"BF3#1 as gold"II# species ð09Ł\ ðAu1"CH1PPh1
CH1#1"S1C5H3#1Ł ð00Ł and ð"Au"C5F4#"SÐS##2Ł ð01Ł as
gold"III# examples[
The use of bidentate phosphines as building blocks
for polymetallic complexes has developed enormously
over the last 19 years and a number of reviews of this
area have appeared ð0Ð4Ł[ Other bidentate ligands such
as di! or polythiolates or thioether have been used less
extensively although good examples in the chemistry
of gold have been reported covering all the oxidation
states of this metal] ðAu3"SÐS#1"PEt2#1Ł ðSÐS ꢂ 0\1!
benzenedithiolate "S1C5H3#\ 2\3!toluenedithiolate
"S1C5H2CH2#Ł ð5\ 6Ł\ ðAu2"SÐS#"PPh2#2Ł"ClO3# ð7Ł or
the benzenehexathiol derivative {{golden wheel||
ð"CSAu"PPh2##5Ł ð8Ł as gold"I# derivatives\ ðAu"ð8Ł
The combination of the two _elds in gold chemistry
is of additional interest because some of the AuÐS
drugs increase their e}ects when a phosphine ligand
is present ð02\ 03Ł not only as antiarthritics but in their
anticancer activity ð04Ł or in the inhibitory e}ects on
HIV!0 ð05\ 06Ł[ In this paper we describe the synthesis
of mainly polynuclear gold"I# or:and gold"III# com!
plexes containing dppm "Ph1PCH1PPh1# or dppe
"Ph1P"CH1#1PPh1#\ by reaction of ðAu1"SÐS#"As!
Ph2#Łn ð7Ł and ðAu"C5F4#"SÐS#"AsPh2#Ł ð07Ł "SÐ
S ꢂ bezenedithiolate or toluenedithiolate# with the
diphosphines[ The crystal structure of the digold"I\
III# complex ðAu1"m!dppm#"C5F4#1"S1C5H3#Ł has been
established by X!ray di}raction[
ꢁAuthor to whom correspondence should be addressed[
1322

1323
Raquel Terroba
S1C5H2CH2#\ ðAuCl"tht#Ł ð08Ł and ðAu"C5F4#"tht#Ł
1[ EXPERIMENTAL
ð19Ł "tht ꢂ tetrahydrothiophene#\ were prepared as
described previously[ All other reagents were com!
mercially available[
1[0[ General procedures
The C\ H and S analyses were carried out on a
Perkin!Elmer 1399 Microanalyser[ Conductivities
were measured in approximately 4×09−3 mol dm−2
acetone solutions\ with a Jenway 3909 conductimeter[
The melting points were measured using a Gallen!
kamp apparatus and are uncorrected[ The infrared
spectra were recorded "3999Ð199 cm−0# on a Perkin!
Elmer 772 spectrophotometer\ using Nujol mulls
between polyethylene sheets[ The NMR spectra were
recorded on a Bruker ARX 299 spectrometer\ in
CDCl2[ Chemical shifts are cited relative to SiMe3
1[2[ Preparation of ðAu1"SÐS#"dppe#Ł ðSÐS ꢂ 0\1!
S1C5H3 "0#\ 2\3!S1C5H2CH2 "1#Ł
To a dichloromethane "29 cm2# suspension of
ðAu1"SÐS#"AsPh2#Łn ðSÐS ꢂ 0\1!S1C5H3 "9[973 g\
9[0 mmol#\ S1C5H2CH2 "9[974 g\ 9[0 mmol#Ł\ was
added dppe "9[939 g\ 9[0 mmol#[ After 2 h the solution
was concentrated in vacuum\ addition of diethylether
led the precipitation of the new complexes as white
"0H#\ 74) H2PO3 "external 20P# and CFCl2 08F#[
"
0
solids "0Ð1#[ H NMR] 0] d ꢂ 7[90 and 5[60 "m\ 3H\
Mass spectra were recorded on VG Autospec LSIMS
Technique using 2!nitrobenzylalcohol as a matrix and
a cesium gun[ The elemental analyses\ conductivities\
yield\ melting point and 20P"0H# data of the new com!
plexes are listed in Table 0[
S1C5H3#^ 6[79Ð6[95 "m\ 19H\ Ph#^ 1[69 "m\ 3H\ !CH1!#[
1] d ꢂ 6[78 "d\ 2JH H ꢂ 7[0 Hz\ 0H\ H4ÐS1C5H2CH2#^
4
6[75 "m\ 0H\ H1ÐS51C5H2CH2#^ 6[44Ð6[24 "m\ 19H\
Ph#^
5[77
"dd\
2JH H ꢂ 7[0 Hz\
2JH H
ꢂ
5
1
5
9[6 Hz\ 0H\ H5ÐS1C5H2CH24#^ 1[54 "m\ 3H\ !CH1!#^
1[59 "s\ 2H\ !CH2#[ Mass spectra\ m:z")#] 0] 821"01#
"M¦#\ 470"3# "ðM−"SÐS#Ł¦#\ 0018"6# "ðM¦AuŁ¦#\
0229"4# "ðM¦"PÐP#Ł¦#[ 1] 835"61# "M¦#\ 470"69#
1[1[ Startin` materials
The starting materials ðAu1"SÐS#"AsPh2#Łn ð7Ł\ "ðM−"SÐS#Ł¦#\ 638"4# "ðM−AuŁ¦#\ 0032"69#
ðAu"C5F4#"SÐS#"AsPh2#Ł ð07Ł "SÐS ꢂ 0\1!S1C5H3\ 2\3! "ðM¦AuŁ¦#\ 0233"0# "ðM¦"PÐP#Ł¦#[
Table 0[ Data for the new complexes 0Ð09
Analysis ")#a
H
20Pc
Complex
Yield ")#
C
S
LMb
mp ">C# Pcoord[
Pfree
−
d
0 ðAu1"0\1!S1C5H3#dppeŁ
58
66
59
68
55
57
54
45
64
56
30[3
"30[04#
30[4
1[7
"2[9#
2[0
"2[1#
1[8
"1[74#
1[7
"2[94#
1[44
"1[2#
2[94
"1[44#
2[9
"1[84#
1[84
"2[04#
1[34
"1[24#
0[84
"1[0#
5[74
"5[8#
5[5
"5[64#
6[5
"6[9#
5[84
"5[8#
7[4
"8[0#
7[3
"7[84#
5[7
"6[1#
5[5
"6[0#
4[14
"4[6#
4[34
"4[0#
179
197e
015e
077
019e
031e
54
21[3"s#
d
1 ðAu1"2\3!S1C5H2CH2#dppeŁ
2 ðAu3"0\1!S1C5H3#1"dppm#1Ł
3 ðAu3"2\3!S1C5H2CH2#1"dppm#1Ł
4 ðAu1"C5F4#1"0\1!S1C5H3#1dppeŁ
5 ðAu1"C5F4#1"2\3!S1C5H2CH2#1dppeŁ
6 ðAu"C5F4#"0\1!S1C5H3#dppmŁ
7 ðAu"C5F4#"2\3!S1C5H2CH2#dppmŁ
8 ðAu1"C5F4#Cl"0\1!S1C5H3#dppmŁ
09 ðAu1"C5F4#1"0\1!S1C5H3#dppmŁ
20[6"s#
−
"30[74#
39[44
"39[4#
39[74
"30[1#
32[14
"31[6#
33[9
"32[4#
49[14
"49[9#
49[24
"49[44#
39[0
f
00
4
f
8
21[8"s#
21[8"s#
−
−
04
19
06
4
13[1"d# −16[1"d#
"48[0#
13[0"d# −16[1"d#
"43[9#
08[5"s#
07[6"s#
17[3"s#
08[6"s#
64
012e
049
−
"28[54#
30[4
"30[14#
8
aCalculated values are given in parentheses[
bIn acetone\ values in V−0 cm1 mol−0
cIn CDCl2 d in ppm\ J in Hz[
dLow solubility[
[
eDecompose without melting[
fSee text[

Dithiolate diphosphine polynuclear gold complexes[
1324
1[3[ Preparation of ðAu3"SÐS#1"dppm#1Ł ðSÐS ꢂ 0\1! Fm#[ Mass spectra\ m:z")#] 6] 777"52# "M¦#\ 610"23#
S1C5H3 "2#\ 2\3!S1C5H2CH2 "3#Ł
"ðM−"C5F4#Ł¦#\ 637"74# "ðM−"SÐS#Ł¦#\ 0974"08#
"ðM¦AuŁ¦#[
7]
891"87#
"M¦#\
624"20#
To a dichloromethane "29 cm2# suspension of "ðM−"C5F4#Ł¦#\ 637"51# "ðM−"SÐS#Ł¦#\ 0988"13#
ðAu1"SÐS#"AsPh2#Łn ðSÐS ꢂ 0\1!S1C5H3 "9[973 g\ "ðM¦AuŁ¦#[
9[0 mmol#\ S1C5H2CH2 "9[974 g\ 9[0 mmol#Ł\ was
added dppm "9[927 g\ 9[0 mmol#[ After 2 h the solu!
1[6[ Preparation of ðAu1"C5F4#X"S1C5H3#"m!dppm#Ł
tion was concentrated in vacuum\ addition of diethyl!
ðX ꢂ Cl "8#\ C5F4 "09#Ł
ether led the precipitation of the new complexes as
yellow solids[ 0H NMR] 2] d ꢂ 7[99 and 5[74 "m\ 7H\
To a dichloromethane solution "19 cm2# of 6
S1C5H3#^ 6[92Ð5[74 "m\ 39H\ Ph#^ 3[55 "m\ 1H\
"9[978 g\ 9[0 mmol# was added ðAuX"tht#Ł ðCl
!CH1!# and 3[01 "t\ J ꢂ 01[7 Hz\ 1H\ !CH1!#[ 3]
"9[921 g\ 9[0 mmol# or C5F4 "9[934 g\ 9[0 mmol#Ł[ After
d ꢂ 6[87Ð5[69 "m\ 35H\ aromatic#^ 3[55 "m\ 1H\
0 h stirring the solution was concentrated in vacuum
!CH1!# and 3[02 "t\ J ꢂ 01[4 Hz\ 1H\ !CH1!#^ 1[22 "s\
and the addition of hexane a}ords the precipitation
5H\ !CH2#[ Mass spectra\ m:z")#] 2] 0585"69#
of the new complexes as pink solids[ 8 0H NMR]
"ðM−"SÐS#Ł¦#\
807"26#
"ðM:1Ł¦#\
1922"01#
d ꢂ 6[62Ð6[20 "m\ 19H\ Ph#\ 5[87 "m\ 3H\ S1C5H3#\
"ðM¦AuŁ¦#[ 1] 0573"6# "M¦#\ 0609"099# "ðM−"SÐ
1
3[04 "{{t||\ JPH ꢂ 8[8 Hz\ 1H\ !CH1!#^ 08F NMR]
S#Ł¦#\ 821"25# "ðM:1Ł¦#\ 1950"17# "ðM¦AuŁ¦#[
d ꢂ −019[9 "m\ 1F\ Fo#\ −045[1 "t\ 2JF F ꢂ 08[8 Hz\
p
m
0F\ Fp#\ −059[3 "m\ 1F\ Fm#[ 09 0H NMR] d ꢂ 6[63Ð
1[4[ Preparation of ð"Au"C5F4#"SÐS##1"m!dppe#Ł ðSÐ 6[18 "m\ 19H\ Ph#\ 5[86 "m\ 3H\ S1C5H3#\ 3[05 "{{t||\
S ꢂ 0\1!S1C5H3 "4#\ 2\3!S1C5H2CH2 "5#Ł
1JPÐH ꢂ 8[7 Hz\ 1H\ !CH1!#^ 08F NMR] d ꢂ −005[0
2
"m\ 1F\ Fo#\ −008[8 "m\ 1F\ Fo#\ −045[2 "t\ JF F
p
m
To a dichloromethane solution "19 cm2# of dppe ꢂ 08[5 Hz\ 0F\ Fp#\ −047[0 "t\ JF F ꢂ 19[9 Hz\ 0F\
2
"9[919 g\ 9[94 mmol# was added ðAu"C5F4# "SÐS# Fp#\ −059[4 "m\ 1F\ Fm# −051[4 "mm\ 1F\ Fm#[ Mass
"AsPh2#Ł ð0\1!S1C5H3 "9[970 g\ 9[0 mmol# or 2\3! spectra\ m:z")#] 8] 0974"099# "ðM−ClŁ¦#\ 834"31#
S1C5H2CH2 "9[971 g\ 9[0 mmol#Ł[ After 0 h stirring the "ðM−Cl−"SÐS#Ł¦#[ 6] 0140"46# "M¦#\ 0974"099#
solution was concentrated in vacuum and the addition "ðM−"C5F4#Ł¦#\ 834"85# "ðM−"C5F4#−"SÐS#Ł¦#[
of hexane a}ords the precipitation of the new com!
p
plexes as a pink solid 4 or a violet one 5[ 4 0H NMR]
1[7[ X!ray determination of compound 09
d ꢂ 6[63Ð6[05 and 5[89 "m\ 13H\ aromatic#\ 2[17 "m\
3H\ !CH1!#^ 08F NMR] d ꢂ −008[2 "m\ 3F\ Fo#\
Single crystals were grown by di}using hexane into
−045[8 "t\ 2JF F ꢂ 19[2 Hz\ 1F\ Fp#\ −050[0 "m\ 3F\
p
m
a dichlorometane solution of complex ðAu1"C5F4#1
"S1C5H3#"m!dppm#Ł "09# at room temperature and
mounted in inert oil[
Fm#[ 5 0H NMR] d ꢂ 6[59Ð6[39 and 5[68 "m\ 12H\
aromatic#\ 2[16 "m\ 3H\ !CH1!#\ 1[17 "s\ 2H\ !CH2#^
08F NMR] d ꢂ −008[5 "m\ 3F\ Fo#\ −046[1 "t\
2JF F ꢂ 08[8 Hz\ 1F\ Fp#\ −059[7 "m\ 3F\ Fm#[ Mass
p
m
spectra\ m:z ")#] 4] 0395"02# "M¦#\ 0155"5# "ðM−"SÐ 1[8[ Crystal data and data collection parameters
S#Ł¦#\ 0988"099# "ðM−"SÐS#−"C5F4#Ł¦#\ 0592"4#
"ðM¦AuŁ¦#[ 5] 0323"4# "M¦#\0179"2# "ðM−"SÐ
C33H17Au1Cl1F09P1S1\ M ꢂ 0226[45\ triclinic\ space
S#Ł¦#\ 0002"14# "ðM−"SÐS#−"C5F4#Ł¦#\ 0520"2# group P!0\ a ꢂ 01[270"2# A\ b ꢂ 02[406"2# A\
Ä
Ä
"ðM¦AuŁ¦#[
c ꢂ 03[4499"6# A[ a ꢂ 78[349"0#>\ b ꢂ 001[349"7#>\
Ä
2
Ä
g ꢂ 091[64"1#>\ V ꢂ 1076[3"6# A \ Z ꢂ 1\ Dc ꢂ 1[920
Mg m−2\ F"999# ꢂ 0161\ l"MoÐKa# ꢂ 9[60958 A\
Ä
1[5[ Preparation of ðAu"C5F4#"SÐS#"dppm#Ł ðSÐ
S ꢂ 0\1!S1C5H3 "6#\ 2\3!S1C5H2CH2 "7#Ł
m ꢂ 6[955 mm−0
\ T ꢂ 049 K[ A red prism of
9[19×9[07×9[03 mm was used\ unit cell dimensions
and intensity data were measured using a Delft Instru!
ments FAST TV area detector di}ractometer pos!
itioned at the window of a rotating!anode generator
and using MoÐKa radiation\ as previously described
ð10Ł[ u range for data collection 0[72 to 13[85>\
−03 ¾ h ¾ 9\ 9 ¾ h ¾ 03\ −04 ¾ k ¾ 9\ 9 ¾ k ¾ 09\
−05²l ¾ 9^ 9 ¾ l ¾ 05^ 7819 re~ections collected\
5939 independent "Rint ꢂ 9[969#[
To a dichloromethane solution "19 cm2# of dppm
"9[927 g\ 9[0 mmol# was added ðAu"C5F4#"SÐ
S#"AsPh2#Ł ð0\1!S1C5H3 "9[970 g\ 9[0 mmol# or 2\3!
S1C5H2CH2 "9[971 g\ 9[0 mmol#Ł[ After 0 h stirring the
solution was concentrated in vacuum and the addition
of hexane a}ords the precipitation of the new com!
0
plexes as pink solids[ 6 H NMR] d ꢂ 6[57Ð6[05 and
1
5[80 "m\ 13H\ aromatic#\ 2[59 "d\ JPÐH ꢂ 09[5 Hz\
1H\ !CH1!#^ 08F NMR] d ꢂ −008[4 "m\ 1F\ Fo#\
−045[7 "t\ 2JF F ꢂ 08[8 Hz\ 0F\ Fp#\ −059[7 "m\ 1F\ 1[09[ Structure solution and re_nement
p
m
Fm#[ 7 0H NMR] d ꢂ 6[63Ð6[98 and 5[79 "m\ 12H\
1
aromatic#\ 2[47 "d\ JPÐH ꢂ 09[2 Hz\ 1H\ !CH1!#\ 1[15
The structure was determined using the PATT
"s\ 2H\ !CH2#^ 08F NMR] d ꢂ −008[4 "m\ 1F\ Fo#\ instruction of SHELXS 75 ð11Ł\ the structure was
−045[8 "t\ 2JF F ꢂ 19[6 Hz\ 0F\ Fp#\ −059[8 "m\ 1F\ re_ned by full!matrix least squares on F91\ using the
p
m

1325
Raquel Terroba
program SHELXL 82 ð12Ł[ All data used were cor! 0609"099# for 3 in accordance with a tetranuclear for!
rected for Lorentz!polarization factors and sub! mulation[
sequently for absorption using the program DIFABS
The 0H NMR shows among other resonances\ two
ð13Ł[ The non!hydrogen atoms were re_ned with aniso! groups of signals for the methylene groups from the
tropic thermal parameters[ All hydrogen atoms were dppm ðFig[ 0"a#Ł[ There are two possibilities for
included in idealised positions[ Re_nement on F1 pro! explaining these two resonances for the methylene
ceeded to R ꢂ 9[9393\ wR ꢂ 9[0916 and goodness of groups] either these signals belong to inequivalent
_t 9[830 for 448 parameters and 37 restrains and methylenes or the CH1 groups are equivalent and the
R ꢂ 9[9404\ wR ꢂ 9[0934 for all data[ In the _nal protons from every !CH1! are inequivalent[ The
Fourier synthesis the electron density ~uctuated in the 0H"20P# shows an AB pattern ðFig[ 0"b#Ł\ so the meth!
−2
Ä
range 0[749 to −0[371 e A
[
ylene groups are equivalent and both signals come
from two inequivalent protons of a CH1 group\ that
are coupled one to another "1JHH ꢂ 01\7 Hz#\ in
accordance with the 0HÐ0H correlation[ The selective
irradiation of 20P "15 and 25 ppm# ðFig[ 0"c#Ł\ shows
that one proton signal is only coupled with the
15 ppm!phosphorus!atoms "the higher _eld signal#\
while the other one is coupled with both ðFig[ 0"c#
and "d#Ł[ The complex signal that persists in the
15 ppm!20P!irradiation ðFig[ 0"c#Ł shows that this sig!
nal is coupled with two 25 ppm!phosphorus!atoms[
All these NMR data and the mass spectra are con!
sistent with a tetranuclear structure for complexes 2
and 3 similar to the one reported for the dmit deriva!
tive ð14Ł "Fig[ 1#\ although other polynuclear struc!
tures are not ruled out[
2[ RESULTS AND DISCUSSION
The substitution of triphenylarsine in ðAu1"SÐ
S#"AsPh2#Łn derivatives by diphosphines takes place in
mild conditions as recently reported for monodentate
phosphines ð7\ 07Ł[ The nuclearity of the new com!
plexes are dependent on the diphosphine used\
Ph1P"CH1#nPPh1 "n ꢂ 0\ dppm^ 1\ dppe# "eqns "0# and
"1##[
0:nðAu1"SÐS#"AsPh2#Łn¦dppe
: ðAu1"SÐS#dppeŁ¦AsPh2 "0#
"SÐS# ꢀ 0\1!S1C5H3 "0#^ 2\3!S1C5H2CH2 "1#
1:nðAu1"SÐS#"AsPh2#Łn¦1dppm
:ðAu3"SÐS#1"dppm#1Ł¦1AsPh2 "1#
When the processes 0 and 1 are undertaken starting
from the gold"III# complex ðAu"C5F4#"SÐS#"AsPh2#Ł\
the nuclearity of new complexes are again dependent
on the diphosphine used[ So with dppe the complexes
are dinuclear "eqn "2## whereas with dppm are mono!
"S!S# ꢀ 0\1!S1C5H3 "2#^ 2\3!S1C5H2CH2 "3#
The proposed nuclearity of the complexes is made nuclear\ with the ligand acting in a monodentate
on the basis of NMR data\ mainly 20P"0H# and in the fashion "eqn "3##[ It is noteworthy that the new prod!
mass spectra of the complexes[ So the 20P"0H# NMR ucts "4Ð7# are obtained independently of the molar
of 0 and 1 show singlets showing two equivalent phos! ratio used in the reactions\ although the best yield
phorus atoms in accordance with a dinuclear ten! "Table 0# are obtained when the ratio shown in the
membered ring structure "Table 0#[ The mass spectra equations are used[
"LSIMS¦# show the parent peaks ð"Au1"SÐS#
1ðAu"C5F4#"SÐS#"AsPh2#Ł¦dppe
"dppe##¦Ł at m:z ")#] 821"01# for 0 and 835"61# for
1\ although higher nuclearity peaks\ such as
ðM¦AuŁ¦ or ðM¦"dppe#Ł¦\ are present in lower
intensities than the parent ion\ probably due to some
ionÐmolecule association as in other thiolate gold
complexes ð7\ 14Ł[ Compound 1 has been described
previously ð15Ł and a dinuclear structure has been
suggested[
: ð"Au"C5F4#"SÐS##1"m!dppe#Ł¦1AsPh2 "2#
SÐS ꢂ S1C5H3 "4#^ S1C5H2CH2 "5#
ðAu"C5F4#"S−S#"AsPh2#Ł¦dppm
: ðAu"C5F4#"S−S#dppmŁ¦AsPh2 "3#
S−S ꢂ S1C5H3"6#^S1C5H2CH2"7#
The 20P"0H# NMR of the dppm complexes "2\ 3#
presents an AA?BB? system\ which by iteration pro!
The 08F NMR of the new complexes consists of
cedures show] dA ꢂ 24[3\ dB ꢂ 14[2 ppm^ JAA? ꢂ 066\ three groups of resonances in a 1]0]1 ratio for the
JAB ꢂ JAꢀ Bꢀ ꢂ 71[1\ JAB? ¼ 9 and JBB? ¼ 9 Hz for 2 and ortho\ para and meta 08F nuclei of the C5F4 group "see
dA ꢂ 24[6\ dB ꢂ 14[6 ppm^ JAA? ꢂ 068\ JAB ꢂ JAꢀ Bꢀ ꢂ Section 1#[ The 20P"0H# NMR of the complexes 6 and
72[0\ JAB? ¼ 9 and JBB? ¼ 9 Hz for 3 showing that in 7 shows two doublets at ¼13 and −16 ppm\ that are
these case a dinuclear structure is ruled out[ The pat! in agreement with one phosphorus atom coordinated
terns of these spectra and the corresponding 0H NMR and the other one free[ By contrast\ the compounds 4
"see below# are very close to those reported for and 5 show a singlet that is in accordance with the
ðAu3"C2S4#1"dppm#1Ł ð14Ł which present an asym! equivalence of both phosphorus atoms "Table 0#[
0
metric tetranuclear structure[ The mass spectra Besides other resonances the H NMR show the sig!
"LSIMS¦# show the parent peak ð"Au3"SÐS#1 nals corresponding to the methylene groups from the
"dppm#1#¦Ł at m:z ")#] 0753"6# for 3 and ð"Au3"SÐS# diphosphine[ The mass spectra "LSIMS¦# show the
"dppm#1#¦Ł or ðMÐ"SÐS#Ł¦ at 0585"69# for 2 and peak corresponding to the molecular ion at m:z ")#

Dithiolate diphosphine polynuclear gold complexes[
1326
Fig[ 0[ 0H NMR of complex 2] "a# without decoupling\ "b# 0H"20P# NMR\ "c# 15 ppm!20P decoupled and "d# 25 ppm!20
P
decoupled[
0395"02# 4\ 0323"4# 5\ 777"52# 6 and 891"87# 7\ in
accordance with the proposed formulation[
The lack of dinuclear derivatives of gold"III# dppm
complexes even when 1]0 ratios are used in processes
3 could be due to space requirement[ So we tried the
reaction with gold"I# complexes which are less space
demanding[ In these cases and starting from tetrah!
ydrothiophene "tht# derivatives ðAuX"tht#Ł "X ꢂ Cl^
C5F4# unsymmetrical digold"I\ III# complexes are
obtained "eqn "4##[
ðAu"C5F4#"S1C5H3#"dppm#Ł¦ðAuX"tht#Ł
: ðAu1"C5F4#X"S1C5H3#"m!dppm#Ł¦tht "4#
Fig[ 1[ Schematic view of structure for ðAu3"C2S4#1"dppm#1Ł
and proposed for complex 2 and 3[
X ꢂ Cl "8#^ C5F4 "09#

1327
Raquel Terroba
The 08F NMR shows the same pattern as that in ðAu"C5F4#"S1C5H3#"SC5H3SPPh2#Ł ð01Ł[ The Au"1#ÐS
the previous compounds and in complex 09 other bond lengths are Au"1#ÐS"0# 1[297"2# and Au"1#ÐS"1#
Ä
three groups of signals appear\ in a typical position 1[185"2# A which are very similar to those observed
for a new C5F4 group bonded to gold"I# "see Section in other bis"dithiolate#gold"III# complexes\ such as
Ä
ðAu"0\1!
1#[ In the mass spectra "LSIMS¦# the base peak ðAu"S1C1"CN#1#1Ł−
"1[298 A#
ð16Ł\
"099)# of both compounds correspond with the spec! S1C5H3#1Ł− "1[294 A#ð17Ł\ ðAu"2\3!S1C5H2CH2#1Ł−
Ä
ies ð"MÐX#¦Ł at m:z 0974 and in complex 09 the "1[176"2# and 1[208"3# A# ð7Ł\ ðAu"C5F4#"S1C5H3#
Ä
molecular peak ðM¦Ł appears at m:z 0140 "46)#[ The PPh2Ł "1[203"0# and 1[188"0# A# ð07Ł\ ðAu"C5F4#
Ä
Ä
resonance corresponding to the !CH1! group in the "S1C5H3#"SC5H3SÐPh2#Ł "1[203"3# and 1[188"3# A#
0H NMR "8\ 09# is a pseudo!triplet\ due to similar ð01Ł[ The Au"1#ÐP"1# distance is 1[225"2# A and is
Ä
Ä
coupling constant with both phosphorus[
similar to ðAu"C5F4#"S1C5H3#"PPh2#Ł "1[239"0# A#
The molecular structure of complex 09 was resolved ð07Ł[ The other phosphorus atom is bonded to the
Ä
by single crystal X!ray di}raction study of its dichloro! gold"I# centre Au"0#ÐP"0# 1[153"2# A and are similar
methane solvate "Fig[ 2#[ Selected bond lengths and to those found in "Au"C5F4#{{P||# arrangement
Ä
angles are given in Table 1[ The complex is dinuclear ðAu"C5F4#"PPh1ÐCHÐPPh1Me#Ł "1[176"1# A# ð18Ł\
with a gold"I# and a gold"III# atoms bridged by the ðAu"C5F4#"PPh1ÐCH"Au"C5F4##ÐPPh1Me#Ł "1[175"3#
Ä
dppm ligand[ The gold"III# centre is bonded to one A# ð18Ł[ The other gold center is in a linear geometry
penta~uorophenyl group\ to one of the phosphorus typical of gold"I# complexes C"0#ÐAu"0#ÐP"0#
of the dppm and to the dithiolate ligand acting as 063[1"2#>[ The gold"I#Ðcarbon bond length is Au"0#Ð
Ä
a chelating anion\ in a square!planar geometry with C"0# 1[928"01# A and is in the range of the latter
Ä
angles C"10#ÐAu"1#ÐS"1# 74[5"2#>\ S"1#ÐAu"1#ÐS"0# complexes\ 1[946"5#\ 1[942 and 1[941"09# A[
89[96"00#>\ C"10#ÐAu"1#ÐP"1# 89[9"2#>\ S"0#ÐAu"1#Ð
Ä
P"1# 83[37"09#>^ this Au"1# atom lies 9[988 A out of
Acknowled`ements*The Spanish authors thank the Dire!
ccion General de Investigacion Cient(_ca y Tecnica "PB84!
the plane formed by the four donor atoms[ The
{{Au"C5F4#"S1C5H3#|| fragment is similar to the
ꢀ
ꢀ
ꢀ
ꢀ
9039# for _nancial support and Ministerio de Educacion y
ꢀ
recently reported ðAu"C5F4#"S1C5H3#"PPh2#Ł ð07Ł and Cultura for a grant "to R[ T[#\ and M[ B[ H[ thanks the
Fig[ 2[ The molecule of complex 09 in the crystal[ Hydrogen atoms and dicholorometane are omitted for clarity[

Dithiolate diphosphine polynuclear gold complexes[
1328
Ä
Table 1[ Selected bond lengths "A# and angles "># for 09
Au"0#ÐC"0#
Au"1#ÐC"10#
Au"1#ÐS"0#
S"0#ÐC"01#
P"0#ÐC"39#
1[928"01#
1[959"00#
1[297"2#
0[647"00#
0[736"09#
Au"0#ÐP"0#
Au"1#ÐS"1#
Au"1#ÐP"1#
S"1#ÐC"00#
P"1#ÐC"39#
1[153"2#
1[185"2#
1[225"2#
0[632"00#
0[709"00#
C"0#ÐAu"0#ÐP"0#
C"10#ÐAu"1#ÐS"0#
C"10#ÐAu"1#ÐP"1#
S"0#ÐAu"1#ÐP"1#
C"00#ÐS"1#ÐAu"1#
C"1#ÐC"0#ÐAu"0#
C"15#ÐC"10#ÐAu"1#
C"010#ÐP"0#ÐC"39#
C"010#ÐP"0#ÐAu"0#
C"100#ÐP"1#ÐC"39#
C"100#ÐP"1#ÐAu"1#
C"110#ÐP"1#ÐAu"1#
063[1"2#
064[2"2#
89[9"2#
C"10#ÐAu"1#ÐS"1#
S"1#ÐAu"1#ÐS"0#
S"1#ÐAu"1#ÐP"1#
C"01#ÐS"0#ÐAu"1#
C"5#ÐC"0#ÐAu"0#
C"11#ÐC"10#ÐAu"1#
C"000#ÐP"0#ÐC"39#
C"000#ÐP"0#ÐAu"0#
C"39#ÐP"0#ÐAu"0#
C"39#ÐP"1#ÐC"110#
C"39#ÐP"1#ÐAu"1#
P"1#ÐC"39#ÐP"0#
74[5"2#
89[96"00#
061[14"00#
091[6"3#
012[1"8#
012[9"8#
093[6"4#
001[3"3#
004[8"2#
097[7"4#
001[1"3#
005[1"5#
83[37"09#
093[9"3#
012[5"7#
010[3"8#
094[9"4#
002[2"3#
094[8"4#
097[0"3#
001[0"2#
Engineering and Physical Sciences Research Committee for 04[ Sadler\ P[ J[ in\ Metal complexes in Cancer Chemo!
support of the X!ray facilities[
therapy\ ed[ K[ B[ Keppler[ VCH\ Weinheim\
0882[
05[ Okada\ T[\ Patterdon\ B[ K[\ Ye\ O[ S[ and
Gurney\ M[ E[\ Virolo`y\ 0882\ 081\ 520[
06[ Blough\ H[ A[\ Richetti\ M[ and Montagnier\ B[
H[\ Chem[ Abstr[\ 0880\ 004\ 063529[
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