Two alternatives for the synthesis of non-cyclic phosphino-methanide derivatives of gold

Article abstract of DOI:10.1016/S0277-5387(98)00181-8

The reaction of phosphine-phosphonium derivatives, such as [AuX(PPh₂CH₂PPh₂Me)]ClO₄ or [Au(C₆F₅)₃(PPh₂CH ₂PPh₂Me)]ClO₄, or non-cyclic

Full text of DOI:10.1016/S0277-5387(98)00181-8

Polyhedron Vol[ 06\ No[ 11\ pp[ 2808Ð2814\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] S9166Ð4276"87#99070Ð7
Two alternatives for the synthesis of non!cyclic
phosphino!methanide derivatives of gold
Eduardo J[ Fernandez\a M[ Concepcion Gimeno\b Antonio Laguna\bꢁ
ꢀ
ꢀ
Jose M[ Lopez!de!Luzuriagaa and Elena Olmosa
ꢀ
ꢀ
a Departamento de Qu(mica\ Universidad de La Rioja\ Obispo Bustamante 2\ 15990 Logrono\ Spain
ꢀ
b Departamento de Qu(mica Inorganica\ Universidad de Zaragoza!CSIC\ ICMA\ 49998 Zaragoza\ Spain
ꢀ
ꢀ
"Received 00 February 0887^ accepted 18 April 0887#
Abstract*The reaction of phosphineÐphosphonium derivatives\ such as ðAuX"PPh1CH1PPh1Me#ŁClO3 or
ðAu"C5F4#2"PPh1CH1PPh1Me#ŁClO3\ or non!cyclic bis"diphenylphosphino#methane!bridging complexes\ as
ðAu"C5F4#1X"PPh1CH1PPh1#Au"C5F4#Ł "XꢂCl\ C5F4# or ðAu"C5F4#"PPh1CH1PPh1#Au"C5F4#Ł\ with ace!
tylacetonate derivatives or gold"I# compounds leads to the synthesis of non!cyclic methanide gold complexes
of the types ðAuX"PPh1C"AuPPh2#1PPh1Me#ŁClO3\ ðAu"C5F4#1X"PPh1CH"AuPPh2#PPh1Me#ŁClO3\
ðAu"C5F4#2"PPh1CHÐ"AuPPh2#PPh1#Au"C5F4#Ł\ ðN"PPh2#1ŁðAu"C5F4#2"PPh1CHÐ"AuX#PPh1#Au"C5F4#Ł or
ðN"PPh2#1Łð"Au"C5F4#2"PPh1CH1PPh1#ÐAu"C5F4##1AuŁ[ Þ 0887 Elsevier Science Ltd[ All rights reserved
Keywords] gold^ bis"diphenylphosphino#methane^ methanide^ methanediide
———————————————————————————————————————————————
INTRODUCTION
cac#"PPh2#Ł the eight!membered ring methanide
ðCH"PPh1AuPPh1#1CHŁ\ previously prepared by
di}erent methods by Schmidbaur ð7\ 7Ł and struc!
turally characterized by Mingos\ ð8Ł is formed with
displacement of triphenylphosphine ð09Ł[ The only
examples of bridging non!cyclic methanides of gold
The chemistry of diphosphines\ mainly of bis"di!
phenylphosphino#methane has been extensively
developed in the past ð0Ł[ By deprotonation of the
methylenic group an anion that can be described by
di}erent resonant forms ð1Ł is obtained and its chem!
istry has been studied by several laboratories pro!
ducing results that have been included in a recent
revision ð2Ł[ We have contributed to this topic with
the preparation of a great number of methanide or
methanediide gold complexes\ as for example the
structurally characterized ðAuR1""PPh1#1CH"AuR##Ł\
described
to
date
are
obtained
from
ðAu"C5F4#2"PPh1CH1PPh1#Ł ð00Ł or its calcogenide
derivatives ð01Ł[
These results show that the formation of cyclic
methanides is more likely than the preparation of open
ones\ probably due to the additional stabilization pro!
duced by the delocalization of the electronic density
through the ring[ This made up our minds to study the
possibility of synthesizing non!cyclic gold methanide
complexes and to obtain this we used two di}erent
strategies[ The _rst one is the use of the phosphinoÐ
phosphonium ligand PPh1CH1PPh1Me¦ that features
a positive charge on the quaternary phosphorus\
which increases the acidity of the methylenic protons\
and where the formation of cycles is avoided because
of the presence of the quaternary phosphorus[ The
second strategy is the employment of gold complexes\
ð3Ł
ðAuR1""PPh1#1C"AuPPh2#1#ŁClO3\
ð5Ł\
ð4Ł
or
ð"RAu#HC"PPh1AuPPh1#1CH"AuR#Ł
ð"Ph2PAu#1C"PPh1AuPPh1#1C"AuPPh2#1Ł"ClO3#1 ð6Ł
"RꢂC5F4#[
However\ in these products the diphosphine acts as
a chelating or bridging ligand\ respectively\ and after
the deprotonation the only possibility for further
coordination is through the methanide carbon atom[
Even when the free phosphine is treated with ðAu"a!
such
as
ðAu"C5F4#1X"PPh1CH1PPh1#Au"C5F4#Ł
"XꢂCl\ C5F4# or ðAu"C5F4#"PPh1CH1PPh1#Au"C5F4#Ł\
with a saturated coordination sphere for the metal
centers\ which also prevents the formation of rings[
ꢁ Author to whom correspondence should be addressed[
Tel[] ¦23!865!650!074^ Fax] ¦23!865!650!076^ E!mail]
alagunaÝposta[unizar[es[
2808

2819
E[ J[ Fernandez et al[
This result di}ers from that previously described in P and AuÐC bonds# is formed\ but its low solubility
which although the formation of rings is avoided\ the did not allow us to complete its characterization[
coordination was possible through two donor atoms
ð01Ł[
The same result is obtained when the methanide
ðAu"C5F4#"PPh1CHPPh1Me#Ł ð02Ł is treated with
ðAu"PPh2#"tht#ŁClO3\ and no sign of formation of
ðAu"C5F4#"PPh1CH"AuPPh2#PPh1Me#ŁClO3
observed[
is
RESULTS AND DISCUSSION
In contrast\ when complexes 0 or 1 are treated with
ðAu"acac#"PPh2#Ł in a 0]1 molar ratio\ both methylenic
protons are substituted by ðAuPPh2Ł¦ groups\ a}ord!
ing the trinuclear species ðAuX"PPh1C"AuP!
Ph2#1PPh1Me#ŁClO3 ðXꢂCl "3#\ C5F4 "4#Ł Scheme 0[
Complexes 3 and 4 are air and moisture stable solids\
soluble in chlorinated solvents and acetone and non
soluble in diethyl ether and hexane[ Their analytical
and spectroscopic data are in accordance with the
proposed formulation\ displaying three resonances
with relative intensities 1]0]0 in their 20P"0H# NMR
spectra[
Non!cyclic methanides are also obtained using pho!
sphinoÐphosphonium derivatives of gold"III#[ Thus\
reaction of ðAu"C5F4#1X"PPh1CH1PPh1Me#ŁClO3
"XꢂCl\ C5F4# with ðN"PPh2#1Ł"acac# in dichlo!
romethane a}ords the previously described species
ðAu"C5F4#1X"PPh1CHPPh1Me#Ł ðXꢂCl "5#\ C5F4 "6#Ł
through an alternative synthetic pathway[ Their ana!
lytical and spectroscopic data agree with those pre!
viously described[ ð02Ł Treatment of the same starting
products with one equivalent of ðAu"acac#"PPh2#Ł
leads to di}erent results than the related gold"I# com!
We have mentioned above two di}erent strategies
for the synthesis of open phosphinoÐmethanide
derivatives[ With regard to the use of
PPh1CH1PPh1Me¦ as ligand we prepared the gold"I#
complex ðAuCl"PPh1CH1PPh1Me#ŁClO3 "0# as starting
material\ by reaction of ðAuCl"tht#Ł "tht!
ꢂtetrahydrothiophene# with an equimolecular
amount of "PPh1CH1PPh1Me#ClO3 "see Scheme 0#[
Complex 0 is obtained as an air and moisture stable
white solid\ with similar physical and spectroscopic
properties to those observed for the previously
described per~uorophenyl derivative 1 ð02Ł[
The use of acetylacetonate "acac# complexes has
been previously reported in the synthesis of ylide or
methanide complexes of gold "Refs[ ð09\ 03\ 03Ł and
references therein#[ When complex 1 is treated with
equimolecular amounts of ðAu"acac#"PPh2#Ł in dichlo!
romethane an initial yellow colour appears\ which
becomes subsequently discoloured with the sim!
ultaneous formation of a white precipitate[ After 0 h of
reaction the solid is _ltered o} and ðAu"C5F4#"PPh2#Ł is
obtained from the solution[ The analytical data for
the insoluble product are in accordance with those
expected for a complex with an stoichiometry ðAu"P!
Ph1CHPPh1Me#ŁClO3[ Its IR spectrum shows two
absorptions at 519 "m# and 0099 "vs\ br# cm−0 ð04Ł due
to the perchlorate ion^ some bands corresponding to
the phosphinoÐphosphonium ligand at about 499 and
784 cm−0\ as well as a band at 475 "m# cm−0\ assigned
to the n"AuÐC# vibration ð05\ 05\ 05\ 05\ 06Ł[ Taking
these data and its insolubility into account\ we pro!
pounds
and
the
monosubstituted
species
ðAu"C5F4#1X"PPh1CH"AuPPh2#PPh1Me#ŁClO3
ðXꢂCl "7#\ C5F4 "8#Ł are now easily isolated "see Sch!
eme 1#[ Complexes 7 and 8 can also be prepared from
the methanide compounds 5 and 6\ respectively\ when
reacted with the appropriate amounts of ðAu"P!
Ph2#"tht#ŁClO3[ Also in contrast with the behavior of
the gold"I# species\ the disubstituted products
ðAu"C5F4#1X"PPh1C"AuPPh2#1PPh1Me#ŁClO3 can not
pose
that
a
polymeric
complex
ðAu"P! be prepared even when an excess "0]2# of ðAu"a!
Ph1CHPPh1Me#"ClO3#Łn "2# "probably featuring AuÐ cac#"PPh2#Ł is employed[
Scheme 0[ RꢂC5F4^ "i# ðAuX"tht#Ł^ "ii# ðAu"acac#"PPh2#Ł^ "iii# ðAu"PPh2#"tht#ŁClO3^ "iv# 1 ðAu"acac#"PPh2#Ł[

Synthesis of non!cyclic phosphino!methanide derivatives of gold
2810
Scheme 1[ RꢂC5F4^ "i# ðN"PPh2#1Ł"acac#^ "ii# ðAu"acac#"PPh2#Ł^ "iii# ðAu"PPh2#"tht#ŁClO3[
Compounds 7 and 8 are obtained as white\ air and
Complex 09 is obtained as a yellow air and moisture
moisture stable solids[ Their 20P"0H# NMR spectra sensitive oil\ which makes its characterization di.cult[
show three resonances with similar relative intensities\ In its IR spectrum a broad signal located at 0073
in accordance with the substitution of only one methy! "m# cm−0\ assigned to the methanide system ð2Ł\ is
lenic proton[ This fact is also con_rmed in their 0H present[ Its 20P"0H# NMR spectrum con_rms the
NMR spectra\ which display one signal due to the presence of the cation\ because a sharp singlet at
remaining hydrogen atom\ as well as a doublet cor! dꢂ10[6 ppm appears[ It also shows two multiplets
responding to the protons of the methyl group[ The with the same intensity\ according with the existence
08F NMR spectrum is in agreement with the cis pos! of two inequivalent phosphorus of the diphosphinoÐ
ition of the penta~uorophenyl groups in 7[
methanide ligand with a penta~uorophenyl group in
Regarding the second strategy mentioned in Section trans position[
0\ the use of dinuclear complexes featuring a saturated
Reaction of 09 with one equivalent of ðAu"P!
coordination sphere for the gold atoms\ the employ! Ph2#"tht#ŁClO3 or ðAuX"tht#Ł "XꢂCl\ C5F4# leads to
ment of ðAu"C5F4#2"PPh1CH1PPh1#Au"C5F4#Ł ð07Ł the displacement of the sulfur donor ligand and the
leads to the same observations than the gold"III# pho! coordination of the non!saturated methanide carbon
sphinoÐphosphonium species[ Thus\ the reaction of to the gold"I# centre a}ording the trinuclear neutral
this dinuclear complex with ðN"PPh2#1Ł"acac# gives rise "00# or anionic "01 and 02# derivatives\ as represented
to
"PPh1CHPPh1#Au"C5F4#Ł "09#\ one of the few anionic thesized directly from ðAu"C5F4#2"PPh1CH1PPh1#
methanides reported to date "Scheme 2#[ Au"C5F4#Ł and ðAu"acac#"PPh2#Ł in a 0]0 molar ratio[
the
synthesis
of
ðN"PPh2#1ŁðAu"C5F4#2 in Scheme 2[ Compound 00 can alternatively be syn!
Scheme 2[ RꢂC5F4^ QꢂðN"PPh2#1Ł^ "i# Q"acac#^ "ii# ðAu"acac#"PPh2#Ł^ "iii# ðAu"PPh2#"tht#ŁClO3^ "iv# ðAuX"tht#Ł[

2811
E[ J[ Fernandez et al[
Besides\ as observed for gold"III# derivatives with
PPh1CH1PPh1Me¦\ the use of an excess of ðAu"a!
cac#"PPh2#Ł does not produce a double deprotonation General
and the monosubstituted product 00 is formed again[
EXPERIMENTAL
Complexes 00\ 01 and 02 are obtained as white
NMR spectra were recorded on a Bruker ARX 299
powders[ They are stable in solid state and in solution\ spectrometer in CDCl2 solutions[ Chemical shifts are
except 01\ which rapidly decomposes in solution[ They quoted relative to SiMe3 "0H\ external#\ CFCl2 "08F\
are soluble in most common organic solvents\ except external# and H2PO3 "74)# "20P\ external#[ All experi!
in hexane and their analytical and spectroscopic data ments were carried out at room temperature and
are in accordance with the proposed formulation "see under nitrogen[
Section 2#[
In order to increase the nuclearity of the products
we can use ðN"PPh2#1ŁðAu"acac#1Ł\ which can at once ðAuCl"PPh1Ch1PPh1Me#ŁClO3 "0#
extract one methylenic proton of two di}erent mol!
ecules of ðAu"C5F4#1X"PPh1CH1PPh1#Au"C5F4#Ł
To a dichloromethane solution of ðAuCl"tht#Ł ð19Ł
"XꢂCl\ C5F4# and coordinate both methanide units "9[953 g\ 9[1 mmol# was added "PPh1CH1PPh1Me#
to the gold"I# center\ a}ording the pentanuclear ClO3 "9[987 g\ 9[1 mmol#[ After 29 min of stirring a
ðN"PPh2#1Łð"Au"C5F4#2"PPh1CHPPh1#Au"C5F4##1AuŁ
"03# "equation 0#[
little amount of precipitate is _ltered over celite and
the solution was concentrated to ca[ 4 ml and diethyl
This complex is obtained as a white solid and it is ether was added to give complex 0 as a white solid[
air and moisture stable in solid state\ but its stability Yield] 79)[ m[p[] 087 "dec#[ !C15H14AuCl1O3P1
decreases in solution[ Its 20P"0H# NMR spectrum is "620[29#\ calcd[ C\ 31[6^ H\ 2[34^ found C\ 31[44^ H\
similar to those registered for 09 and 01\ featuring a 2[2[ Lm] 004 V−0 cm1 mol−0[ !20P"0H#NMR] d 11[9 "d\
singlet at dꢂ10[6 ppm\ corresponding to the cation\ 0P\ AuÐPPh1#\ ð1J"PP¦#ꢂ3[7 HzŁ# and 07[1 "m\ 0P\
and two multiplets due to both types of phosphorus PPh1Me#^ !0H NMR
d
3[4 "dd\ 1H\ CH1\
of the methanide unit[ In spite of complex 03 having ð1J"HP#ꢂ7[3\ 1J"HP#ꢂ4[3 HzŁ# and 1[3 "d\ 2H\ Me\
two chiral carbon atoms and thus two pairs of enanti! ð1J"HP#ꢂ5[6 HzŁ#[
omers which can be present at the same time "RR\ SS
and RS\ SR#\ the 08F and 0H NMR spectra show only
one set of signals[
ðAu"PPh1CHPPh1Me#ŁClO3 "2#
Finally\ we have studied the behavior of
ðAu"C5F4#"PPh1CH1PPh1#Au"C5F4#Ł ð08Ł[ The reac!
"a# To a dichloromethane solution of 1 ð02Ł "9[975 g\
tion with one equivalent of ðAu"acac#"PPh2#Ł gives rise 9[0 mmol# was added ðAu"acac#"PPh2#Ł ð10Ł "9[944 g\
to the substitution of one methylenic hydrogen\ 9[0 mmol# and the solution initially turned yellow\ but
a}ording
ðAu"C5F4#"PPh1CH"AuPPh2#PPh1# after a few minutes it became discoloured with the
Au"C5F4#Ł "04#\ while an excess of the acetylacetonate appearance of 2 as a white solid[ The mixture was
derivative does not lead to further substitutions\ stirred for 0 h and complex 2 "yield] 76)# was then
recovering always complex 04 "Scheme 3#[ This is a _ltered o} and ðAu"C5F4#"PPh2#Ł was isolated from
white stable solid\ soluble in common organic the _ltrate[
solvents\ except in hexane[ Its 20P"0H# NMR spec!
"b#
A
dichloromethane
solution
of
trum shows two resonances at dꢂ39[7 "t# and 25[7 ðAu"C5F4#"PPh1CHPPh1Me#Ł ð02Ł "9[965 g\ 9[0 mmol#
"d# ppm\ with a relative intensity 0]1 and in its 0H was treated with ðAu"PPh2#"tht#ŁClO3 ð11Ł "9[954 g\
NMR spectrum a pseudotriplet of doublets centered 9[0 mmol# and a white precipitate appears[ After 0 h
at dꢂ2[8 ppm\ due to the methylinic proton appears[ the precipitation was complete and _ltration of the

Synthesis of non!cyclic phosphino!methanide derivatives of gold
2812
Scheme 3[ RꢂC5F4^ "i# ðAu"acac#"PPh2#Ł[
solid a}orded 2 "yield] 71)# while ðAu"C5F4#"PPh2#Ł 9[01 mmol#[ After 1 h of stirring the solvent was evap!
was recovered from the solution[ C15H13AuClO3P1 orated to dryness in a vacuum and 04 ml of diethyl
"583[73#\ calcd[ C\ 33[84^ H\ 2[4^ found C\ 33[64^ H\ ether was added to precipitate the ðN"PPh2#1ŁClO3 for!
1[8[
med in the reaction\ which is removed by _ltration
over celite[ Concentration of the _ltrate and addition
of hexane led to complexes 5 "yield] 84)# or 6 "yield]
87)# as white solids[ Their analytical and spec!
troscopic data agree with those previously described
ð02Ł[
ðAu"PPh1C"AuPPh2#1PPh1Me#ŁClO3 ðXꢀCl "3#\
C5F4 "4#Ł
To a solution of 0 "9[962 g\ 9[0 mmol# or 1 "9[975 g\
9[0 mmol# in 19 ml of dichloromethane was added
ðAu"acac#"PPh2#Ł "9[009 g\ 9[1 mmol# and after 1 h of
stirring a little amount of precipitate is _ltered over
celite[ The solvent was then evaporated in a vacuum
and 19 ml of diethyl ether was added to give complexes
3 "yield] 69)# or 4 "yield] 74)# as white solids[ 3]
m[p[] 029 "dec#[ C51H42Au2Cl1O3P3 "0536[79#\ calcd[ C\
34[1^ H\ 2[14^ found C\ 34[14^ H\ 2[5[ Lm]
84 V−0 cm1 mol−0[ !20P"0H# NMR] d 26[5 "dd\ 1P\
PPh2\ ð2J"PP#ꢂ00\ 2J"PP¦#ꢂ5[2 HzŁ#\ 21[4 "t\ 0P\
AuÐPPh1# and 11[5 "t\ 0P\ PPh1Me#^ !0H NMR] d 1[2
"d\ 2H\ Me\ ð1J"HP#ꢂ02[8 HzŁ#[ 4] m[p[] 031 "dec#[ !
C57H42Au2ClF4O3P3 "0668[26#\ calcd[ C\ 34[7^ H\ 2[9^
found C\ 34[8^ H\ 1[84[ Lm] 093 V−0 cm1 mol−0[ !20P"
0H# NMR] d 26[5 "m\ 1P\ PPh2#\ 33[8 "m\ 0P\ AuÐ
ðAu"C5F4#1X"PPh1CH"AuPPh2#PPh1Me#ŁClO3
ðXꢀCl "7#\ C5F4 "8#Ł
"a#
A
dichloromethane
solution
of
ðAu"C5F4#1X"PPh1CH1PPh1Me#ŁClO3 ð9[095 g "Cl# or
9[008 g "C5F4#\ 9[0 mmolŁ was treated with ðAu"a!
cac#"PPh2#Ł "9[944 g\ 9[0 mmol#[ The mixture was stir!
red for 1 h and the solvent was then evaporated to ca[
4 ml[ 19 ml of diethyl ether was added to precipitate
complexes 7 "yield] 89)# or 8 "yield] 54)# as white
solids[
"b# To a solution of ðAu"C5F4#1X"PPh1CHPPh1Me#Ł
ð9[985 g "Cl# or 9[009 g "C5F4#\ 9[0 mmolŁ in 19 ml of
dichloromethane was added ðAu"PPh2#"tht#ŁClO3
"9[954 g\ 9[0 mmol# and after 29 min of stirring the
solution was concentrated in a vacuum[ Addition of
diethyl ether gave complexes 7 "yield] 72)# or 8 "yield]
51)# as white solids[ 7] m[p[] 84 "dec#[ !C45H28Au!
1Cl1F09O3P2 "0412[48#\ calcd[ C\ 33[04^ H\ 1[5^ found
0
PPh1# and 12[6 "m\ 0P\ PPh1Me#^ H NMR] d 1[3 "d\
2H\ Me\ ð1J"HP#ꢂ6[7 HzŁ#^ !08F NMR] d −004[2 "m\
1F\ o!F#\ −048[4 "t\ 0F\ p!F\ ð2J"FF#ꢂ08[4 HzŁ# and
−051[7 "m\ 1F\ m!F#[
ðAu"C5F4#1X"PPh1CHPPh1Me#Ł ðXꢀCl "5#\ C5F4 "6#Ł C\ 33[34^ H\ 1[24[ Lm] 029 V−0 cm1 mol−0[ !20P"0H#
NMR] d 28[4 "{{t||\ 0P\ PPh2\ ð2Nꢂ8[7 HzŁ#\ 16[3 "dm\
To a solution of ðAu"C5F4#1X"PPh1CH1PPh1Me! 0P\ AuÐPPh1# and 10[2 "dd\ 0P\ PPh1Me\
#ŁClO3 ð02Ł ð9[095 g "Cl# or 9[008 g "C5F4#\ 9[0 mmolŁ in ð1J"PP¦#ꢂ18 HzŁ#^ !0H NMR] d 4[1 "{{td||\ 0H\ CH\ ð
2
dichloromethane was added ðN"PPh2#1Ł"acac# "9[965 g\ 1J"HP#ꢂ03[2\ J"HP#ꢂ7[7 HzŁ# and 1[5 "d\ 2H\ Me\
Fig[ 0[

2813
E[ J[ Fernandez et al[
ð1J"HP#ꢂ03[0 HzŁ#^ !08F NMR] d!019[2 "m\ 0F\ o!F#\ ðN"PPh2#1ŁðAu"C5F4#2"PPh1Ch"AuX#PPh1#Au"C5F4#Ł
−010[6 "m\ 0F\ o!F#\ −045[3 "t\ 0F\ p!F\ ðXꢀCl "01#\ C5F4 "02#Ł
ð2J"FF#ꢂ08[2 HzŁ#\ −048[3 "m\ 0F\ m!F#\ −059[3 "m\
0F\ m!F#\ −010[7 "m\ 0F\ o!F#\ −011[0 "m\ 0F\ o!F#\
To a freshly prepared solution of 09 "9[0 mmol#
−045[4 "t\ 0F\ p!F\ ð2J"FF#ꢂ08[9 HzŁ#\ −059[5 "m\ in dichloromethane was added ðAuCl"tht#Ł "9[921 g\
0F\ m!F# and −059[7 "m\ 0F\ m!F#[ 8] m[p[] 003 9[0 mmol# or ðAu"C5F4#"tht#Ł ð12Ł "9[934 g\ 9[0 mmol#
"dec#[ !C51H28Au1ClF04O3P2 "0544[04#\ calcd[] C\ 34[9^ and the solution turned rapidly colourless[ After
H\ 1[3^ found C\ 34[4^ H\ 1[34[ Lm] 29 min of stirring the solvent was evaporated in a
015 V−0 cm1 mol−0[ !20P"0H# NMR] d 27[5 "m\ 0P\ vacuum and hexane was added to precipitate com!
PPh2#\ 12[3 "m\ 0P\ AuÐPPh1# and 06[3 "m\ 0P\ plexes 01 "yield] 64)# or 02 "yield] 69)# as white
PPh1Me#^ !0H NMR] d 2[5 "m\ 0H\ CH# and 1[0 "d\ solids[ 01] m[p[] 52 "dec#[ !C74H40Au2ClF19NP3
2H\ Me\ ð1J"HP#ꢂ02[0 HzŁ#^ !08F NMR] d−008[0 "m\ "1105[39#\ calcd[ C\ 35[94^ H\ 1[2^ N\ 9[5^ found C\
1F\ o!F#\ −044[6 "t\ 0F\ p!F\ ð2J"FF#ꢂ08[8 HzŁ#\ 34[7^ H\ 1[24^ N\ 9[3^ 02] m[p[] 64 "dec#[
!
−048[5 "m\ 1F\ m!F#\ −019[6 "m\ 1F\ o!F#\ −045[4 C80H40Au2F14NP3 "1236[85#\ calcd[] C\ 35[44^ H\ 1[1^
"t\ 0F\ p!F\ ð2J"FF#ꢂ19[2 HzŁ# and −059[7 "m\ 1F\ N\ 9[5^ found C\ 35[5^ H\ 1[3^ N\ 9[4[ Lm]
m!F#[
70 V−0 cm1 mol−0[ !20P"0H# NMR] d 28[3 "m\ 0P\
Au"I#ÐPPh1#\ 11[3 "m\ 0P\ Au"III#ÐPPh1# and 10[6 "s\
1P\ ðN"PPh2#1Ł¦#^ !0H NMR] d 2[44 "{{t||\ 0H\ CH\
ðNꢂ8[3 HzŁ#^ !08F NMR] d−007[0 "m\ 3F\ o!F#\
−048[4 "t\ 1F\ p!F\ ð2J"FF#ꢂ10[6 HzŁ#\ −051[3 "m\
of 3F\ m!F#\ −019[1 "m\ 1F\ o!F#\ −048[2 "t\ 0F\ p!F\ ð
ðN"PPh2#1ŁðAu"C5F4#2"PPh1CHPPh1#Au"C5F4#Ł "09#
To
a
diethyl
ether
solution
ðAu"C5F4#2"PPh1CH1PPh1#Au"C5F4#Ł ð07Ł "9[033 g\ 2J"FF#ꢂ19[1 HzŁ#\ −052[4 "m\ 1F\ m!F#\ −004[1 "m\
9[0 mmol# was added ðN"PPh2#1Ł"acac# "9[965 g\ 1F\ o!F#\ −048[8 "t\ 0F\ p!F\ ð2J"FF#ꢂ08[4 HzŁ#\
9[01 mmol# and the solution turned yellow[ After 1 h −053[1 "m\ 1F\ m!F#\ −005[1 "m\ 1F\ o!F#\ −059[3
of stirring the excess of ðN"PPh2#1Ł"acac# was removed "t\ 0F\ p!F\ ð2J"FF#ꢂ19[2 HzŁ# and −053[6 "m\ 1F\
by _ltration and the solution was dried in a vacuum m!F#[
giving complex 09 as a yellow oil[ !20P"0H# NMR] d
20[0 "m\ 0P\ Au"I#ÐPPh1#\ 07[4 "m\ 0P\ Au"III#ÐPPh1#
ðN"PPh2#1Łð"Au"C5F4#2"PPh1CHPPh1#Au"C5!
and 10[6 "s\ 1P\ ðN"PPh2#1Ł¦#[
F4##1AuŁ "03#
A
dichloromethane solution of ðAu"C5F4#2
ðAu"C5F4#2"PPh1CH"AuPPh2#PPh1#Au"C5F4#Ł "00#
"PPh1CH1PPh1#Au"C5F4#Ł "9[033 g\ 9[0 mmol# was tre!
ated with ðN"PPh2#1ŁðAu"acac#1Ł ð4\ 13Ł "9[921 g\
9[94 mmol# and the solution turned rapidly yellow\
which disappeared after 1 h of reaction[ A little
amount of solid was _ltered over celite and the solu!
tion was concentrated in a vacuum[ 19 ml of hexane
was added to precipitate complex 03 as a white solid[
Yield] 53)[ m[p[] 75[ !C023H61Au4F39NP5 "2515[22#\
calcd[ C\ 33[3^ H\ 1[9^ N\ 9[3^ found C\ 33[44^ H\ 0[74^
N\ 9[24[ Lm] 002 V−0 cm1 mol−0[ !20P"0H# NMR] d
17[9 "m\ 1P\ Au"I#ÐPPh1#\ 00[2 "m\ 1P\ Au"III#ÐPPh1#
and 10[6 "s\ 1P\ ðN"PPh2#1Ł¦#^ !0H NMR] d 2[43 "{{t||\
0H\ CH\ ðNꢂ8[2 HzŁ#^ !08F NMR] d−008[0 "m\ 7F\
o!F#\ −043[2 "t\ 3F\ p!F\ ð2J"FF#ꢂ08[2 HzŁ#\ −047[6
"m\ 7F\ m!F#\ −019[2 "m\ 3F\ o!F#\ −044[3 "t\ 1F\ p!
F\ ð2J"FF#ꢂ08[4 HzŁ#\ −048[5 "m\ 3F\ m!F#\ −003[8
"m\ 3F\ o!F#\ −045[4 "t\ 1F\ p!F\ ð2J"FF#ꢂ19[9 HzŁ#
and −050[0 "m\ 3F\ m!F#[
"a#
A
dichloromethane
solution
of
ðAu"C5F4#2"PPh1CH1PPh1#Au"C5F4#Ł
"9[033 g\
9[0 mmol# was treated with ðAu"acac#"PPh2#Ł "9[944 g\
9[0 mmol#[ The mixture was stirred for 1 h and a little
amount of solid was _ltered over celite[ The solvent
was then evaporated to ca[ 4 ml and hexane was added
to precipitate complex 00 as a white solid[ Yield] 49)[
"b# To a freshly prepared solution of 09 "9[0 mmol#
in dichloromethane was added ðAu"PPh2#"tht#ŁClO3
"9[954 g\ 9[0 mmol# and the solution turned rapidly
colourless[ The solution was stirred for 29 min and the
solvent was then dried in a vacuum[ Addition of
diethyl ether led to the precipitation of the
ðN"PPh2#1ŁClO3 formed in the reaction\ which was
removed by _ltration over celite[ Concentration of the
_ltrate and addition of hexane gave complex 00 as a
white solid[ Yield] 39)[ m[p[] 039 "dec#[
!
C56H25Au2F19P2 "0893[54# calcd[] C\ 31[1^ H\ 0[8^
found C\ 30[4^ H\ 1[9[ Lm] 09 V−0 cm1 mol−0[ !20P" ðAu"C5F4#"PPh1CH"AuPPh2#PPh1#Au"C5F4#Ł "04#
0H# NMR] d 28[1 "{{t||\ 0P\ PPh2\ ðNꢂ8[7 HzŁ#\ 25[7
"m\ 0P\ Au"I#ÐPPh1# and 11[2 "m\ 0P\ Au"III#ÐPPh1#^ !
A
dichloromethane solution of ðAu"C5F4#
0H NMR] d 2[5 "m\ 0H\ CH#^ !08F NMR] d−007[6 "PPh1CH1PPh1#Au"C5F4#Ł "9[001 g\ 9[0 mmol# was tre!
"m\ 3F\ o!F#\ −047[1 "t\ 1F\ p!F\ ð2J"FF#ꢂ19[5 HzŁ#\ ated with ðAu"acac#"PPh2#Ł "9[944 g\ 9[0 mmol#[ The
−050[0 "m\ 3F\ m!F#\ −010[4 "m\ 1F\ o!F#\ −046[8 mixture was stirred for 0 h and a little amount of
"t\ 0F\ p!F\ ð2J"FF#ꢂ19[5 HzŁ#\ −050[7 "m\ 1F\ m!F#\ solid was _ltered over celite[ The solvent was then
−005[0 "m\ 1F\ o!F#\ −048[1 "t\ 0F\ p!F\ evaporated to ca[ 4 ml and hexane was added to pre!
ð2J"FF#ꢂ08[2 HzŁ# and −052[0 "m\ 1F\ m!F#[
cipitate complex 04 as a white solid[ Yield] 57)[ m[p[]

Synthesis of non!cyclic phosphino!methanide derivatives of gold
2814
mart(n\ F[ and Jones\ P[ G[\ Or`anometallics\
ꢀ
029 "dec#[ !C44H25Au2F09P2 "0469[50#\ calcd[ C\ 31[94^
H\ 1[2^ found C\ 30[0^ H\ 1[6[ Lm] 3 V−0 cm1 mol−0[ !
20P"0H#NMR] d 39[7 "t\ 0P\ PPh2\ ð2J"PP#ꢂ03[4 HzŁ#
and 25[7 "d\ 1P\ Au"I#ÐPPh1#^ !0H NMR] d 2[8 "td\
0882\ 01\ 2873[
00[ Fernandez\ E[ J[\ Gimeno\ M[ C[\ Jones\ P[ G[\
ꢀ
ꢀ
Laguna\ A[\ Laguna\ M[\ Lopez!de!Luzuriaga\ J[
M[\ Or`anometallics\ 0884\ 03\ 1807[
0H\ CH\ ð1J"HP#ꢂ03[3\ 2J"HP#ꢂ6[0 HzŁ#^
!
08F
01[ Alvarez\ B[\ Fernandez\ E[ J[\ Gimeno\ M[ C[\
ꢀ
NMR] d−004[2 "m\ 3F\ o!F#\ −059[7 "t\ 1F\ p!F\ ð
Jones\ P[ G[\ Laguna\ A[ and Loꢀpez!de!Luzur!
2J"FF#ꢂ08[5 HzŁ# and −053[1 "m\ 3F\ m!F#[
iaga\ J[ M[\ Polyhedron "in press#[
ꢀ
02[ Uson\ R[\ Laguna\ A[\ Laguna\ M[\ Lazaro\ I[\
ꢀ
Morata\ A[\ Jones\ P[ G[ and Sheldrick\ G[ M[\ J[
Chem[ Soc[ Dalton Trans[\ 0875\ 558[
Acknowled`ements*We thank the Direccion General de
ꢀ
Investigacion Cient(_ca y Tecnica "No[ PB83!9968# for _n!
ꢀ
ꢀ
ꢀ
03a[ Vicente\ J[\ Chicote\ M[ T[\ Saura!Llamas\ I[\
ancial support[
Jones\ P[ G[\ Meyer!Base\ K[ and Erdbrugger\ C[
Ã
Ã
F[\ Or`anometallics\ 0877\ 6\ 886[
03b[ Vicente\ J[\ Chicote\ M[ T[ and Lagunas\ M[ C[\
Inor`[ Chem[\ 0882\ 21\ 2637[
04[ Hathaway B[ J[ and Underhill\ A[ E[\ J[ Chem[
Soc[\ 0850\ 2980[
05a[ Schmidbaur\ H[ and Franke\ R[\ An`ew[ Chem[\
0862\ 74\ 338[
05b[ Schmidbaur\ H[ and Franke\ R[\ An`ew[ Chem[
Int[ Ed[ En`l[\ 0862\ 01\ 305[
05c[ Schmidbaur\ H[ and Franke\ R[\ Inor`[ Chim[
Acta\ 0864\ 02\ 74[
05d[ Schmidbaur\ H[ and Franke\ R[\ Chem[ Ber[\
0864\ 097\ 0210[
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