Synthesis and crystallographic characterisation of silver complexes with the ligand diferrocenylphenylphosphine

Article abstract of DOI:10.1016/S0277-5387(98)00129-6

Diferrocenylphosphine (PFc₂Ph) reacts with Ag(TfO) or [Ag(TfO)(PR₃)] (TfO = trifluoromethanesulfonate) to afford the three-coordinate complexes [Ag(TfO)(PFc₂Ph)₂] or [Ag(TfO)(PFc₂Ph)(PR₃)]

Full text of DOI:10.1016/S0277-5387(98)00129-6

Polyhedron Vol[ 06\ No[ 10\ pp[ 2570Ð2577\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] S9166Ð4276"87#99018Ð5
Synthesis and crystallographic characterisation
of silver complexes with the ligand
diferrocenylphenylphosphine
M[ Concepcion Gimeno\a Peter G[ Jones\b Antonio Lagunaaꢁ
ꢀ
and Cristina Sarrocaa
aDepartamento de Qu(mica Inorganica\ I[C[M[A[ Universidad de Zaragoza!CSIC E!49998 Zaragoza\
ꢀ
ꢀ
Spain
bInstitut fur Anorganische und Analytische Chemie der Technischen Universitat\ Postfach 2218\ D!27912
Ã
Ã
Braunschweig\ Germany
"Received 00 February 0887^ accepted 16 March 0887#
Abstract*Diferrocenylphosphine "PFc1Ph# reacts with Ag"TfO# or ðAg"TfO#"PR2#Ł "TfO
~uoromethanesulfonate# to a}ord the three!coordinate complexes ðAg"TfO#"PFc1Ph#1Ł
ꢂ
tri!
or
ðAg"TfO#"PFc1Ph#"PR2#Ł "PR2ꢂPPh1Me\ PPh2#\ respectively[ The complex ðAg"TfO#"PFc1Ph#1Ł further reacts
−
with bidentate ligands\ such as bis"diphenylthiophosphoryl#methane "dptpm# or S1CNEt1 leading to the
cationic\ ðAg"PFc1Ph#1"dptpm#ŁTfO\ or neutral\ ðAg"S1CNEt1#"PFc1Ph#1Ł\ four!coordinate complexes[ The reac!
tion with 0\09!phenanthroline "phen# gives to the four!coordinate ðAg"TfO#"PFc1Ph#"phen#Ł[ Þ 0887 Elsevier
Science Ltd[ All rights reserved[ Þ 0887 Elsevier Science Ltd[ All rights reserved
Keywords] Silver^ Ferrocene^ Diferrocenylphenylphosphine
———————————————————————————————————————————————
The study of the coordination chemistry of fer!
rocenylphosphines\ such as the diphosphine 0\0?!
RESULTS AND DISCUSSION
The reaction of Ag"TfO# "TfO
ꢂ
tri!
diferrocenyl!
phenylphosphine "PFc1Ph# in diethyl ether\ in a 0]1
molar ratio\ gives suspension from which
bis"diphenylphosphino#ferrocene\ has attracted
a
~uoromethanesulfonate#
with
great deal of interest because the resultant complexes
often _nd applications in homogeneous catalysis\
in organic synthesis\ manipulation of materials and
production of _ne chemicals ð0\ 1Ł[ However\
diferrocenylphenylphosphine "PFc1Ph#\ although
synthesised more than three decades ago\ by inter!
action of ferrocene with dichlorophenylphosphine in
the presence of anhydrous aluminium chloride ð2Ł\ has
scarcely been studied[ Only very few complexes\ such
as ðM"CO#4"PFc1Ph#Ł "MꢂMo or W#\ ðCoMe
"DH#1"PFc1Ph#Ł "DH ꢂ dimethylglioximate#\ ðNi
"acac#1"PFc1Ph#Ł ð3Ł or the gold derivative
a
ðAg"TfO#"PFc1Ph#1Ł 0 can be isolated "Scheme 0#[
Other mononuclear complexes with two di}erent
phosphines\ ðAg"TfO#"PFc1Ph#"PR2#Ł "PR2ꢂPPh1Me
1\ PPh2 2#\ can be prepared by reaction of
ðAg"TfO#"PR2#Ł with the ferrocenylphosphine in
dichloromethane[ Complexes 0Ð2 are yellow solids\
air! and moisture stable[ They behave as 0]0 elec!
trolytes in acetone solution\ which con_rms an ionic
nature\ ðAg"PFc1Ph#"PR2#ŁTfO\ in solution[ In the IR
spectra\ the tri~uoromethanesulfonate group gives
ðAuCl"PFc1Ph#Ł ð4Ł\ have been reported\ but no silver rise to strong absorptions at 0514 "br# ðn"SO2#Ł\ 0114
derivative has been described so far[
ðnsym"CF2#Ł and 0448 ðnas"CF2#Ł cm−0
[
In the positive!ion liquid secondary ion mass spec!
tra "LSIMS# the cation peaks ðAg"PFc1Ph#"PR2#Ł¦
appear at m:z 0952 "0\ 49# and 736 "2\ 46)#[ Addition!
ally\ other fragments in the spectrum of 2 correspond
to ðAg"PPh2#1Ł¦ "522\ 74# and ðAg"PFc1Ph#1Ł¦ "0952\
14)#[
Here we report on the synthesis of mononuclear
three! or four coordinate silver"I# complexes that con!
tain one or two diferrocenylphenylphosphine ligands[
ꢁ Author to whom correspondence should be addressed[
Fax] ¦23 865 650076^ E!mail] alagunaÝposta[unizar[es
2570

2571
M[ C[ Gimeno et al[
Scheme 0[ "i# 0:1 Ag"TfO# or ðAg"TfO#"PR2#Ł\ "ii# 0¦P"S#Ph1CH1PPh1"S# or NaS1CNEt1\ "iii# 0¦phen[
0
Ä
The H NMR spectra of complexes 0Ð2 show the 1[379"0# A and slightly longer than those found in
four di}erent protons of the P"C4H3# rings as four ðAg1"PPh2#1"SPPh1CHPPh1CHCO1Me#ŁClO3\ 1[261"2#
Ä
multiplets or as a broad multiplet and the equivalent and 1[393"2# A ð6Ł[ The AgÐO bond length of 1[234"6#
Ä
protons of the C4H4 rings as a singlet "see Table 0#[ A is smaller than in the preceding dinuclear com!
Ä
In the spectrum of complex 2 the resonances due to pound\ 1[377"6# A ð6Ł\ but longer than in
complex 0 are also present[ In the 20P"0H# NMR spec! ðAg"NO2#"3!NO1C4H3NO#1Ł\ 1[253"2# and 1[207"2# A
Ä
trum of 0\ CDCl2 at −44>C\ two doublets are ð7Ł[ The cyclopentadienyl rings are as expected parallel
observed as a consequence of chemically equivalent and planar[ The rings are staggered by 02\ 07 and 02>
phosphorus atoms coupled to 096Ag and 098Ag nuclei[ for Fe"1#\ Fe"2# and Fe"3#\ respectively\ but by 18> for
Complexes 1 and 2 present an AB system\ both Fe"0#\ around the Cp = = = Cp axis "Cp ꢂ centre of
coupled to the two silver nuclei "Table 0#[ In the spec! cyclopentadienyl ring# de_ned by the torsion angles
trum of 2 the resonances due to complex 0 and CÐCpÐCpÐC[ The FeÐCp distances are in the range
ðAg"PPh2#1Ł¦ ðtwo doublets at d −2[1\ J"AgP# 593[2\ 0[528"2#Ð0[549"2# A[
Ä
413[9 HzŁ are also observed\ indicating the existence
We have studied the reactivity of complex 0 with
of a ligand exchange equilibrium of 2 and the cor! bidentate ligands such as bis"diphenylthio!
responding homoleptic species\ although complex 2 is phosphoryl#methane "dptpm#\ S1CNEt−1 "from NaS1
predominant[ In complex 1 only signals of very low CNEt1# or 0\09!phenanthroline "phen#[ Treatment
intensity at
d
−1 "ðAg"PFc1Ph#1Ł¦# and −3 of equimolecular amounts of 0 with the _rst two
"ðAg"PPh1Me#1Ł¦# are present[
ligands a}ords the four!coordinate cationic or neutral
The structure of complex 0 was con_rmed by X!ray complexes\ ðAg"PFc1Ph#1"dptpm#ŁTfO "3# and
di}raction analysis[ The molecule is shown in Fig[ 0\ ðAg"S1CNEt1#"PFc1Ph#1Ł "4#[ They are air! and moist!
with selected bond lengths and angles in Table 1[ ure stable yellow solids[ The IR spectrum of 3 shows
The tri~uoromethanesulfonate is coordinated by one bands at 0147 "s\ br#\ 0113 "s# and 0046 "s# cm−0\ from
oxygen to the silver atom[ The silver presents a some! the TfO anion\ and the n"P
what distorted trigonal!planar coordination\ prob! 446 "m# cm−0[ A band at 0404 "m# cm−0 in the IR spec!
ably due to the steric requirements of the phosphines\ trum of 4 is attributable to n"C N# of the dithi!
1
S# vibration appears at
1
with angles P"1#ÐAgÐP"0# of 024[19"5#\ O"0#ÐAgÐP"0# ocarbamate ligand[ In the LSIMS spectra the
of 093[5"1# and O"0#ÐAgÐP"1# of 019[1"1#>[ The silver molecular peak does not appear\ but the peaks
atom lies only 9[90 A out of the plane of the two assigned to the fragments ðAg"PFc1Ph#"L!L#Ł¦ at m:z
Ä
phosphorus and oxygen atoms[ The AgÐP distances 0924 "0\ 49# and 736 "2\ 46)# are present[ Complex 3
Ä
ð1[349"1# and 1[334"1# AŁ are similar to those found is an 0]0 electrolyte in acetone solution\ but 4 behaves
in other tri!coordinate silver complexes as nonconductor in solution[
ðAg"dppf#"PPh2#ŁClO3 ðdppfꢂ0\0?!bis"diphenylpho!
sphino#ferroceneŁ ð5Ł which range from 1[313"0# to the expected four resonances for the P"C4H3# protons
0
The H NMR spectra of complexes 3 and 4 show

Synthesis and crystallographic characterisation of silver complexes
2572
Table 0[ 0H and 20P!"0H# NMR data for complexes 0Ð5
0H
20P
L
Complex
P"C4H3# "C4H4#
L
PFc1Ph
0 ðAg"TfO#"PFc1Ph#1Ł
3[16"m# 3[96"m#
3[35"m#
3[41"m#
−1"dd#a
J"AgP# 466[9\
490[0
3[56"m#
3[06"m# 2[89"m# 1[15"s#
1 ðAg"TfO#"PFc1Ph#"PPh1Me#Ł
2 ðAg"TfO#"PFc1Ph#"PPh2#Ł
3 ðAg"PFc1Ph#1"dptpm#ŁTfO
4 ðAg"S1CNEt1#"PFc1Ph#1Ł
5 ðAg"TfO#"PFc1Ph#"phen#Ł
−1a
−2[7
3[17"m#
3[23"m#
3[26"m#
3Ð4"m#
6Ð7"m#
J"AB# 24[7
J"AgP# 592[2\
408[7
J"AgP# 455[9\ 369[1
00[7
3[93"m# 6Ð7"m#
00[94a
J"AB# 24[7
J"AgP# 593[2\
333[5
J"AgP# 471[8\ 311[1
34[7"s#
3[98"m# 3[93"m# 3[46"t#
3[18"m#
3[25"m#
3[39"m#
3[4"dd#b
J"PH# 03[2
J"AgP# 539[8\
444[6
3[97"m# 3[09"m# 0[26"t#
6[0 "dd#b
J"AgP# 487[0\
406[7
3[29"m#
3[20"m#
3[23"m#
3[96"q#
J"HH# 5[85
3[07"m# 3[94"m# 6[33"m#
−4[3"d\ br#a
3[11"m#
3[39"m#
3[32"m#
6[83"d#
7[45"d#
8[21"m#
Javer[ 331
a Recorded in CDCl2 at −44>C\ b Recorded in "CD2#1CO at −74>C\ coupling constant in Hz^ s ꢂ singlet\ d ꢂ doublet\
dd ꢂ two doublets\ t ꢂ triplet\ m ꢂ multiplet\ br ꢂ broad[
Fig[ 0[ The molecule of complex 0 in the crystal showing the atom!numbering scheme\ radii are arbitrary[ H atoms are
omitted for clarity[

2573
M[ C[ Gimeno et al[
Ä
Table 1[ Selected bond lengths ðAŁ and angles ð>Ł for complex 0[
AgÐO"0#
AgÐP"0#
1[234"6#
1[349"1#
0[701"5#
0[792"5#
0[713"5#
019[1"1#
024[19"5#
AgÐP"1#
1[334"1#
0[794"6#
0[718"5#
0[701"5#
0[288"6#
093[5"1#
P"0#ÐC"00#
P"0#ÐC"40#
P"1#ÐC"30#
SÐO"0#
O"0#ÐAgÐP"0#
C"00#ÐP"0#ÐC"10# 091[8"2#
C"10#ÐP"0#ÐC"40# 094[1"2#
P"0#ÐC"10#
P"1#ÐC"20#
P"1#ÐC"50#
O"0#ÐAgÐP"1#
P"1#ÐAgÐP"0#
C"00#ÐP"0#ÐC"40# 092[1"2#
C"00#ÐP"0#ÐAg
C"40#ÐP"0#ÐAg
C"20#ÐP"1#ÐC"50# 092[4"2#
019[8"1#
001[4"1#
C"10#ÐP"0#ÐAg
C"20#ÐP"1#ÐC"30# 090[4"2#
C"30#ÐP"1#ÐC"50# 092[3"2#
009[5"1#
C"20#ÐP"1#ÐAg
C"50#ÐP"1#ÐAg
029[9"1#
094[6"1#
C"30#ÐP"1#ÐAg
SÐO"0#ÐAg
098[7"1#
014[9"3#
and a singlet for the C4H4 rings "Table 0#[ The CH1 TfO−[ In the LSIMS spectrum the cation peak
groups of 3 appears as a triplet at 3[46 ppm ðJ"PH#\ ðAg"PFc1Ph#"phen#Ł¦ appears at m:z 654 as the most
03[2 HzŁ and ethyl groups of 4 are present as a quartet intense one[
0
"CH1\ 3[96 ppm\ J"HH# 5[85 Hz# and a triplet "CH2\
The H NMR spectrum of 5 shows the expected
0[26 ppm#[ The 20P"0H# NMR spectrum of 3\ resonances of the ferrocenylphosphine "Table 0# and
"CD2#1CO at −74>C\ shows a singlet for the two phos! four multiplets at 6[33\ 6[83\ 7[45 and 8[21 ppm due
phorus of the diphosphine and two doublets for the to the eight protons of the phenanthroline[ The phos!
phosphorus of the ferrocenylphosphine coupled with phorus atom appears as a broad doublet "CDCl2\
the 096Ag and 098Ag nuclei[ In complex 4 only the −44>C#\ due to the coupling with the silver nuclei\ in
resonance due to the phosphorus coupled to the silver the 20P"0H# NMR spectrum[
nuclei "two doublets# is observed[
The molecule of complex 5 is shown in Fig[ 2 with
The crystal structure of complex 4 has been estab! selected bond lengths and angles in Table 3[ The silver
lished by X!ray di}raction[ The compound crystallises atom presents a distorted tetrahedral geometry\ lying
Ä
as a chloroform solvate[ The molecule is shown in Fig[ 9[28 A out of the plane formed by the two nitrogen
1\ with selected bond lengths and angles in Table 2[ and phosphorus atoms in the direction of the tri~ate
Ä
The silver atom is coordinated to two phosphines oxygen O"0#\ with AgÐO"0# 1[515"2# A[ The inter!
and one chelating dithiocarbamate ligand and has a planar angle between AgN"0#N"1# and AgPO"0# is
distorted tetrahedral geometry[ The distortion arises 77>[ The restricted {{bite|| of the phenanthroline\ N"0#Ð
from the restricted bite of the dithiocarbamate\ S"0#Ð AgÐN"1# 61[01"09#>\ represents one major deviation
Ä
AgÐS"1# 56[39"5#>\ whereas the other angles are wider from ideal geometry[ The AgÐP bond\ 1[2334"01# A\ is
than ideal\ P"1#ÐAgÐS"1# 020[62"6# or P"0#ÐAgÐS"0# shorter than in complex 0 or in other three!coordinate
015[76"6#>[ The dihedral angle between the planes AgÐ derivatives\ such as ðAg"dppf#"PPh2#ŁClO3\ 1[313"0# to
Ä
P"0#ÐP"1# and AgÐS"0#ÐS"1# is 55>[ The cyclo! 1[379"0# A ð5Ł\ or ðAg""PPh1#1C1B8H09#"PPh2#Ł\
Ä
pentadienyl rings of Fe"0#\ Fe"1#\ Fe"2# and Fe"3# are 1[2863"09# to 1[3831"09# A ð00Ł\ re~ecting the cor!
staggered by 09\ 1\ 08 and 04>\ respectively\ around respondingly weak Ag coordination to N and O atoms
the Cp = = = Cp axis[ The AgÐP distances are 1[499"1# in 5[ The phenanthroline is asymmetrically coor!
Ä
and
1[417"1# A\
similar
to
those
in dinated through two di}erent AgÐN bonds of 1[178"2#
Ä
ðAg""PPh1#1C1B09H09#"dptpm#ŁClO3\ 1[415"1# and and 1[240"2# A which are of the same order as those
Ä
1[421"1# A ð8Ł\ or in other four!coordinate complexes\ found in other phenanthroline complexes\ such as
such as ðAg"dppe#1Ł¦ ð09Ł[ However the two di}erent ðAg""PPh1#1C1B09H09#"phen#ŁClO3 ð8Ł or ðAg"dppf#
Ä
AgÐS distances\ 1[594"1# and 1[628"1# A\ are longer "phen#ŁClO3 ð5Ł[ The shorter AgÐN distance is asso!
than in ðAg""PPh1#1C1B09H09#"dptpm#ŁClO3\ 1[439"1# ciated with the widest angle\ PÐAgÐN"0# 031[00"6#>[
Ä
and 1[477"1# A ð8Ł[
The ferrocene systems display twists of 6 and 06>
Complex 0 reacts with equimolecular amounts of for Fe"0# and Fe"1#\ respectively[
0\09!phenanthroline in a di}erent way^ substitution
of one ferrocenylphosphine is now observed to give
ðAg"TfO#"PFc1Ph#"phen#Ł "5#[ Complex 5 is an air!
and moisture stable light orange solid[ It behaves General
as an 0]0 electrolyte in acetone solution\ which indi!
EXPERIMENTAL
cates the dissociation of the tri~uoromethanesul!
Infrared spectra were recorded in the range 3999Ð
fonate ligand to give the ions ðAg"PFc1Ph#"phen#Ł¦ 199 cm−0 on a Perkin!Elmer 772 spectrophotometer

Synthesis and crystallographic characterisation of silver complexes
2574
Fig[ 1[ Molecular structure of complex 4 in the crystal[ H atoms are omitted for clarity[
Ä
Table 2[ Selected bond lengths ðAŁ and angles ð>Ł for complex 4[
AgÐP"0#
AgÐS"0#
P"0#ÐC"0#
P"0#ÐC"30#
P"1#ÐC"20#
S"0#ÐC"59#
NÐC"59#
NÐC"50#
P"0#ÐAgÐP"1#
P"1#ÐAgÐS"0#
P"1#ÐAgÐS"1#
C"0#ÐP"0#ÐAg
C"30#ÐP"0#ÐAg
C"20#ÐP"1#ÐAg
C"59#ÐS"0#ÐAg
C"59#ÐNÐC"52#
C"52#ÐNÐC"50#
NÐC"59#ÐS"0#
NÐC"50#ÐC"51#
1[499"1#
1[594"1#
0[688"6#
0[742"6#
0[712"6#
0[622"7#
0[239"8#
0[371"8#
004[84"6#
094[69"6#
020[62"6#
005[4"1#
001[6"1#
019[9"2#
78[0"2#
AgÐP"1#
AgÐS"1#
1[417"1#
1[628"1#
0[700"6#
0[796"6#
0[724"6#
0[610"7#
0[349"09#
P"0#ÐC"00#
P"1#ÐC"10#
P"1#ÐC"40#
S"1#ÐC"59#
NÐC"52#
P"0#ÐAgÐS"0#
P"0#ÐAgÐS"1#
S"0#ÐAgÐS"1#
C"00#ÐP"0#ÐAg
C"10#ÐP"1#ÐAg
C"40#ÐP"1#ÐAg
C"59#ÐS"1#ÐAg
C"59#ÐNÐC"50#
NÐC"59#ÐS"1#
S"1#ÐC"59#ÐS"0#
NÐC"52#ÐC"53#
015[75"6#
092[95"6#
56[39"5#
007[8"1#
006[8"1#
001[0"1#
74[9"2#
019[8"6#
010[3"5#
007[3"3#
001[2"6#
011[4"6#
005[5"5#
019[0"5#
003[8"6#
using Nujol mulls between polyethylene sheets[ Con! on a Varian Unity 299 spectrometer and a Bruker
ductivities were measured in ca[ 4×09−3 mol dm−2 ARX 299 spectrometer in CDCl2 or "CD2#1CO[
solutions with a Philips 8498 conductimeter[ C and H Chemical shifts are cited relative to SiMe3 "0H\ exter!
analyses were carried out with a Perkin!Elmer 1399 nal# and 74) H2PO3 "20P\ external#[ The starting com!
microanalyser[ Mass spectra were recorded on a VG plexes ðAg"TfO#"PR2#Ł "PR2ꢂPPh1Me\ PPh2# where
autospec\ with the LSIMS technique\ using nitro! prepared by reaction of equimolar amounts of
benzyl alcohol as matrix[ NMR spectra were recorded Ag"TfO# and the ligand PR2 in dichloromethane[

2575
M[ C[ Gimeno et al[
Fig[ 2[ The molecule of complex 5 in the crystal[ H atoms are omitted for clarity[
Ä
Table 3[ Selected bond lengths ðAŁ and angles ð>Ł for complex 5[
AgÐN"0#
AgÐN"1#
PÐC"10#
PÐC"20#
N"0#ÐC"09B#
N"1#ÐC"09A#
C"2#ÐC"3#
C"3A#ÐC"09B#
C"4#ÐC"5#
C"5A#ÐC"6#
C"6#ÐC"7#
C"09A#ÐC"09B#
N"0#ÐAgÐP
PÐAgÐN"1#
PÐAgÐO"0#
C"10#ÐPÐC"00#
C"00#ÐPÐC"20#
C"00#ÐPÐAg
C"1#ÐN"0#ÐC"09B#
C"09B#ÐN"0#ÐAg
C"8#ÐN"1#ÐAg
N"0#ÐC"1#ÐC"2#
C"2#ÐC"3#ÐC"3A#
C"3#ÐC"3A#ÐC"4#
C"5#ÐC"4#ÐC"3A#
C"6#ÐC"5A#ÐC"09A#
C"09A#ÐC"5A#ÐC"5#
C"6#ÐC"7#ÐC"8#
N"1#ÐC"09A#ÐC"5A#
C"5A#ÐC"09A#ÐC"09B#
N"0#ÐC"09B#ÐC"09A#
1[178"2#
1[240"2#
0[799"2#
0[719"2#
0[251"3#
0[244"4#
0[248"5#
0[309"4#
0[231"5#
0[391"5#
0[252"5#
0[324"4#
0[31[00"6#
024[90"6#
009[08"6#
090[1"1#
094[94"03#
004[43"00#
007[2"2#
005[2"1#
016[4"2#
012[4"3#
008[8"3#
012[4"3#
010[1"3#
006[2"3#
008[1"3#
007[5"3#
011[1"2#
008[0"2#
007[2"2#
AgÐP
AgÐO"0#
PÐC"00#
1[2334"10#
1[515"2#
0[799"2#
0[205"3#
0[215"3#
0[283"4#
0[284"5#
0[322"4#
0[310"5#
0[306"4#
0[283"4#
N"0#ÐC"1#
N"1#ÐC"8#
C"1#ÐC"2#
C"3#ÐC"3A#
C"3A#ÐC"4#
C"5#ÐC"5A#
C"5A#ÐC"09A#
C"7#ÐC"8#
N"0#ÐAgÐN"1#
N"0#ÐAgÐO"0#
N"1#ÐAgÐO"0#
C"10#ÐPÐC"20#
C"10#ÐPÐAg
C"20#ÐPÐAg
C"1#ÐN"0#ÐAg
C"8#ÐN"1#ÐC"09A#
C"09A#ÐN"1#ÐAg
C"3#ÐC"2#ÐC"1#
C"3#ÐC"3A#ÐC"09B#
C"09B#ÐC"3A#ÐC"4#
C"4#ÐC"5#ÐC"5A#
C"6#ÐC"5A#ÐC"5#
C"7#ÐC"6#ÐC"5A#
N"1#ÐC"8#ÐC"7#
N"1#ÐC"09A#ÐC"09B#
N"0#ÐC"09B#ÐC"3A#
C"3A#ÐC"09B#ÐC"09A#
61[01"09#
89[17"8#
81[52"09#
091[9"1#
004[62"00#
004[26"01#
014[3"1#
007[0"2#
003[1"1#
007[7"3#
006[7"2#
007[6"3#
010[6"3#
012[4"3#
019[1"3#
012[6"3#
007[6"2#
010[5"2#
019[0"2#

Synthesis and crystallographic characterisation of silver complexes
2576
Table 4[ Details of data collection and structure re_nement for the complexes 0\ 4 and 5[
Compound
Chemical Formula
Crystal habit
0
C42H35AgF2Fe3O2P1S
yellow prism
9[69×9[49×9[19
Triclinic
PÞ0
4 = CHCl2
C47H46AgCl2Fe3NP1S1
yellow plate
9[39×9[39×9[09
Triclinic
PÞ0
5
C28H20AgF2Fe1N1O2PS
yellow plate
9[39×9[29×9[04
Triclinic
PÞ0
Crystal size:mm
Crystal system
Space group
Ä
a:A
00[608"3#
02[484"3#
04[587"3#
62[45"2#
65[47"2#
78[47"2#
1217[6"01#
1
00[284"1#
01[043"1#
19[929"2#
66[660"03#
68[056"09#
66[870"03#
1510[5"6#
1
00[041"3#
00[619"3#
03[913"4#
66[84"2#
78[15"2#
79[26"2#
0657[7"00#
1
Ä
b:A
Ä
c:A
a:>
b:>
g:>
2
Ä
U:A
Z
Dc:g cm−2
0[629
0[576
0[619
M
F"999#
0102[06
0113
0220[62
0241
804[15
819
T:>C
−099
−099
−029
1umax:>
49
49
44
m"Mo!Ka#:cm−0
Transmission
No[ of re~ections measured
No[ of unique re~ections
Rint
07[9
9[64Ð9[82
7503
7066
9[923
06[71
*
8309
7853
04[10
9[637Ð9[775
7395
7023
9[016
9[957
Ra "F×3s"F##
wRb "F1\ all re~[#
No[ of re~ections used
No[ of parameters
No[ of restraints
Sc
9[943
9[034
7066
593
341
0[905
0[152
9[943
9[012
7814
531
367
9[840
9[7
9[927
9[978
7090
358
9
0[985
9[330
−2
Ä
Max[ Dr:eA
a R "F#ꢂS>Fo=−=Fc>:S=Fo=\
b
wR "F1#ꢂðS"w"Fo1−F1c#1#:S"w"Fo1#1#Ł9[4^ w−0ꢂs1"Fo1#¦"aP#1¦bP\ where PꢀðFo1¦1F1cŁ:2 and a and b are constants
adjusted by the program
c SꢀðS"w"F1o−F1c#1#:"n−p#Ł9[4\ where n is the number of data and p the number of parameters[
ðA`"TfO#"PFc1Ph#1Ł "0#
"Found] C\ 41[94^ H\ 2[84^ S\ 2[3[ Calc[ for
C39H25AgF2Fe1O2P1S] C\ 41[24^ H\ 2[74^ S\ 2[3)#[
To a suspension of PFc1Ph ð2Ł "9[985 g\ 9[1 mmol# Complex 2] Yield 75)\ LM 000 V−0 cm1 mol−0
in diethyl ether "19 cm2# was added Ag"TfO# "9[910 g\ "Found] C\ 43[0^ H\ 2[74^ S\ 2[94[ Calc[ for
9[0 mmol#[ The mixture was stirred for 0 h and then C34H27AgF2Fe1O2P1S] C\ 43[14^ H\ 2[74^ S\ 2[1)#[
_ltered[ The product was dissolved in dichlo!
romethane "19 cm2# and the solution was concentrated
ðA`"PFc1Ph#1"dptpm#ŁTfO "3#
to ca[ 4 cm2[ Addition of diethyl ether "04 cm2# gave
complex 0 as a yellow solid[ Yield 68)\ LM
010 V−0 cm1 mol−0 "Found] C\ 41[94^ H\ 2[4^ S\ 2[9[
Calc[ for C42H35AgF2Fe3O2P1S] C\ 41[4^ H\ 2[6^ S\
1[5)#[
To a solution of complex 0 "9[010 g\ 9[0 mmol# in
dichloromethane was added
"19 cm2#
P"S#Ph1CH1PPh1"S# ð01Ł "9[934 g\ 9[0 mmol# and the
mixture was stirred for 0 h[ The solution was con!
centrated to ca[ 4 cm2 and addition of diethyl ether
"04 cm2# gave complex 3 as a yellow solid[ Yield 59)\
LM 039 V−0 cm1 mol−0 "Found] C\ 45[14^ H\ 3[04^ S\
5[2[ Calc[ for C67H57AgF2Fe3O2P3S2] C\ 45[24^ H\ 3[0^
S\ 4[7)#[
ðA`"TfO#"PFc1Ph#"PR2#Ł "PR2ꢂPPh1Me "1#\ PPh2 "2##
To a solution of PFc1Ph "9[937 g\ 9[0 mmol# in
dichloromethane "14 cm2# was added ðAg"TfO#"PR2#Ł
"9[935 g\ PR2ꢂPPh1Me^ 9[941\ PR2ꢂPPh2^ 9[0 mmol#
and the mixture was stirred for 0 h[ The solution was ðA`"S1CNEt1#"PFc1Ph#1Ł "4#
concentrated to ca[ 4 cm2 and addition of hexane
"04 cm2# gave complex 1 and 2 as a yellow solids[
To a dichloromethane solution "19 cm2# of complex
Complex 1] Yield 54)\ LM 095 V−0 cm1 mol−0 0 "9[010 g\ 9[0 mmol# was added NaS1CNEt1 "9[912 g\

2577
M[ C[ Gimeno et al[
9[0 mmol#[ The mixture was stirred for 3 h and then order "~exibility of coordination geometry at silver#[
_ltered o} to remove the sodium tri! Crystal data are given in Table 4[
~uoromethanesulfonate[ The solvent was evaporated
under vacuum to ca[ 4 cm2^ addition of diethyl ether
"04 cm2# a}orded complexes 4 as a yellow solid[ Yield
57) "Found] C\ 44[8^ H\ 3[2^ N\ 0[04^ S\ 4[0[ Calc[
for C46H45AgFe3NP1S1] C\ 45[34^ H\ 3[54^ N\ 0[04^ S\
4[1)#[
Acknowled`ements*We thank the Direccion General de
ꢀ
Investigacion Cientꢀ(_ca y Tecnica "No[ PB86!0909!C91!90#
ꢀ
ꢀ
and the Fonds der Chemischen Industrie for _nancial
support[
REFERENCES
ðA`"TfO#"PFc1Ph#"phen#Ł "5#
0[ Togni\ A[ and Hayashi\ T[\ Ed[\ Ferrocenes[
Homo`eneus Catalysis\ Or`anic Synthesis and
Materials Science\ VCH\ Weinheim\ Germany\
0884 "and references cited therein#[
1[ See for example "a# Cullen\ W[ R[ and Woollins\
J[ D[\ Coord[ Chem[ Rev[\ 0871\ 28\ 0^ "b# Hayashi\
T[ and Kumada\ M[\ Acc[ Chem[ Res[\ 0871\ 04\
284[
2[ Sollot\ G[ P[\ Mertwoy\ H[ E[\ Portnoy\ S[ and
Snead\ J[ L[\ J[ Or`[ Chem[\ 0852\ 17\ 0989[
3[ Kotz\ J[ C[ and Nivert\ C[ L[\ J[ Or`anomet[
Chem[\ 0862\ 41\ 276[
To a dichloromethane solution "19 cm2# of complex
0 "9[010 g\ 9[0 mmol# was added 0\09!phenanthroline
"9[907 g\ 9[0 mmol#[ The mixture was stirred for 0 h
and then the solution was concentrated under vacuum
to ca[ 4 cm2^ addition of diethyl ether "04 cm2# a}orded
complexes 5 as a light orange solid[ Yield 64)\ LM
039 V−0 cm1 mol−0 "Found] C\ 40[8^ H\ 2[34^ N\ 2[94^
S\ 2[64[ Calc[ for C28H20AgF2Fe1N1O2PS] C\ 41[5^ H\
2[3^ N\ 2[94^ S\ 2[4)#[
4[ Jones\ P[ G[\ Erdbrugger\ C[ F[\ Hohbein\ R[ and
Ã
Schwarzmann\ E[\ Acta Cryst[\ 0877\ C33\ 0291[
5[ Gimeno\ M[ C[\ Jones\ P[ G[\ Laguna\ A[ and
Sarroca\ C[\ J[ Chem[ Soc[\ Dalton Trans[\ 0884\
0362[
6[ Gimeno\ M[ C[\ Jones\ P[ G[\ Laguna\ A[ and
Villacampa\ M[ D[\ J[ Chem[ Soc[\ Dalton Trans[\
0884\ 794[
Crystal Structure Determinations
The crystals were mounted in inert oil on glass _bres
and transferred to the cold gas stream of a Siemens
R2 "0# or P3 "4# or a STOE Stadi3 "5# di}ractometers
equipped with an LT!1 low temperature attachment[
Data were collected using monochromated MoKa
7[ Aoyama\ T[\ Yamamaka\ M[ and Ohba\ S[\ Saito\
V[\ Acta Cryst[\ 0889\ C35\ 651[
Ä
radiation "lꢂ9[60962 A#[ Scan type v "0\4# or v:u "5#[
Cell constants were re_ned from setting angles "0\4#
or 2v angles of ca[ 59 re~ections in the range 1u 09Ð
14>[ Absorption corrections were applied on the basis
of C!scans "0\5#[ Structures were solved by the heavy!
atom method and re_ned on F1 using the program
SHELXL!82 ð02Ł[ All non!hydrogen atoms were
re_ned anisotropically[ Hydrogen atoms were
included using a riding model[ A system of restraints
to light!atom displacement!factor components was
used[ Special re_nement details for 0] The high dis!
placement parameters of O"0# may indicate some dis!
8[ Bembenek\ E[\ Crespo\ O[\ Gimeno\ M[ C[\ Jones\
P[ G[ and Laguna\ A[\ Chem[ Ber[\ 0883\ 016\ 724[
09[ Harker\ C[ S[ W[ and Tiekink\ E[ R[ T[\ J[ Coord[
Chem[\ 0889\ 10\ 176[
00[ Crespo\ O[\ Gimeno\ M[ C[\ Jones\ P[ G[ and
Laguna\ A[\ J[ Chem[ Soc[\ Dalton Trans[\ 0885\
3472[
01[ Davison\ A[ and Reger\ D[ L[\ Inor`[ Chem[\ 0860\
09\ 0856[
02[ Sheldrick\ G[M[\ SHELXL!82[ A pro`ram for
Crystal Structure Re_nement\ University of Got!
Ã
tingen\ Germany\ 0882[