Hydrocarbon bridged metal complexes, xliv. Donor-acceptor substituted Schiff bases of polyenes with transition metals

Article abstract of DOI:10.1016/S0277-5387(98)00290-3

Schiff bases 1-10 were obtained by condensation of L-valine and o-aminophenol with donor and ferrocenyl substituted carotinoid aldehydes. From these Schiff bases and chloro-bridged complexes [ (R₃P) (Cl)M(μ-Cl)]₂ (M=Pd, Pt), [ (η⁵-C₅Me₅) (Cl)Ir (μ-Cl)]₂ and [ (p-cymene) (Cl)Ru (μ-Cl)]₂ a series of mono and heterobimetallic compounds 11-45 was synthesized. The structures of [p-MeO-C₆H₄-CHN-C₆H₄-O-Ru (Cl) (p-cymene)] 16, [ferrocenyl-CHN-C₆H₄-O-Ir (Cl) (Cp*)] 23, [ (p-Me₂NC₆H ₄-CHCH-C(Me)CH-CHCH-CHC(Me)-CHN-C₆H₄-O-Pd (Cl)PEt₃] 42 and of the condensation product from [ (η⁶-aniline)Cr (CO)₃] with 9-ferrocenyl-2,7-dimethylnonatetraene-1-al 46 were determined by X-ray diffraction.

Full text of DOI:10.1016/S0277-5387(98)00290-3

\
PERGAMON
Polyhedron 07 "0888# 114Ð131
Hydrocarbon bridged metal complexes\ XLIV[ DonorÐacceptor
substituted Schi} bases of polyenes with transition metals0\ 1
Oliver Briel\ Armin Fehn\ Kurt Polborn2\ Wolfgang Beckꢀ
Institut fur Anorganische Chemie der Universitat\ Meiserstrasse 0\ D!79222 Munich\ Germany
Ã
Ã
Abstract
Schi} bases 0Ð09 were obtained by condensation of L!valine and o!aminophenol with donor and ferrocenyl substituted carotinoid
aldehydes[ From these Schi} bases and chloro!bridged complexes ð"R2P#"Cl#M"m!Cl#Ł1 "MꢁPd\ Pt#\ ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 and
ð"p!cymene#"Cl#Ru"m!Cl#Ł1 a series of mono and heterobimetallic compounds 00Ð34 was synthesized[ The structures of ðp!MeOÐ
C5H3ÐCH1NÐC5H3ÐOÐRu"Cl#"p!cymene#Ł 05\ ðferrocenylÐCH1NÐC5H3ÐOÐIr"Cl#"Cpꢀ#Ł 12\ ð"p!Me1NC5H3ÐCH1CHÐ
C"Me#1CHÐCH1CHÐCH1C"Me#ÐCH1NÐC5H3ÐOÐPd"Cl#PEt2Ł 31 and of the condensation product from ð"h5!aniline#Cr"CO#2Ł
with 8!ferrocenyl!1\6!dimethylnonatetraene!0!al 35 were determined by X!ray di}raction[ Þ 0888 Elsevier Science Ltd[ All rights
reserved[
Keywords] Schi} bases^ Polyenes^ Transition metal complexes
0[ Introduction
new non!linear optical materials ð44Ð46Ł[ No or weak
NLO responses could be measured ð45\46Ł[ Delaire syn!
thesized ferrocene containing Schi} base ligands which
showed enhanced non!linear optical responses after com!
plexation ð47Ł[ Organic Schi} bases of retinal show excep!
tional high NLO responses ð48Ð50Ł and an arylamine
derivative of retinal was used as ligand in a pyr!
azolylborate Mo"II# complex ð51Ł[ We wanted to combine
these _ndings\ and in continuation of our studies on
polyene bridged complexes of Schi} bases from vitamine
A dialdehydes ð52Ł synthesized new retinal containing
Schi} base complexes as well as further pushÐpull poly!
enes with Schi} base metal components as electron
accepting groups[
Recently unsymmetrically substituted dinuclear com!
plexes with organic p!electron bridges and complexes
with organic electron donating or accepting ligands have
found increasing attention due to their potential non!
linear optical properties ð1Ð3Ł[ A large number of unsym!
metrical s!acetylide bridged complexes have been
reported ð4Ð12Ł " for important symmetric conjugated
poly!yne bridged complexes see Refs[ ð13Ð25Ł#\ whereas
pure polyene bridged systems are rather rare ð26Ð33Ł[
Metal containing non!linear optical materials have vari!
ous advantages compared to pure organic materials\ as
the high polarizability of the d!electrons of the metals\
charge!transfer processes with large extinction
coe.cients\ or various reversible oxidation states of metal
centers may lead to large non!linear optical responses ð1Ð
3Ł[ The _rst ferrocene containing metal!organic com!
pound with second order non!linearities ð34Ł triggered
intensive investigations of metallocene compounds ð35Ð
46Ł[
1[ Results and discussion
We obtained the Schi} base compounds 0Ð09 by con!
densation of several unsaturated aldehydes with L!valine
and o!aminophenol[ Compound 2 ð53Ł was previously
reported ð54Ł[3 For the preparation of 3Ð6 L!valine is
dissolved in a NaOMe:MeOH solution\ then toluene and
the aldehydes are added[ After stirring for 01Ð13 h in the
dark the solvent is evaporated and ethanol is added[
Also Schi} base complexes have been synthesized as
ꢀ Corresponding author[ Fax] ¦38!78!489!1103[
0 Part XLIII see Bentele\ H[!J[ et al[\ Z[ Naturforsch[\ 0886\ 41b\ 0196
ð0Ł[
1 Dedicated to Professor Wolfgang Steglich on the occasion of his
54th birthday[
3 Schi} bases from ferrocenaldehyde and a!amino acids were used as
ligands[
2 X!ray structure determination[
9166!4276:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[
PII] S9166!4276 "87#99189!2

115
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
Compounds 3Ð6 precipitated as sodium salts after stirring
for 01Ð61 h[ Compounds 0Ð2\ 7 and 09 were synthesized
by heating the aldehydes and o!aminophenol in toluene\
and separating the produced water in a trap funnel[ Com!
pound 8 was obtained by stirring the aldehyde with o!
aminophenol and Na1SO3 in dichloromethane[ All new
compounds are hygroscopic and sensitive to light and
were stored in the dark under nitrogen[ In the IR spectra
of 0Ð2 and 7Ð09 intensive absorptions of the C1N and
C1C groups at ½0489Ð0519 cm−0 are characteristic[ For
3Ð6 intensive broad absorptions of the COO groups at
½0599Ð0559 cm−0 overlay the absorptions of the C1C
and C1N groups[ The appearance of one signal for the
imine group in the 0H NMR spectra at d¼7 ppm proves
the formation of only one stereoisomer "E or Z#[ All
other signals appear with the expected shifts and coupling
patterns[
vatochromism is observed for most complexes[ For exam!
ple complex 33 and 34 show negative solvatochromism\
and as the absorption at higher wavelengths is more
sensitive to di}erences in polarity we assign it to a MLCT
band[
A further heterobimetallic pushÐpull polyene complex
35 was obtained by condensation of 8!ferrocenyl!1\6!
dimethylnonatetraen!0!al
with
h5!anilintricarbon!
ylchromium in dichloromethane[ As expected three IR
bands of the carbonyl ligands are observed at 0762\ 0783
and 0850 cm−0[ The single signal for the imine proton in
the 0H NMR spectrum proves formation of a single
product "E or Z#[
1[0[ Crystal structural determinations of 05\ 12\ 31 and 35
Single crystals of 05\ 12 and 35 were obtained by
di}usion of n!pentane into a dichloromethane solution[
Structure 0[
Reactions of 0Ð09 with the chloro!bridged complexes
of palladium"II# and platinum"II# ð"R2P#"Cl#M"m!Cl#Ł1\
ð"h5!p!cymene#"Cl#Ru"m!Cl#Ł1 and with ð"h4!C4Me4#
"Cl#Ir"m!Cl#Ł1 in methanol gave the complexes 00Ð34[ The
complexes 14Ð17\ 20Ð23\ 31Ð34 with polyene components
are due to their donorÐacceptor substitution deep red to
black substances\ whereas compounds 18 and 29 and 24Ð
26\ substituted with weaker electron donating groups
appear as yellow to orange substances[
The crystal which was obtained for 31 by di}usion of n!
pentane into a dichloromethane:methanol solution was
the trans isomer and crystallized as 31=9[4CH2OH[ In all
cases the C1N bond has E con_guration and the bond
Ä
lengths between 0[157"3# and 0[184"3# A are typical for
C1N double bonds ð55\56Ł[ The iminophenolate ligand
in 05\ 12 and 31 deviates slightly from planarity[
However\ the _ve!membered ring is in an envelope con!
formation with a folding angle at the NÐO vector of
approximately 04> "05\ 12# and 17> "31#[ As a conse!
By coordination of the Schi} bases a characteristic
down_eld shift of the 0H NMR N1C"H# signals is
observed[ For the palladium"II# and platinum"II# com!
plexes formation of cis and trans isomers concerning the
NÐMÐL con_guration is observed[ The ratio of the iso!
mers could be obtained from the integral intensities of
Ä
quence of this folding\ the metal atoms lie ca[ 9[34 A "05#\
Ä
Ä
9[25 A "12# and 9[67 A "31# above the iminophenolate
plane[ In the latter case\ the PdÐPÐClÐOÐN unit\ which
is quite distorted from planarity\ includes an angle of 23>
with the plane of the chelate ligand[ The C1N bond is
always twisted out of the plane of the iminophenolate
ligand\ with twist angles of 7> "05#\ 09> "12# and 06> "31#[
Twisting is much larger in the {{aldehyde|| part\ with
torsion angles NÐCÐCÐC of ca[ 31> "05#\ 02>:17> "12# and
01>:05> "31#\ which implies that the metal cannot take
part in extended p!conjugation with the aro!
matic:polyene part of the molecule[
0
the two 20P NMR signals and of the imine H NMR
resonances which gave for each isomer a doublet with
3JHP coupling constants of ca[ 02 Hz "cis# and of ca[ 6 Hz
"trans#[ For the platinum complexes preferred formation
of the trans isomers was observed which is in accordance
with our previous work on similar complexes ð52Ł[ The
palladium complexes were formed with varying ratio of
the cis:trans isomers[ After complexation the 02C NMR
signals of the HC1N group are shifted down_eld by ca[
3Ð6 ppm due to the electron!withdrawing e}ect of the
complex fragment[ All complexes show intensive absorp!
tions in the UV:Vis spectra which can be attributed to
CT transitions of the donor acceptor groups[ Sol!
An interesting aspect of the ferrocenyl derivative 12 is
Ä
the fact that the imino carbon atom lies 9[07 A below the
cyclopentadienyl plane of the metallocene[ "See Fig[ 0Fig[
1\ Tables 0 and 1[#
The two phenyl rings at the ends of the Schi} base
ligands in 31 are canted by 07>[ This is not only a conse!

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
116
Structure 1[
Structure 2[

117
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
Structure 3[
quence of the aforementioned twist at the C1N bond\
but also of a second twist of 4[4> along the bond C07Ð
C08 between the planes C07ÐC16 and C02ÐC07[
molecules\ i[e[ the dipoles of the molecules compensate
each other in the crystal[
31 has a cut!o} in its UV:Vis spectrum beyond 649 nm[
Therefore a NLO measurement was not possible since the
compound absorbs light in the range of the detection region[
However a rough estimation of the NLO activity of the
compound is possible by calculating the bond length alter!
nation "BLA#[ This molecular parameter is de_ned as the
di}erence between the average carbonÐcarbon single and
double bond lengths in the polymethine backbone[ It was
shown theoretically and experimentally\ that there is a
relation between the _rst hyperpolarizability of donorÐ
acceptor substituted polyenes and their BLA coe.cients
An even larger twist angle of ca 03[4> within the poly!
ene skeleton is observed in the ferrocenylÐbenchrotenyl
complex 35[ This twist occurs along the bond C05ÐC06
between the planes N0ÐC09ÐC05 and C05ÐC08[ This lat!
ter plane includes an angle of ca[ 08> with the plane of
the cyclopentadienyl ring\ while the former is twisted out
of the plane of the aniline ligand by approximately 27>[
Again\ as a consequence of this multiple twisting\ the
aromatic ends of the polyene system cannot take part in
the p!conjugation[ In contrast to the _rst three structures\
the imino group takes part in the conjugation\ since the
torsion angle N0ÐC09ÐC00ÐC01 is only 4>[
For 05 and 12 the MÐCl\ MÐN\ MÐO "MꢁIr\ Ru#
bonds show no unusual behavior[ Lengths lie in the
expected regions ð55\56Ł[
Selected bond angles and bond lengths are summarized
in Table 2[ Figure 2 shows a distorted square planar
coordination "Cl#"P#Pd"O\N#[ The unit cell contains four
molecules with a head!to!tail arrangement of the
Ä
ð57Ð60Ł[ For compound 31 the BLA coe.cient is 9[988 A
describing a rather weak donorÐacceptor pair\ although
indicating some NLO activity[
The unit cell of 35 contains two molecules which are
arranged in a head!to!tail alignment[ In contrast McCle!
verty ð40Ł observed rod!like molecules with bulky sub!
stituents crystallizing in non head!to!tail con_gurations[
Ä
The BLA coe.cient results in 9[093 A referring to a weak
donorÐacceptor pair[ "See Fig[ 3\ Tables 3 and 4[#

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
118
Fig[ 0[ Molecular structure and atomic labelling scheme of 05[ 39) thermal ellipsoids are shown for the non!hydrogen atoms^ hydrogen atoms have
arbitrary radii[
Fig[ 1[ Molecular structure and atomic labelling scheme of 12[ 19) thermal ellipsoids are shown for the non!hydrogen atoms^ hydrogen atoms have
arbitrary radii[
Table 0
Ä
Selected bond lengths "A# and angles "># of 05
Ru"0A#ÐO"0A#
Ru"0A#ÐCl"0A#
N"0A#ÐC"5A#
O"0A#ÐRu"0A#ÐN"0A#
N"0A#ÐRu"0A#ÐCl"0A#
C"5A#ÐN"0A#ÐRu"0A#
1[934"1#
1[312"8#
0[322"3#
68[99"09#
78[97"7#
098[3"1#
Ru"0A#ÐN"0A#
N"0A#ÐC"6A#
1[022"2#
0[184"3#
O"0A#ÐRu"0A#ÐCl"0A#
C"6A#ÐN"0A#ÐRu"0A#
C"6A#ÐN"0A#ÐC"5A#
74[82"7#
020[3"1#
007[7"2#

129
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
Structure 4[
2[ Experimental
dꢁ7[53 "s\ 0H\ HC1N#\ 6[77 "d\ 1H\ 2Jꢁ7[4#\ 6[29Ð6[17
"m\ 0H#\ 6[19Ð5[78 "m\ 3H#\ 2[89 "s\ 2H\ CH2#[ C03H02NO1
"116[1#] calcd[ C 63[91\ H 4[62\ N 5[06^ found C 62[74\ H
4[75\ N 4[70[
All operations were carried out under nitrogen using
Schlenk technique[ Solvents were dried by distillation
from sodium:benzophenone or calcium hydride[ The
NMR spectra were recorded with a Jeol GSX 169 "0H]
169 MHz^ 02C] 57 MHz^ 20P] 098 MHz# or a Jeol EX 399
"0H] 399 MHz^ 02C] 099 MHz#[ IR] 4ZDX FT[ UV:Vis]
Philips PU 7609[ The starting complexes ð"R2P#"Cl#M"m!
Cl#Ł1 "MꢁPd\ Pt# ð61Ł\ ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 ð62Ł\
1 from ð"o\p!dimethoxy#benzaldehydeŁ and o!ami!
nophenol[ Yellow hygroscopic powder[ IR "KBr\ cm−0#]
0
nꢁ0507 vs\ 0599 s "C1N\ C1C#[ H NMR "169 MHz\
½
CDCl2#] dꢁ8[95 "s\ 0H\ CH1N#\ 7[01 "d\ 0H\ 2Jꢁ7[6#\
2
3
2
6[18 "dd\ 0H\ Jꢁ6[8\ Jꢁ0[4#\ 6[04 "ddd\ 0H\ Jꢁ6[4\
2Jꢁ6[9\ Jꢁ0[3#\ 5[88 "dd\ 0H\ Jꢁ7[9\ Jꢁ0[4#\ 5[78
3
2
3
2
2
3
2
ð"p!cymene#"Cl#Ru"m!Cl#Ł1
ð63Ł\
and
ðh5!anilineŁ
"ddd\ 0H\ Jꢁ6[6\ Jꢁ6[4\ Jꢁ0[3#\ 5[59 "dd\ 0H\ J
ꢁ7[5\ 3Jꢁ1[1#\ 5[38 "d\ 0H\ 3Jꢁ1[1#\ 2[89 "s\ 2H\ CH2#\
2[78 "s\ 2H\ CH2#[ C04H03NO2 "145[2#] calcd[ C 69[94\ H
4[72\ N 4[33^ found C 58[46\ H 4[83\ N 4[44[
chromiumtricarbonyl ð64Ł were prepared by literature
procedures[
0 from ð"p!methoxy#benzaldehydeŁ and o!amino!
phenol[ White powder[ IR "KBr\ cm−0#] nꢁ0513 vs\
2 from ferrocenealdehyde and o!aminophenol[ Dark
½
0590 s "C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#]
red powder[ IR "KBr\ cm−0#] nꢁ0505 vs\ 0482 vs\ 0471
½

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
120
Table 1
Selected bond lengths "A# and angles "># of 12
Ä
Ir"0#ÐO"0#
Ir"0#ÐCl"0#
N"0#ÐC"01#
O"0#ÐIr"0#ÐCl"0#
1[942"7#
1[288"2#
0[351"03#
73[4"2#
Ir"0#ÐN"0#
N"0#ÐC"06#
N"0#ÐIr"0#ÐCl"0#
O"0#ÐIr"0#ÐN"0#
1[093"8#
0[176"03#
78[6"2#
68[1"3#
Table 2
Selected bond distances "A# and bond angles "># for complex 31
Ä
Pd"0#ÐO"0#
Pd"0#ÐP"0#
N"0#ÐC"02#
N"1#ÐC"14#
C"19#ÐC"10#
C"07#ÐC"08#
C"05#ÐC"06#
C"03#ÐC"04#
O"0#ÐPd"0#ÐN"0#
N"0#ÐPd"0#ÐCl"0#
C"02#ÐN"0#ÐPd"0#
1[995"0#
1[1211"03#
0[172"5#
0[279"6#
0[228"7#
0[233"6#
0[231"6#
0[237"6#
79[40"03#
86[71"09#
023[1"2#
Pd"0#ÐN"0#
Pd"0#ÐCl"0#
N"0#ÐC"01#
1[020"3#
1[1834"02#
0[314"5#
0[344"6#
0[334"6#
0[324"6#
0[320"6#
0[336"5#
81[57"00#
019[5"3#
093[4"2#
C"10#ÐC"11#
C"08#ÐC"19#
C"06#ÐC"07#
C"04#ÐC"05#
C"02#ÐC"03#
O"0#ÐPd"0#ÐP"0#
C"02#ÐN"0#ÐC"01#
C"01#ÐN"0#ÐPd"0#
Fig[ 2[ Molecular structure and atomic labelling scheme of 31[ 19) thermal ellipsoids are shown for the non!hydrogen atoms^ hydrogen atoms have
arbitrary radii[
vs "C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#] dꢁ7[47
"s\ 0H\ CH1N#\ 6[12Ð5[77 "m\ 3H\ Har#\ 3[79 "s\ 1H\
C4H3#\ 3[41 "s\ 1H\ C4H3#\ 3[11 "s\ 4H\ C4H4#[ C06H04N!
OFe "294[05#] calcd[ C 55[76\ H 3[83\ N 3[48^ found C
55[39\ H 4[92\ N 3[32[
CD2OD#] dꢁ6[73 "s\ 0H\ HC1N#\ 5[80Ð5[14 "m\ 5H\
Hol#\ 3[33 "d\ 2Jꢁ0[6 Hz\ 1H\ C4H3#\ 3[16 "ct\ 2Jꢁ0[6 Hz\
1H\ C4H3#\ 3[98 "s\ 4H\ C4H4#\ 1[15 ðm\ 0H\ CH"CH2#1Ł\
1[99 "s\ 5H\ CH2#\ 9[84:9[71 ðd\ 2Jꢁ5[5 Hz\ 2H\ d\ 2J
ꢁ5[5 Hz\ 2H\ CH"CH2#1Ł[ 02C NMR "099[4 MHz\
CD2OD#] dꢁ079[16 "CO1#\ 056[94 "HC1N#\ 039[65:
028[30:025[58:023[56:020[84:029[84:018[96:017[89 "Col#\
3 from 8!ferrocenyl!1\6!dimethylnonatetraenal ð65Ł
and L!valine[ Orange Powder[ 0H NMR "169 MHz\

121
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
Structure 5[
Structure 6[
75[22 "CHCO1#\ 73[89 "ipso!C4H3#\ 69[14 "C4H4#\
69[23:56[85 "C4H3#\ 21[60 ðCH"CH2#1Ł\ 19[38:08[46
ðCH"CH2#1Ł\ 01[70:01[11 "CH2#[
1[14 ðm\ 0H\ CH"CH2#1Ł\ 1[94:1[91 "each s\ 5H\ CH2#\
9[84:9[71 ðd\ 2Jꢁ5[6 Hz\ 2H\ d\ 2Jꢁ5[6 Hz\ 2H\
CH"CH2#1Ł[
4 from 8!phenyl!1\6!dimethylnonatetraenal ð65Ł and L!
5
from
8!ð"3!dimethylamino#!phenylŁ!1\6!dime!
valine[ Yellow hygroscopic powder[ IR "Nujol\ cm−0#] n
thylnonatetraenal ð66\ 67Ł and L!valine[ Dark red powder[
½
ꢁ0593 vs\ br "CO1\ C1N\ C1C#[ 0H NMR "169 MHz\
IR "KBr\ cm−0#] nꢁ0509 vs "CO \ C1N#\ 0478 sh
½
1
2
0
CD2OD#] dꢁ6[75 "s\ 0H\ HC1N#\ 6[36 "d\ Jꢁ6[4 Hz\
"C1C#[ H NMR "169 MHz\ CD2OD#] dꢁ6[73 "s\ 0H\
HC1N#\ 6[39Ð5[51 "m\ 09H\ Hol\ Har#\ 1[83 ðs\ 5H\
N"CH2#1Ł\ 1[19 ðm\ 0H\ CH"CH2#1Ł\ 1[91:1[90 "each s\ 5H\
2
2
1H\ Har#\ 6[29 ðd"d#\ Jꢁ6[4 Hz\ Jꢁ6[1 Hz\ 1H\ Har#\
6[10 "d\ 2Jꢁ6[2 Hz\ 0H\ Har#\ 6[11Ð5[07 "m\ 5H\ Hol#\

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
122
Fig[ 3[ Molecular structure and atomic labelling scheme of 35[ 29) thermal ellipsoids are shown for the non!hydrogen atoms^ hydrogen atoms have
arbitrary radii[
Table 3
Ä
Selected bond distances "A# and bond angles "># for complex 35
N"0#ÐC"09#
C"09#ÐC"00#
C"01#ÐC"02#
C"03#ÐC"04#
C"05#ÐC"06#
C"07#ÐC"08#
0[157"3#
0[338"4#
0[324"4#
0[311"4#
0[347"4#
0[352"4#
N"0#ÐC"3#
0[397"3#
0[239"4#
0[220"4#
0[233"4#
0[224"4#
019[4"2#
C"00#ÐC"01#
C"02#ÐC"03#
C"04#ÐC"05#
C"06#ÐC"07#
C"09#ÐN"0#ÐC"3#
Torsion angles
C"09#ÐN"0#ÐC"3#ÐC"4#
27[2
C"09#ÐN"0#ÐC"3#ÐC"8#
033[2
Table 4
Crystallographic data for complexes 05\ 12\ 31 and 35ꢀ
05
12
31
35
Empirical formula
Molecular weight
Crystal color\ habit
Crystal dimensions "mm2#
Crystal system
C13H15ClNO1Ru
385[87
red needles
9[02×9[16×9[42
triclinic
C16H18ClFeIrNO
556[90
red brown needles
9[02×9[19×9[42
monoclinic
P10:c
00[625"2#
08[522"4#
01[928"6#
C20[49H33ClN1O0[49PPd
536[40
C29H16CrFeNO2
446[27
brown plates
9[09×9[16×9[42
triclinic
dark green plates
9[42×9[32×9[02
monoclinic
P10:n
01[4334"6#
09[7970"7#
14[936"1#
¹
¹
Space group
P0
P0
Ä
a "A#
00[0442"09#
00[464"2#
06[282"1#
83[806"03#
87[588"6#
83[824"03#
1199[5"5#
3
6[3327"01#
00[289"1#
05[154"1#
096[971"8#
81[859"09#
78[820"01#
0205[2"2#
1
Ä
b "A#
Ä
c "A#
a ">#
b ">#
g ">#
007[31"3#
82[495"5#
2
Ä
V "A #
1339"1#
3
0[705
2278[4"3#
3
0[158
Z
Dcalc "g cm−2
#
0[499
0[395
Absorption correction
Transmission Tmin:Tmax
N
c scans
9[7380:9[8889
5327
c scans
9[5982:9[8876
2426
c scans
9[7445:9[8878
3713
c scans
9[7521:9[8887
2756
N9
Final R
indices ðI×1s"I#Ł
R indices "all data#
5972
2256
3692
2537
R0ꢁ9[9183\ wR1ꢁ9[9706
R0ꢁ9[9450\ wR1ꢁ9[0511
R0ꢁ9[9270\ wR1ꢁ9[0271
R0ꢁ9[9333\ wR1ꢁ9[0338
R0ꢁ9[9240\ wR1ꢁ9[0960
R0ꢁ9[9257\ wR1ꢁ9[9782
R0ꢁ9[9546\ wR1ꢁ9[0639
R0ꢁ9[9376\ wR1ꢁ9[0144
ꢀ
For all structure determinations] Tꢁ184 K\ Nonius CAD3 or MACH2\ programs] SHELXS!75\ SHELXL!82\ further details of the structure
determinations "without structure factor table# are available from the Cambridge Crystallographic Data Center on quoting the depository numbers
CCDC!090638 "05#\ !090649 "12#\ !090640 "35#\ !090641 "31# "e!mail] depositÝchemcrys[cam[ac[uk#[

123
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
2
2
CH2#\ 9[84:9[71 ðd\ Jꢁ5[5 Hz\ 2H\ d\ Jꢁ5[6 Hz\ 2H\
CH"CH2#1Ł[
nylŁ!1\6!dimethylnonatetraenal ð66\ 67Ł were re~uxed
with 044 mg "0[4 mmol# of o!aminophenol in 49 ml of
toluene for 3 h[ The cool solution was evaporated to 19 ml
and then centrifugated[ The product precipitated when
29 ml n!pentane was added to the solution[ Brown hygro!
6 from all!trans!retinal and L!valine[ Yellow hygro!
scopic powder[ IR "KBr\ cm−0#] nꢁ0506 sh\ 0487 vs br
½
"CO1\ C1N\ C1C#[ 0H NMR "169 MHz\ CDCl2#]
dꢁ7[22 "d\ 2Jꢁ8[2 Hz\ 0H\ HC1N#\ 6[99Ð5[04 "m\ 5H\
Hol#\ 2[29 "d\ 2Jꢁ7[1 Hz\ 0H\ CHCO1#\ 1[12 ðm\ 0H\
CH"CH2#1Ł\ 1[01:0[88:0[69 "each s\ each 2H\ CH2#\ 1[98Ð
0[49 "m\ 5H\ CH1#\ 0[91 ðs\ 5H\ C"CH2#1Ł\ 9[83:9[72 ðd\
scopic powder\ 299 mg "45)#[ IR "KBr\ cm−0#] nꢁ0598
½
s "C1N#\ 0475 m\ 0430 vs "C1C#[ 0H NMR "399 MHz\
CDCl2#] dꢁ7[22 "s\ 0H\ CH1N#\ 6[25 "d\ 1H\ 2J
ꢁ7[8 Hz\ C5H3#\ 6[10 "d\ 0H\ H3#\ 6[03 "t\ 0H\ 2Jꢁ6[4 Hz\
H2#\ 5[88Ð5[52 "m\ 8H\ C5H3\ H1\0\ol#\ 5[25 "d\ 0H 2J
ꢁ00[6 Hz\ Hol#\ 2[99 "s\ 5H\ N"CH2#1#\ 1[02:1[97 "each s\
each 2H\ CH2#[ C16H16FeNO=9[4H1O "336[0#] calcd[ C
61[41\ H 5[20\ N 2[02^ found C 61[67\ H 5[58\ N 2[07[
2
2Jꢁ5[6 Hz\ 2H\ d\ Jꢁ5[6 Hz\ 2H\ CH"CH2#1Ł[ UV:Vis
"MeOH\ nm\ lg o#] lmaxꢁ259 "3[44#[
7] 414 mg "2 mmol# of p!dimethylaminocinnamic alde!
hyde and 229 mg "2 mmol# of o!aminophenol were
re~uxed in 79 ml of toluene for 1 h[ Reduction of the
volume of solution and addition of 49 ml n!pentane led
to precipitation of the crude product[ Orange hygroscopic
2[0[ General procedure for the synthesis of the complexes
00Ð13 with the Schiff bases 0Ð2
powder\ 699 mg "76)#[ IR "KBr\ cm−0#] nꢁ0500 s\ 0599
½
vs\ 0466 vs\ 0463 vs "C1N\ C1C#[ 0H NMR "399 MHz\
9[0 mmol of Schi} base 0Ð2 was stirred in 09 ml of
methanol\ and 9[0 mmol of NaOMe in methanol was
added[ To the resulting solution 9[94 mmol
ð"R2P#"Cl#Pd"m!Cl#Ł1 "RꢁEt\ n!Bu\ Ph#\ ð"Et2P#"Cl#Pt"m!
Cl#Ł1\ ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 or ð"h5!p!cymene#
"Cl#Ru"m!Cl#Ł1 was added in one portion[ The complexes
00Ð07 precipitated after 29 min stirring[ Centrifugation
and washing with cold methanol gave crude products
after drying in vacuo[ 08Ð13 were stirred for 1 h at room
temperature\ before the solvent was evaporated in vacuo\
and 09 ml of dichloromethane was added[ Further stir!
ring for 1 h and then centrifugation yielded deep coloured
solutions of the products\ which were puri_ed by chro!
matography on cellulose::CH1Cl1:n!pentane[
2
CDCl2#] dꢁ7[34 "d\ 0H\ Jꢁ8[1 Hz\ HC1N#\ 6[35 "d\
2
2
1H\ Jꢁ7[5 Hz\ Me1NC5H3#\ 6[11 "dd\ 0H\ Jꢁ6[5 Hz\
3Jꢁ0[4 Hz\ H3#\ 6[03 "d"t#\ 0H\ Jꢁ6[5 Hz\ Jꢁ0[3 Hz\
2
3
2
2
H2#\ 6[01 "d\ 0H\ Jꢁ04[4 Hz\ Hol#\ 5[87 "dd\ 0H\ Jꢁ
7[9 Hz\ 3Jꢁ0[2 Hz\ H0#\ 5[84 "dd\ 0H\ 2Jꢁ04[4 Hz\
2Jꢁ7[8 Hz\ Hol#\ 5[77 "d"t#\ 0H\ 2Jꢁ7[0 Hz\ 3Jꢁ0[3 Hz\
2
H1#\ 5[61 "d\ 1H\ Jꢁ7[8 Hz\ Me1NC5H3#\ 2[94 "s\ 5H\
N"CH2#1#[ 02C NMR "56 MHz\ CDCl2#] dꢁ048[22
"HC1N#\ 040[88:040[23:034[09:025[31:018[05:016[73:
012[56: 012[36:008[75:004[37:003[52:000[82 "Car\ Col#\
39[02 "N"CH2#1#[ UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ309
"3[72#[ C06H07N1 "155[0#] calcd[ C 65[56\ H 5[70\ N 09[40^
found C 65[06\ H 5[81\ N 09[31[
8] A solution of 239 mg "9[87 mmol# of 8!ferrocenyl!
1\6!dimethylnonatetraenal ð65Ł and 84 mg of o!ami!
nophenol in 19 ml of dichloromethane containing 2 g of
Na1SO3 was stirred at room temperature for 2 d[ The
reaction can be followed by the disappearance of the
aldehyde IR absorption[ The mixture was centrifugated\
the solution was separated and evaporated[ The crude
product was washed several times with 4 ml portions of
n!pentane to remove unreacted aldehyde[ Red powder\
2[1[ Complex of 0 with ð"Et2P#"Cl#Pt"m!Cl#Ł1 00
Red powder[ IR "KBr\ cm−0#] nꢁ0591 vs\ 0473 s\
½
"C1N\ C1C#\ 225 vw "PtÐCl#[ 0H NMR "399 MHz\
3
CDCl2#] dꢁ7[81 "d\ 0H\ JHPꢁ02[3\ CH1N#\ 7[29 "d\
2
2
3
1H\ Jꢁ7[6#\ 6[25 "dd\ 0H\ Jꢁ7[0\ Jꢁ0[3#\ 5[88 "dd\
2
2
2
0H\ Jꢁ7[1\ Jꢁ6[4#\ 5[84 "d\ 1H\ Jꢁ7[6#\ 5[64 "dd\
2
3
2
2
0H\ Jꢁ7[1\ Jꢁ0[2#\ 5[41 "dd\ 0H\ Jꢁ6[4\ Jꢁ6[6#\
2[77 "s\ 2H\ CH2#\ 0[85Ð0[74 "m\ 5H\ PCH1#\ 0[20Ð0[10
"m\ 8H\ PCH1CH2#[ 20P NMR "098 MHz\ CH1Cl1#]
dꢁ3[26 "0JPPtꢁ2522[5#\ 2[03 "0JPPtꢁ2673[4#\ "09]5#[
UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ342 "2[81#\ "MeOH\
nm\ lg o#] lmaxꢁ322 "3[90#[ C19H16NO1ClPPt "463[8#]
calcd[ C 30[67\ H 3[62\ N 1[33^ found C 30[00\ H 3[55\ N
1[31[
219 mg "62)#[ IR "KBr\ cm−0#] nꢁ0504 m "C1N#\
½
0
0475 m\ 0449 vs "C1C#[ H NMR "399 MHz\ CDCl2#]
dꢁ7[22 "s\ 0H\ N1CH#\ 6[11 "d\ 2Jꢁ7[25 Hz\ 0H\ Har#\
2
2
6[04 "t\ Jꢁ6[5 Hz\ 0H\ Har#\ 5[88 "d\ Jꢁ8[1 Hz\ 0H\
Har#\ 5[78Ð5[77 "m\ 1H\ Har\ Hol#\ 5[67Ð5[64 "m\ 1H\ Hol#\
5[41:5[37 "each d\ 2Jꢁ04[6\ 2Jꢁ05[9\ 1H\ FcÐCH1CH#\
2
5[20 "d\ Jꢁ00[3 Hz\ 0H\ Hol#\ 3[32 "m\ 1H\ C4H3#\ 3[20
"m\ 1H\ C4H3#\ 3[02 "s\ 4H\ Cp#\ 1[02 "s\ 2H\ CH2#\ 1[94
"s\ 2H\ CH2#[ 02C NMR "099 MHz\ CDCl2#] dꢁ059[54
"C1N#\ 041[18\ 031[42\ 028[45\ 025[93\ 024[74\ 023[85\
029[65\ 018[61\ 017[55\ 017[11\ 016[70\ 008[87\ 004[25\
003[52\ 72[18\ 58[22\ 55[86\ 01[79\ 00[58[ UV:Vis "CH1Cl1\
nm\ lg o#] lmaxꢁ317 "3[83#[ C16H16FeNO=9[4H1O "336[0#]
calcd[ C 61[41\ H 5[20\ N 2[02^ found C 61[67\ H 5[58\ N
2[07[
2[2[ Complex of 0 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 01
Orange powder[ IR "KBr\ cm−0#] nꢁ0590 vs\ 0472 s
½
"C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#] dꢁ7[56 "d\
0H\ 3JHPꢁ02[9\ CH1N#\ 7[05 "d\ 1H\ 2Jꢁ7[7#\ 6[17 "m\
0H#\ 5[88 "dd\ 0H\ 2Jꢁ5[8\ 2Jꢁ5[6#\ 5[84 "d\ 1H\
2
2
2Jꢁ7[6#\ 5[60 "d\ 0H\ Jꢁ7[1#\ 5[41 "dd\ 0H\ Jꢁ6[4\
09] 274 mg "0[32 mmol# of 8!ð"3!dimethylamino#!phe!
2Jꢁ6[5#\ 2[77 "s\ 2H\ OCH2#\ 0[85Ð0[76 "m\ 5H\ PCH1#\

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
124
2
0[24Ð0[16 "m\ 8H\ PCH1CH2#[ 20P NMR "25[2 MHz\
CH1Cl1#] dꢁ24[69\ 22[46 "3]0#[ C19H16NO1ClPPd "375[2#]
calcd[ C 38[39\ H 4[48\ N 1[76^ found C 37[83\ H 4[76\ N
1[56[
0[98 "d\ 5H\ Jꢁ6[0\ CH"CH2#1#[ UV:Vis "CH1Cl1\ nm\
lg o#] lmaxꢁ303 "3[98#\ "MeOH\ nm\ lg o#] lmaxꢁ281
"2[86#[ C13H15NO1ClRu "385[8#] calcd[ C 47[99\ H 4[16\
N 1[71^ found C 46[44\ H 4[94\ N 1[66[
2[3[ Complex of 1 with ð"Et2P#"Cl#Pt"m!Cl#Ł1 02
2[7[ Complex of 1 with ð"Cpꢀ#"Cl#Ir"m!Cl#Ł1 06
Red powder[ IR "KBr\ cm−0#] nꢁ0592 vs\ 0480 vs\
Red powder[ IR "KBr\ cm−0#] nꢁ0593 vs\ 0483 m\
½
½
0470 s"C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#]
0468 s "C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#]
3
2
2
dꢁ8[11 "d\ 0H\ JHPꢁ02[0\ CH1N#\ 7[73 "d\ 0H\ Jꢁ
dꢁ8[05 "s\ 0H\ CH1N#\ 8[02 "d\ 0H\ Jꢁ7[4#\ 6[33 "d\
7[6#\ 6[28 "dd\ 0H\ 2Jꢁ7[1\ Jꢁ0[5#\ 5[86 "dd\ 0H\ Jꢁ
0H\ 2Jꢁ7[4#\ 6[99Ð5[88 "m\ 1H#\ 5[46Ð5[41 "dd\ 0H\
3
2
2
2
3
3
7[0\ Jꢁ6[9#\ 5[64 "dd\ 0H\ Jꢁ7[3\ Jꢁ0[2#\ 5[46Ð5[41
"m\ 1H#\ 5[39 "d\ 0H\ 2Jꢁ1[2#\ 2[89 "s\ 2H\ OCH2#\ 2[77
"s\ 2H\ OCH2#\ 0[83Ð0[75 "m\ 5H\ PCH1#\ 0[20Ð0[12 "m\
8H\ PCH1CH2#[ 20P NMR "098 MHz\ CH1Cl1#] dꢁ4[29
"0JPPtꢁ2513[4#\ 3[97 "0JPPtꢁ2644[4#\ "0]3#[ UV:Vis
"CH1Cl1\ nm\ lg o#] lmaxꢁ342 "2[81#\ "MeOH\ nm\ lg o#]
lmaxꢁ322 "3[90#[ C10H18NO2ClPPt "593[8#] calcd[ C
30[69\ H 3[72\ N 1[20^ found C 30[32\ H 3[36\ N 1[18[
2Jꢁ7[5\ Jꢁ1[4#\ 5[36Ð5[31 "m\ 1H#\ 2[83:2[78 "each s\
each 2H\ OCH2#\ 0[28 "s\ 04H\ C4"CH2#4#[ C14H18NO2ClIr
"508[0#] calcd[ C 37[49\ H 3[61\ N 1[15^ found C 36[02\ H
3[66\ N 1[13[
2[8[ Complex of 1 with ð"p!cymene#"Cl#Ru"m!Cl#Ł1 07
Red powder[ IR "KBr\ cm−0#] nꢁ0500 vs\ 0478 s\ 0465
½
vs "C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#] dꢁ8[97
"s\ 0H\ CH1N#\ 7[68 "d\ 0H\ 2Jꢁ7[1#\ 6[28 "d\ 0H\ 2Jꢁ
7[1#\ 6[99Ð5[81 "m\ 1H#\ 5[57 "dd\ 0H\ 2Jꢁ7[4\ 3Jꢁ0[6#\
2[4[ Complex of 1 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 03
Red powder[ IR "KBr\ cm−0#] nꢁ0500 vs\ 0484 vs\
5[44 "d\ 0H\ Jꢁ0[8#\ 5[31 "dd\ 0H\ Jꢁ6[4\ Jꢁ6[1#\
3
2
2
½
0468 s"C1N\ C1C#[ 0H NMR "399 MHz\ CDCl2#]
dꢁ7[88 "d\ 0H\ 2Jꢁ02[6\ CH1N#\ 7[44 "d\ 0H\ 2Jꢁ7[7#\
4[25:4[98:3[67:3[43 "each d\ 3H\ Jꢁ4[7:4[7:4[8:4[6\ h5!
2
C5H3# 2[88:2[82 "each s\ each 2H\ OCH2# 1[53 "sep\ 0H\
2Jꢁ6[1\ CH"CH2#1#\ 1[12 "s\ 2H\ CH2# 0[00 "dd\ 5H\
2Jꢁ5[8\ 3Jꢁ0[5\ CH"CH2#1#[ UV:Vis "CH1Cl1\ nm\ lg o#]
lmaxꢁ309 "2[73#\ "MeOH\ nm\ lg o#] lmaxꢁ280 "3[99#[
C14H17NO2ClRu "416[9#] calcd[ C 45[87\ H 4[24\ N 1[55^
found C 45[15\ H 4[39\ N 1[47[
2
2
2
6[29 "d\ 0H\ Jꢁ6[6#\ 5[87 "dd\ 0H\ Jꢁ6[6\ Jꢁ6[5#\
2
3
2
5[60 "dd\ 0H\ Jꢁ6[6\ Jꢁ0[4#\ 5[46 "dd\ 0H\ Jꢁ6[5\
3Jꢁ0[8#\ 5[41 "dd\ 0H\ Jꢁ6[4\ Jꢁ6[5#\ 5[39 "d\ 0H\
3Jꢁ1[9#\ 2[77:2[76 "each s\ each 2H\ CH2#\ 0[84Ð0[75 "m\
5H\ PCH1#\ 0[24Ð0[14 "m\ 8H\ PCH1CH2#[ 20P NMR
"098 MHz\ CH1Cl1#] dꢁ23[98\ 21[08 "4]1#[ UV:Vis
"CH1Cl1\ nm\ lg o#] lmaxꢁ303 "3[92#\ "MeOH\ nm\ lg o#]
lmaxꢁ283 "2[75#[ C10H18NO2ClPPd "405[2#] calcd[ C
37[74\ H 4[54\ N 1[60^ found C 36[62\ H 4[08\ N 1[68[
2
2
2[09[ Complex of 2 with ð"n!Bu2P#"Cl#Pd"m!Cl#Ł1 08
Dark red oil[ IR "CH1Cl1\ cm−0#] nꢁ0482 vs "C1N#[
½
0H NMR "169 MHz\ CDCl2#] dꢁ7[29 "d\ 3JHPꢁ5[9\ 0H\
HC1N#\ 6[22Ð6[16 "m\ 0H#\ 5[83Ð5[76 "m\ 0H#\ 5[63Ð
5[60 "m\ 0H#\ 5[20Ð5[17 "m\ 0H#\ 3[55 "s\ 1H\ C4H3#\ 3[43
"s\ 1H\ C4H3#\ 3[24 "s\ 4H\ C4H4#\ 0[87Ð0[34 "m\ 07H\
PCH1CH1CH1#\ 0[94Ð9[77 "m\ 8H\ PCH1CH1CH1CH2#[
02C NMR "57 MHz\ CDCl2#] dꢁ058[64 "HC1N#\
059[54:027[10:017[72:010[76:007[47:002[12 "C!arom[#\
61[48:61[95 "C4H3#\ 60[00 "C4H4#\ 15[07 "PCH1
CH1CH1CH2#\ 13[13 "d\ Jꢁ05 Hz\ PCH1CH1CH1CH2#\
11[07 "d\ Jꢁ18[6 Hz\ PCH1CH1CH1CH2#\ 02[65 "PCH1
2[5[ Complex of 0 with ð"Cpꢀ#"Cl#Ir"m!Cl#Ł1 04
Orange red powder[ IR "KBr\ cm−0#] nꢁ0595 vs\ 0482
½
0
vs\ 0468 s"C1N\ C1C#[ H NMR "399 MHz\ CDCl2#]
2
dꢁ7[80 "s\ 0H\ CH1N#\ 7[32 "d\ 1H\ Jꢁ7[7#\ 6[28 "d\
2
2
0H\ Jꢁ7[2#\ 6[91 "d\ 1H\ Jꢁ7[6#\ 5[88Ð5[74 "m\ 1H#\
5[33 "dd\ 0H\ 2Jꢁ6[6\ 2Jꢁ6[1#\ 2[73 "s\ 2H\ OCH2#\ 0[30
"s\ 04H\ C4"CH2#4#[ UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ313
"3[90#\ "MeOH\ nm\ lg o#] lmaxꢁ309 "2[77#[ C13H16N!
O1ClIrÐH1O "596[0#] calcd[ C 36[37\ H 3[70\ N 1[20^
found C 36[13\ H 3[73\ N 1[03[
CH1CH1CH2#[ 20P NMR
"25 MHz\ CH1Cl1#]
dꢁ14[8:13[32 "0]09#[ C18H30NOClPFePd "536[0#] calcd[
C 42[67\ H 5[28\ N 1[05^ found C 42[99\ H 5[96\ N 1[93[
2[6[ Complex of 0 with ð"p!cymene#"Cl#Ru"m!Cl#Ł1 05
2[00[ Complex of 2 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 19
Red powder[ IR "KBr\ cm−0#] nꢁ0592 vs\ 0482 s\ 0471
½
vs "C1N\ C1C#[ 0H NMR "169 MHz\ CDCl2#] dꢁ8[95
Red powder[ IR "KBr\ cm−0#] nꢁ0489 s\ 0469 vs
½
2
"s\ 0H\ CH1N#\ 7[20 "d\ 1H\ 2Jꢁ7[1#\ 6[27 "dd\ 0H\ J
"C1N\ C1C#\ 242 vw "PdÐCl#[ 0H NMR "399 MHz\
ꢁ7[1\ 3Jꢁ0[2#\ 6[97 "d\ 1H\ 2Jꢁ8[9#\ 6[92Ð5[82 "m\ 1H#\
5[32 "dd\ 0H\ 2Jꢁ6[4\ 2Jꢁ6[2#\ 4[27:4[03:3[62:3[50 "each
CDCl2#] dꢁ7[18 "d\ 0H\ JHPꢁ4[8\ HC1N#\ 6[20 "cd\
3
0H#\ 5[81Ð5[77 "ct\ 0H#\ 5[62Ð5[69 "cd\ 0H#\ 5[29Ð5[15
"ct\ 0H#\ 3[55 "ct\ 1H\ C4H3#\ 3[43 "ct\ 1H\ C4H3#\ 3[24
"s\ 4H\ C4H4#\ 0[85Ð0[77 "m\ 5H\ PCH1CH2#\ 0[23Ð0[17
2
d\ 3H\ Jꢁ5[9:4[6:4[7:5[9\ h5!C5H3# 2[82 "s\ 2H\ OCH2#
1[51 "sep\ 0H\ 2Jꢁ5[8\ CH"CH2#1#\ 1[15 "s\ 2H\ CH2#

125
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
"m\ 8H\ PCH1CH2#[ 20P NMR "25 MHz\ CH1Cl1#]
dꢁ20[86:10[22 "0]09#[ C12H18NOClPFePd "453[1#] calcd[
C 38[91\ H 4[08\ N 1[38^ found C 37[84\ H 4[36\ N 1[37[
79[77:62[75:61[55:60[70:69[38 "C4H3#\ 69[16 "C4H4#\
29[82:18[63:10[85:07[70 "C!alkyl#[ C16H17NOClFeRu
"463[8#] calcd[ C 45[30\ H 3[80\ N 1[33^ found C 44[61\ H
4[06\ N 1[29[
2[01[ Complex of 2 with ð"Ph2P#"Cl#Pd"m!Cl#Ł1 10
2[05[ General procedure for the synthesis of the complexes
14Ð26 with the Schiff bases 3Ð6
Dark red powder[ IR "KBr\ cm−0#] nꢁ0501 w\ 0477 s
½
0458 vs "C1N\ C1C#\ 241 vw "PdÐCl#[ 0H NMR
"399 MHz\ CDCl2#] dꢁ7[30 "d\ 0H\ 3JHPꢁ5[3\ CH1N#\
6[67Ð6[27 "m\ 04H\ C5H4#\ 6[17 "cd\ 0H#\ 5[72Ð5[67 "ct\
0H#\ 5[49Ð5[37 "cd\ 0H#\ 5[14Ð5[10 "ct\ 0H#\ 3[52 "ct\
1H\ C4H3#\ 3[42 "ct\ 1H\ C4H3#\ 3[24 "s\ 4H\ C4H4#[ 20P
NMR "25 MHz\ CH1Cl1#] dꢁ14[9[ C24H18NOClPFePd
"697[4#] calcd[ C 48[23\ H 3[02\ N 0[87^ found C 47[86\ H
3[94\ N 1[97[
9[0 mmol of 3Ð6 was dissolved in 4 ml of methanol
and added dropwise to a suspension of 9[94 mmol of the
chloro!bridged complexes ð"R2P#"Cl#M"m!Cl#Ł1 "MꢁPd\
RꢁEt\ Bu\ Ph\ Tol\ MꢁPt\ RꢁBu# or ð"h4!C4Me4#
"Cl#Ir"m!Cl#Ł1 in 2Ð4 ml of methanol[ The clear solution
was stirred for 0Ð4 h[ Then the solvent was removed in
vacuo[ The crude product was stirred in dichloromethane
for at least 0 h[ After removal of suspended NaCl by
centrifugation\ either hexane was added to the solution to
precipitate the complexes\ or the products were extracted
with diethylether\ or the complexes were puri_ed by chro!
matography[ After removal of the solvent in vacuo at
room temperature the crude products were obtained[
2[02[ Complex of 2 with ð"Et2P#"Cl#Pt"m!Cl#Ł1 11
Red powder[ IR "KBr\ cm−0#] nꢁ0480 s\ 0458 vs
½
"C1N\ C1C#\ 239 vw "PtÐCl#[ 0H NMR "169 MHz\
3
CDCl2#] dꢁ7[41 "d\ 0H\ JHPꢁ4[8\ HC1N#\ 6[35 "d\
0H\ 2Jꢁ7[2#\ 5[80 "t\ 0H\ 2Jꢁ6[6#\ 5[68 "d\ 0H\ 2Jꢁ7[4#\
2
2
5[21 "t\ 0H\ Jꢁ6[1#\ 3[60 "ct\ 1H\ Jꢁ1[0\ C4H3#\ 3[59
2[06[ Complex of 3 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 14
2
"ct\ 1H\ Jꢁ0[6\ C4H3#\ 3[26 "s\ 4H\ C4H4#\ 0[88Ð0[78
"m\ 5H\ PCH1CH2#\ 0[22Ð0[10 "m\ 8H\ PCH1CH2#[ 20P
NMR "098 MHz\ CH1Cl1#] dꢁ4[12 "0JPtPꢁ2517[4#:2[60
"87]1#[ C12H18NOClPFePt "541[7#] calcd[ C 31[20\ H 3[37\
N 1[04^ found C 31[37\ H 3[27\ N 1[94[
Dark red powder[ 0H NMR "399 MHz\ CDCl2#]
3
dꢁ6[52 "d\ JHPꢁ02[6 Hz\ 0H\ N1CH#\ 5[88Ð5[15 "m\
2
2
5H\ Hol#\ 3[31 "m\ 1H\ C4H3#\ 3[20 ðd"d#\ Jꢁ0[4 Hz\ J
ꢁ1[9 Hz\ 1H\ C4H3#\ 3[00 "s\ 4H\ Cp#\ 2[48 ðd"d#\ 2J
ꢁ7[7 Hz\ 3Jꢁ1[3 Hz\ 0H\ a!CHŁ\ 2[15 ðm\ 0H\
CH"CH2#1Ł\ 1[40 "s\ 2H\ CH2#\ 1[91 "s\ 2H\ CH2#\ 0[89Ð
0[70 ðm\ 5H\ P"CH1CH2#2Ł\ 0[16 ðd"t#\ 3Jꢁ06[3 Hz\ 2J
ꢁ6[5 Hz\ 8H\ P"CH1CH2#2Ł\ 0[13:0[05 ðeach d\ 2J
2[03[ Complex of 2 with ð"Cpꢀ#"Cl#Ir"m!Cl#Ł1 12
Orange powder[ IR "KBr\ cm−0#] nꢁ0487 s\ 0471 vs
½
"C1N\ C1C#[ 0H NMR "169 MHz\ CDCl2#] dꢁ7[69 "s\
ꢁ5[3 Hz\ Jꢁ5[7 Hz\ each 2H\ CH"CH2#1Ł[ 02C NMR
2
2
0H\ HC1N#\ 6[24 "d\ 0H\ Jꢁ7[1#\ 6[90Ð5[82 "m\ 1H#\
"099 MHz\ CDCl2#] dꢁ068[08 "CO1#\ 069[09 "C1N#\
035[76\ 026[08\ 020[00\ 029[34\ 018[38\ 018[23\ 015[86
"Col#\ 75[68 "a!C#\ 71[87 "ipso!C4H3#\ 58[21 "C4H4#\
56[99:55[84 "C4H3#\ 22[74 ðCH"CH2#1Ł\ 08[74:08[51
5[32 "ct\ 0H#\ 5[13 "s\ 0H\ C4H3#\ 3[52Ð3[46 "m\ 2H\
C4H3#\ 3[29 "s\ 4H\ C4H4#\ 0[31 "s\ 04H\ C4"CH2#4#[ 02C
NMR "099 MHz\ CDCl2#] dꢁ057[60 "C1N#\ 047[09:
031[82:018[18:008[68:004[15:003[12 "C!arom[#\ 73[84
"C4"CH2#4#\ 68[73:63[21:61[50:61[06:60[93 "C4H3#\ 69[11
"C4H4#\ 7[77 "CH2#[ C16H18NOClFeIr "556[0#] calcd[ C
37[46\ H 3[27\ N 1[09^ found C 37[39\ H 3[34\ N 0[88[
0
ðCH"CH2#1Ł\ 03[29 ðd\ JCPꢁ21[9 Hz\ P"CH1CH2#2Ł\
1
04[10:01[73 "CH2#\ 6[52 ðd\ JCPꢁ2[9 Hz\ P"CH1CH2#2Ł[
20P NMR "25[16 MHz\ CH1Cl1#] dꢁ23[79 s "099)#[
UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ302 "3[44#\ "MeOH\
nm\ lg o#] lmaxꢁ300 "3[58#[ C21H34ClFeNO1PPd "693[3#]
calcd[ C 43[45\ H 5[33\ N 0[88^ found C 44[04\ H 5[48\ N
0[72[
2[04[ Complex of 2 with ð"p!cymene#"Cl#Ru"m!Cl#Ł1 13
Red powder[ IR "KBr\ cm−0#] nꢁ0488 s\ 0468 vs
½
0
"C1N\ C1C#\ 235 vw "RuÐCl#[ H NMR "399 MHz\
2[07[ Complex of 3 with ð"n!Bu2P#"Cl#Pd"m!Cl#Ł1 15
2
CDCl2#] dꢁ7[70 "s\ 0H\ HC1N#\ 6[25"d\ 0H\ Jꢁ7[0#\
2
2
2
5[88 "d\ 0H\ Jꢁ6[3#\ 5[83 "dd\ 0H\ Jꢁ6[1\ Jꢁ7[1#\
Dark red powder\ m[p[ 89>C[ IR "KBr\ cm−0#] nꢁ0548
½
2
5[31 "dd\ 0H\ Jꢁ6[6\ 2Jꢁ5[7#\ 5[00 "s\ 0H\ C4H3#\ 4[24
vs "COO#[ 0H NMR "399 MHz\ CDCl2#] dꢁ6[43 "d\
"d\ 0H\ 2Jꢁ4[9\ h5!C5H3#\ 4[18 "d\ 0H\ 2Jꢁ4[9\ h5!C5H3#\
3JHPꢁ02[8 Hz\ 0H\ N1CH#\ 5[72Ð5[07 "m\ 5H\ Hol#\ 3[23
2
2
2
2
2
3[86 "d\ 0H\ Jꢁ5[0\ h5!C5H3#\ 3[78 "d\ 0H\ Jꢁ5[9\ h5!
C5H3#\ 3[63 "s\ 0H\ C4H3#\ 3[52 "s\ 1H\ C4H3#\ 3[18 "s\ 4H\
C4H4#\ 1[46 "m\ 0H\ CH"CH2#1#\ 1[16 "s\ 2H\ CH2#\ 0[94
"dd\ 5H\ CH"CH2#1#[ 02C NMR "099 MHz\ CDCl2#]
dꢁ057[44 "C1N#\ 047[47:028[38:018[26:019[96:003[56:
003[22 "C!arom[#\ 73[27:71[81:71[01:70[15 "C!h5!arom[#\
"d\ Jꢁ0[6 Hz\ 1H\ C4H3#\ 3[12 ðd"d#\ Jꢁ0[6 Hz\ Jꢁ
1[9 Hz\ 1H\ C4H3#\ 3[93 "s\ 4H\ Cp#\ 2[38 ðd"d#\ 2J
ꢁ8[9 Hz\ 3Jꢁ1[3 Hz\ 0H\ a!CHŁ\ 2[07 ðm\ 0H\
CH"CH2#1Ł\ 1[33:0[83 "each s\ each 2H\ CH2#\ 0[66Ð
0[57:0[50Ð0[41:0[50Ð0[12 ðeach m\ each 5H\ P"CH1
CH1CH1CH2#2Ł\ 0[05:0[95 ðeach d\ 2Jꢁ5[5 Hz\ 2Jꢁ

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
126
5[7 Hz\ each 2H\ CH"CH2#1Ł\ 9[77 ðt\ 2Jꢁ6[2 Hz\ 8H\
P"CH1CH1CH1CH2#2Ł[ 02C NMR "099 MHz\ CDCl2#]
dꢁ068[02 "CO1#\ 069[20 "C1N#\ 035[77\ 039[75\ 026[01\
020[20\ 029[49\ 018[36\ 018[26\ 016[95 "Col#\ 76[92 "a!
C#\ 72[94 "ipso!C4H3#\ 58[23 "C4H4#\ 56[02:55[85 "C4H3#\
22[72 ðCH"CH2#1Ł\ 14[77 ðP"CH1CH1CH1CH2#2Ł\ 13[02
"3[51#[ C25H34ClFeIrNO1 "796[2#] calcd[ C 42[45\ H 4[51\
N 0[63^ found C 42[17\ H 4[68\ N 0[64[
2[10[ Complex of 4 with ð"n!Bu2P#"Cl#Pd"m!Cl#Ł1 18
Orange powder\ m[p[ 63>C[ IR "KBr\ cm−0#] nꢁ0545
½
ðd\ JCPꢁ02[6 Hz\ P"CH1CH1CH1CH2#2Ł\ 10[24 ðd\ 0J
vs "COO#[ 0H NMR "399 MHz\ CDCl2#] dꢁ6[53 "d\
3JHPꢁ03[6 Hz\ 0H\ N1CH#\ 6[33 "d\ 2Jꢁ6[7 Hz\ 1H\
2
CPꢁ20[2 Hz\
P"CH1CH1CH1CH2#2Ł\
08[78:08[50
2
2
ðCH"CH2#1Ł\ 02[69 ðP"CH1CH1CH1CH2#2Ł\ 04[01:01[76
"CH2#[ 20P NMR "56 MHz\ CH1Cl1#] dꢁ16[15 s "099)#[
UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ300 "3[41#\ "MeOH\
nm\ lg o#] lmaxꢁ320 "3[55#[ C27H46ClFeNO1PPd "677[4#]
calcd[ C 46[77\ H 6[18\ N 0[67^ found C 47[24\ H 6[22\ N
0[79[
Har#\ 6[22 ðd"d#\ Jꢁ6[7 Hz\ Jꢁ6[2 Hz\ 1H\ HarŁ\ 6[12
2
ðd"d#\ Jꢁ6[2 Hz\ 0H\ HarŁ\ 5[86Ð5[24 "m\ 5H\ Hol#\ 2[47
ðd"d#\ 2Jꢁ8[9 Hz\ 3JHPꢁ1[3 Hz\ 0H\ a!CHŁ\ 2[20 ðm\ 0H\
CH"CH2#1Ł\ 1[43:1[95 "each s\ each 2H\ CH2#\ 0[76Ð
0[64:0[61Ð0[48:0[43Ð0[32 ðeach m\ each 5H\ P"CH1
CH1CH1CH2#2Ł\ 0[14:0[03 ðeach d\ 2Jꢁ5[5 Hz\ 2J
2
ꢁ5[7 Hz\ each 2H\ CH"CH2#1Ł\ 9[85 ðt\ Jꢁ6[1 Hz\ 8H\
2[08[ Complex of 3 with ð"n!Bu2P#"Cl#Pt"m!Cl#Ł1 16
P"CH1CH1CH1CH2#2Ł[ 02C NMR "099 MHz\ CDCl2#]
dꢁ067[81 "CO1#\ 069[01 "C1N#\ 75[74 "a!C#\ 22[60
ðCH"CH2#1Ł\ 14[66 ðP"CH1CH1CH1CH2#2Ł\ 12[85 ðd\
Dark red powder\ m[p[ 66>C[ IR "KBr\ cm−0#] nꢁ0563
½
vs "COO#[ 0H NMR "399 MHz\ CDCl2#] dꢁ6[76 "d\
3JHPꢁ02[1 Hz\ 0H\ N1CH#\ 5[80Ð5[07 "m\ 5H\ Hol#\ 3[24
"d\ 2Jꢁ1[9 Hz\ 1H\ C4H3#\ 3[13 ðct\ 2Jꢁ1[9 Hz\ 1H\
C4H3#\ 3[94 "s\ 4H\ Cp#\ 2[57 ðd"d#\ 2Jꢁ8[0 Hz\ 3Jꢁ
1[6 Hz\ 0H\ a!CHŁ\ 2[09 ðm\ 0H\ CH"CH2#1Ł\ 1[49:0[84
"each s\ each 2H\ CH2#\ 0[67Ð0[55:0[48Ð0[49:0[34Ð0[25
ðeach m\ each 5H\ P"CH1CH1CH1CH2#2Ł\ 0[05:0[95 ðeach
2JCPꢁ02[6 Hz\
0JCPꢁ29[5 Hz\
P"CH1CH1CH1CH2#2Ł\
P"CH1CH1CH1CH2#2Ł\
10[04
08[65:08[49
ðd\
ðCH"CH2#1Ł\ 02[59 ðP"CH1CH1CH1CH2#2Ł\ 12[84:04[93
"CH2#[ 20P NMR "098 MHz\ CH1Cl1#] dꢁ16[85 s "72)#\
14[73 s "06)#[ C23H42ClNO1PPd "579[5#] calcd[ C 59[99\
H 6[74\ N 1[95^ found C 48[88\ H 6[66\ N 1[95[
2
2
d\ Jꢁ5[2 Hz\ Jꢁ5[7 Hz\ each 2H\ CH"CH2#1Ł\ 9[77 ðt\
2Jꢁ6[0 Hz\ 8H\ P"CH1CH1CH1CH2#2Ł[ 02C NMR
"099 MHz\ CDCl2#] dꢁ068[68 "CO1#\ 069[03 "C1N#\
036[47\ 030[07\ 026[45\ 020[11\ 029[40\ 018[61\ 018[36\
016[06 "Col#\ 74[48 "a!C#\ 72[90 "ipso!C4H3#\ 58[24 "C4H4#\
56[04:56[99 "C4H3#\ 22[45 ðCH"CH2#1Ł\ 14[51 ðP"CH1
CH1CH1CH2#2Ł\ 12[86 ðd\ 2JCPꢁ02[7 Hz\ P"CH1
CH1CH1CH2#2Ł\ 19[16 ðd\ 0JCPꢁ27[1 Hz\ P"CH1
CH1CH1CH2#2Ł\ 08[71:08[32 ðCH"CH2#1Ł\ 02[62 ðP"CH1
CH1CH1CH2#2Ł\ 04[93:01[82 "CH2#[ 20P NMR "098 MHz\
CH1Cl1#] dꢁ−2[81 s "0JPtPꢁ2477 Hz\ 099)#[ UV:Vis
"CH1Cl1\ nm\ lg o#] lmaxꢁ314 "3[47#\ "MeOH\ nm\ lg o#]
lmaxꢁ311 "3[72#[ C27H46ClFeNO1PPt=9[4H1O "775[1#]
calcd[ C 40[49\ H 5[59\ N 0[47^ found C 40[36\ H 5[57\ N
0[44[
2[11[ Complex of 4 with ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 29
Orange powder\ m[p[ 066Ð068>C[ IR "KBr\ cm−0#] n
½
0
ꢁ0542 vs "COO\ C1N#[ H NMR "399 MHz\ CDCl2#]
dꢁ7[94 "s\ 0H\ N1CH#\ 6[34 "d\ Jꢁ6[7 Hz\ 1H\ Har#\
2
2
2
6[23 ðd"d#\ Jꢁ6[7 Hz\ Jꢁ6[2 Hz\ 1H\ HarŁ\ 6[13 ðd"d#\
2Jꢁ6[2 Hz\ 0H\ HarŁ\ 6[93Ð5[24 "m\ 5H\ Hol#\ 2[48 ðd\ J
2
ꢁ8[7 Hz\ 0H\ a!CHŁ\ 2[97 ðm\ 0H\ CH"CH2#1Ł\ 1[07:1[96
"each s\ each 2H\ CH2#\ 0[48 ðs\ 04 H\ C4"CH2#4#Ł\
2
0[13:9[88 ðeach d\ Jꢁ5[7 Hz\ each 2H\ CH"CH2#1Ł[ 02C
NMR "099 MHz\ CDCl2#] dꢁ067[58 "CO1#\ 060[33
"C1N#\ 74[33 ðC4"CH2#4Ł\ 73[46 "a!C#\ 20[38 ðCH"CH2#1Ł\
19[30:08[53 ðCH"CH2#1Ł\ 03[55:02[94 "CH2#\ 8[30
ðC4"CH2#4Ł[
2[12[ Complex of 5 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 20
2[19[ Complex of 3 with ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 17
Red powder[ IR "KBr\ cm−0#] nꢁ0548 vs "COO\
½
Dark red powder[ IR "KBr\ cm−0#] nꢁ0544 vs "COO\
C1N#\ 0596 "C1C#[ 0H NMR "169 MHz\ CDCl2#]
½
0
3
C1N#\ 0599 sh "C1C#[ H NMR "399 MHz\ CDCl2#]
dꢁ6[45 "d\ JHPꢁ03[9 Hz\ 0H\ N1CH#\ 6[22Ð5[13 "m\
2
3
dꢁ6[43 "s\ 0H\ N1CH#\ 6[19Ð5[07 "m\ 5H\ Hol#\ 3[23 "d\
09H\ Har\ Hol#\ 2[40 ðd"d#\ Jꢁ00[1 Hz\ Jꢁ1[6 Hz\ 0H\
a!CHŁ\ 2[08 ðm\ 0H\ CH"CH2#1Ł\ 1[81 ðs\ 5H\ N"CH2#1Ł\
1[35:0[88 "each s\ each 2H\ CH2#\ 0[75Ð0[62 ðm\ 5H\
P"CH1CH2#2Ł\ 0[12 ðd"t#\ 3Jꢁ06[7 Hz\ 2Jꢁ6[5 Hz\ 8H\
P"CH1CH2#2Ł\ 0[03:0[00 ðeach d\ 2Jꢁ5[6 Hz\ 2Jꢁ5[7 Hz\
each 2H\ CH"CH2#1Ł[ 02C NMR "099 MHz\ CDCl2#]
dꢁ068[20 "CO1#\ 069[39 "C1N#\ 049[27 "CarÐN#\ 036[90\
030[43\ 026[20\ 029[55\ 018[79\ 017[51\ 016[88\ 015[71
"Col#\ 016[74\ 014[36\ 001[20 "Car#\ 75[68 "a!C#\ 71[87
"ipso!C4H3#\ 39[29 ðN"CH2#1Ł\ 22[80 ðCH"CH2#1Ł\
08[77:08[54 ðCH"CH2#1Ł\ 03[21 ðd\ 0JCPꢁ21[0 Hz\
2
2Jꢁ0[6 Hz\ 1H\ C4H3#\ 3[12 ðct\ Jꢁ0[6 Hz\ 1H\ C4H3#\
3[01 "s\ 4H\ Cp#\ 2[45 ðd\ 2Jꢁ8[8 Hz\ 0H\ a!CHŁ\ 2[98 ðm\
0H\ CH"CH2#1Ł\ 1[05:1[92 "each s\ each 2H\ CH2#\ 0[48
2
ðs\ 04 H\ C4"CH2#4#Ł\ 0[14:9[88 ðeach d\ Jꢁ5[7 Hz\ each
2H\ CH"CH2#1Ł[ 02C NMR "099 MHz\ CDCl2#]
dꢁ067[42 "CO1#\ 060[39 "C1N#\ 74[64 "a!C#\ 74[25
ðC4"CH2#4Ł\ 72[91 "ipso!C4H3#\ 58[29 "C4H4#\ 56[96:55[81
"C4H3#\ 20[32 ðCH"CH2#1Ł\ 19[32:08[50 ðCH"CH2#1Ł\
03[45:01[80 "CH2#\ 8[26 ðC4"CH2#4Ł[ UV:Vis "CH1Cl1\ nm\
lg o#] lmaxꢁ305 "3[54#\ "MeOH\ nm\ lg o#] lmaxꢁ307

127
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
P"CH1CH2#2Ł\ 04[08:01[85 "CH2#\ 6[57 ðP"CH1CH2#2Ł[
20P NMR "098 MHz\ CDCl2#] dꢁ23[62 s "74)#\ 21[70 s
"04)#[ UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ347 "3[67#\
1[34:0[80 "each s\ each 2H\ CH2#\ 0[64Ð0[48:0[43Ð
0[31:0[31Ð0[20 ðeach m\ each 5H\ P"CH1CH1CH1CH2#2Ł\
0[01:0[90 ðeach d\ 2Jꢁ5[7 Hz\ 2Jꢁ5[7 Hz\ each 2H\
CH"CH2#1Ł\ 9[72 ðt\ 2Jꢁ6[1 Hz\ 8H\ P"CH1
CH1CH1CH2#2Ł[ 02C NMR "099 MHz\ CDCl2#]
dꢁ068[52 "CO1#\ 058[81 "C1N#\ 049[94 "CarÐN#\ 036[49\
030[47\ 026[34\ 029[54\ 018[63\ 017[39\ 016[74\ 015[68
"Col#\ 016[68\ 014[10\ 001[09 "Car#\ 74[17 "a!C#\ 39[97
"MeOH\
nm\
lg o#]
lmaxꢁ349
"3[48#[
C29H34ClN1O1PPd=0[4H1O "554[4#] calcd[ C 43[03\ H
6[16\ N 3[10^ found C 43[39\ H 6[22\ N 3[15[
2[13[ Complex of 5 with ð"n!Bu2P#"Cl#Pd"m!Cl#Ł1 21
ðN"CH2#1Ł\
22[30
ðCH"CH2#1Ł\
14[35
ðP"CH1
Dark red powder[ IR "KBr\ cm−0#] nꢁ0548 vs "COO\
CH1CH1CH2#2Ł\ 12[68 ðd\ 2JCPꢁ02[7 Hz\ P"CH1
CH1CH1CH2#2Ł\ 19[00 ðd\ 0JCPꢁ26[3 Hz\ P"CH1
CH1CH1CH2#2Ł\ 08[53:08[16 ðCH"CH2#1Ł\ 02[47 ðP"CH1
CH1CH1CH2#2Ł\ 03[71:01[74 "CH2#[ 20P NMR "098 MHz\
CH1Cl1#] dꢁ−3[24 "0JPtPꢁ2489 Hz\ 83)#\ −5[95 s
"5)#[ UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ369 "4[92#\
"MeOH\ nm\ lg o#] lmaxꢁ351 "3[58#[ C25H47ClN1O1PPt
"701[3#] calcd[ C 42[11\ H 6[19\ N 2[34^ found C 41[87\ H
6[29\ N 2[25[
½
0
C1N#\ 0597 vs "C1C#[ H NMR "169 MHz\ CDCl2#]
dꢁ6[44 "d\ JHPꢁ03[9 Hz\ 0H\ N1CH#\ 6[29Ð5[19 "m\
3
2
3
09H\ Har\ Hol#\ 2[44 ðd"d#\ Jꢁ00[9 Hz\ Jꢁ1[4 Hz\ 0H\
a!CHŁ\ 2[11 ðm\ 0H\ CH"CH2#1Ł\ 1[81 ðs\ 5H\ N"CH2#1Ł\
1[35:0[88 "each s\ each 2H\ CH2#\ 0[62Ð0[52:0[50Ð
0[49:0[35Ð0[27 ðeach m\ each 5H\ P"CH1CH1CH1CH2#2Ł\
0[06:0[96 ðeach d\ 2Jꢁ5[5 Hz\ 2Jꢁ5[5 Hz\ each 2H\
CH"CH2#1Ł\ 9[78 ðt\ 2Jꢁ6[2 Hz\ 8H\ P"CH1
CH1CH1CH2#2Ł[ 02C NMR "099 MHz\ CDCl2#]
dꢁ068[26 "CO1#\ 069[29 "C1N#\ 049[21 "CarÐN#\ 036[98\
030[43\ 026[17\ 029[69\ 018[78\ 017[61\ 017[95\ 015[84
"Col#\ 016[80\ 014[44\ 001[25 "Car#\ 39[15 ðN"CH2#1Ł\ 22[70
ðCH"CH2#1Ł\ 14[73 ðP"CH1CH1CH1CH2#2Ł\ 13[93 ðd\
2[16[ Complex of 6 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 24
Yellow orange powder\ m[p[ 75Ð77>C[ IR "KBr\
0
cm−0#] nꢁ0546 vs "COO\ C1N#[ H NMR "169 MHz\
½
2JCPꢁ01[3 Hz\
P"CH1CH1CH1CH2#2Ł\
P"CH1CH1CH1CH2#2Ł\
10[17
08[71:08[43
ðd\
CDCl2#] dꢁ7[45:7[94 ðeach d"d#\ 2Jꢁ00[2 Hz\
0JCPꢁ29[6 Hz\
3JHPꢁ5 Hz\ 2Jꢁ09[1 Hz\ JHPꢁ03[2 Hz\ 0H\ N1CH\
3
2
3
ðCH"CH2#1Ł\ 02[52 ðP"CH1CH1CH1CH2#2Ł\ 04[91:01[78
"CH2#[ 20P NMR "25[2 MHz\ CH1Cl1#] dꢁ16[12 s "77)#\
14[00 s "01)#[ UV:Vis "CH1Cl1\ nm\ lg o#] lmaxꢁ347
"3[53#\ "MeOH\ nm\ lg o#] lmaxꢁ343 "3[42#[
C25H47ClN1O1PPd=9[4H1O "621[7#] calcd[ C 48[90\ H
7[14\ N 2[71^ found C 48[98\ H 7[97\ N 2[65[
"0]0#Ł\ 6[32Ð5[98 "m\ 5H\ Hol#\ 2[61 ðd"d#\ Jꢁ5[2 Hz\ J
ꢁ2[1 Hz\ 0H\ a!CHŁ\ 1[59 ðm\ 0H\ CH"CH2#1Ł\
1[10:1[90:0[61 "each s\ each 2H\ CH2#\ 0[80Ð0[34 ðm\ 5H\
P"CH1CH2#2Ł\ 0[34 ðd"t#\ 3Jꢁ06[4 Hz\ 2Jꢁ6[4 Hz\ 8H\
P"CH1CH2#2Ł\ 0[11:0[04 ðeach d\ 2Jꢁ5[6 Hz\ 2Jꢁ5[6 Hz\
each 2H\ CH"CH2#1Ł\ 0[92 ðs\ 5H\ C"CH2#1Ł[ 02C NMR
"099 MHz\ CDCl2#] dꢁ068[81 "CO1#\ 053[98 "C1N#\
040[41\ 039[11\ 026[95\ 025[73\ 024[98\ 020[98\ 018[50\
018[15\ 017[80\ 014[33 "Col#\ 72[70 "a!C#\ 28[31
ðCH1C"CH2#1Ł\ 23[94 ðCH"CH2#1Ł\ 22[43 ðCH"CH2#1Ł\
21[83 ðCH1C"CH2#ꢁŁ\ 17[66 ðCH"CH2#1Ł\ 08[30:08[00
2[14[ Complex of 5 with ð"Ph2P#"Cl#Pd"m!Cl#Ł1 22
Dark red powder[ IR "KBr\ cm−0#] nꢁ0550 vs "COO\
½
C1N#\ 0596 vs "C1C#[ 0H NMR "89 MHz\ CDCl2#]
dꢁ6[7Ð5[9 "m\ 15H\ N1CH\ Har\ Hol#\ 2[1 ðm\ 0H\ a!
CHŁ\ 2[9 ðs\ 5H\ N"CH2#1Ł\ 1[4 ðm\ 0H\ CH"CH2#1Ł\ 1[9:0[8
"each s\ each 2H\ CH2#\ 0[0 ðd\ br\ 5H\ CH"CH2#1Ł[ 02C
NMR "56 MHz\ CDCl2#] dꢁ067[69 "CO1#\ 069[52
"C1N#\ 027[34\ 023[29\ 020[10\ 017[24\ 016[83\ 014[21
"C5H4#\ 036[29\ 030[48\ 026[33\ 029[54\ 018[61\ 017[00\
016[53\ 015[65 "Col#\ 016[98\ 014[16\ 001[06 "C5H3#\ 75[48
"a!C#\ 39[06 ðN"CH2#1Ł\ 22[72 ðCH"CH2#1Ł\ 08[68:08[42
ðCH"CH2#1Ł\ 04[43:01[89 "CH2#[ 20P NMR "098 MHz\
0
ðCH"CH2#1Ł\ 07[88 ð"CH1#1Ł\ 03[95 ðd\ JCPꢁ20[2 Hz\
1
P"CH1CH2#2Ł\ 10[44:02[96:01[65 "CH2#\ 6[42 ðd\ JCPꢁ
2[0 Hz\ P"CH1CH2#2Ł[ 20P NMR "098 MHz\ CH1Cl1#]
dꢁ22[14 s "43)#\ 21[48 s "35)#[ UV:Vis "MeOH\ nm\
lg o#] lmaxꢁ305 "3[26#\ "toluene\ nm#] lmaxꢁ391[
C20H40ClNO1PPd "531[5#] calcd[ C 46[83\ H 7[99\ N 1[07^
found C 46[21\ H 6[86\ N 1[99[
2[17[ Complex of 6 with ð"n!Bu2P#"Cl#Pt"m!Cl#Ł1 25
CH1Cl1#] dꢁ16[16
s
"5)#\ 13[65
s
"83)#[
C31H35ClN1O1PPd=H1O "681[6#] calcd[ C 52[53\ H 4[87\
N 2[42^ found C 52[38\ H 5[94\ N 2[44[
Orange powder[ IR "KBr\ cm−0#] nꢁ0569 vs "COO\
½
0
2
C1N#[ H NMR "169 MHz\ CDCl2#] dꢁ7[28 ðd"d#\ J
ꢁ09[4 Hz\ JHPꢁ02[9 Hz\ 0H\ N1CHŁ\ 6[38 "d\ 2J
3
2[15[ Complex of 5 with ð"n!Bu2P#"Cl#Pt"m!Cl#Ł1 23
ꢁ09[4 Hz\ 0H\ CHÐCH1N#\ 6[02Ð5[00 "m\ 4H\ Hol#\
2
3
2[73 ðd"d#\ Jꢁ5[4 Hz\ Jꢁ2[3 Hz\ 0H\ a!CHŁ\ 1[52 ðm\
0H\ CH"CH2#1Ł\ 1[97:1[99:0[61 "each s\ each 2H\ CH2#\
0[74Ð0[64:0[54Ð0[45:0[41Ð0[33 ðeach m\ each 5H\ P"CH1
CH1CH1CH2#2Ł\ 0[19:0[07 ðeach d\ 2Jꢁ6[9 Hz\ 2J
ꢁ6[1 Hz\ each 2H\ CH"CH2#1Ł\ 0[92 ðs\ 5H\ C"CH2#1Ł\
9[84 ðm\ 8H\ P"CH1CH1CH1CH2#2Ł[ 02C NMR
Dark red powder[ IR "KBr\ cm−0#] nꢁ0564 vs "COO\
½
0
C1N#\ 0597 vs "C1C#[ H NMR "169 MHz\ CDCl2#]
3
dꢁ6[71 "d\ JHPꢁ01[8 Hz\ 0H\ N1CH#\ 6[15Ð5[06 "m\
09H\ Har\ Hol#\ 2[52 ðd"d#\ 2Jꢁ8[0 Hz\ 3Jꢁ1[7 Hz\ 0H\ a!
CHŁ\ 2[94 ðm\ 0H\ CH"CH2#1Ł\ 1[74 ðs\ 5H\ N"CH2#1Ł\

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
128
"099 MHz\ CDCl2#] dꢁ079[75 "CO1#\ 052[78 "C1N#\
2[20[ Complex of 7 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 27
041[09\ 039[47\ 026[48\ 026[08\ 024[21\ 020[33\ 029[12\
018[71\ 018[07\ 014[84 "Col#\ 71[68 "a!C#\ 28[40
ðCH1C"CH2#1Ł\ 23[02 ðCH"CH2#1Ł\ 22[39 ðCH"CH2#1Ł\
22[94 ðCH1C"CH2#ꢁŁ\ 17[75 ðCH"CH2#1Ł\ 14[36 ðP"CH1
CH1CH1CH2#2Ł\ 12[81 ðd\ 2JCPꢁ02[9 Hz\ P"CH1
CH1CH1CH2#2Ł\ 19[02 ðd\ 0JCPꢁ26[3 Hz\ P"CH1
CH1CH1CH2#2Ł\ 08[29:08[97 ðCH"CH2#1Ł\ 08[97 ð"CH1#1Ł\
03[95 ðd\ 0JCPꢁ20[2 Hz\ P"CH1CH2#2Ł\ 10[44:02[96:01[65
"CH2#\ 02[52 ðP"CH1CH1CH1CH2#2Ł\ 10[53:02[21:01[78
"CH2#[ 20P NMR "098 MHz\ CH1Cl1#] dꢁ−1[51 s "7)#\
−3[82 s "0JPPtꢁ2410 Hz\ 81)#[ UV:Vis "MeOH\ nm\
lg o#] lmaxꢁ277 "3[02#[ C26H50ClNO1PPt "702[3#] calcd[ C
43[52\ H 6[45\ N 0[61^ found C 43[36\ H 6[58\ N 0[51[
Red powder[ IR"KBr#] nꢁ0481 vs "C1N#\ 0469s\ 0449
½
vs[ 0H NMR "399 MHz\ CDCl2#] dꢁ7[44 "dd\ 0H\
3Jꢁ8[8 Hz\ 2Jꢁ04[3 Hz\ HC1N#\ 7[23 "dd\ 0H\
2
2
2Jꢁ8[7 Hz\ Jꢁ03[3 Hz\ Hol#\ 6[40 "d\ 1H\ Jꢁ8[9 Hz\
2
Me1NC5H3#\ 6[06 "d\ 0H\ Jꢁ7[4 Hz\ Har#\ 6[94 "d\ 0H\
2Jꢁ04[4 Hz\ Hol#\ 5[83 "t\ 0H\ Jꢁ6[0\ Har#[ 5[56Ð5[53
2
2
"m\ 2H\ Har\ Me1NC5H3#\ 5[35 "t\ 0H\ Jꢁ5[7 Hz\ Har#\
2[92 "s\ 5H\ N"CH2#1#\ 0[85Ð0[76 "m\ 5H\ PCH1CH2#\
0[22Ð0[14 "m\ 8H\ PCH1CH2#[ 02C NMR "099 MHz\
CDCl2#]
dꢁ050[8
"HC1N#\
040[65:037[50:
029[20 : 017[83 : 013[06 : 010[87 : 007[14 : 005[37 : 004[09:
0
000[78 "Col\ Car#\ 39[96 ðN"CH2#1Ł\ 03[07 "d\ JCPꢁ
20[3 Hz\ PCH1#\ 6[74 "PCH1CH2#[ 20P NMR "098 MHz\
CDCl2#] dꢁ20[71 s "54)#\ 20[05 s "24)#[ UV:Vis]
"CH1Cl1\ nm\ lg o#] lmaxꢁ342 "3[46# br[ C12H21ClN1OPPd
"413[0#] calcd[ C 43[13\ H 5[22\ N 4[49^ found C 42[01\ H
4[83\ N 4[46[
2[18[ Complex of 6 with ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 26
Yellow orange powder[ IR "KBr\ cm−0#] nꢁ0550 vs
½
"COO\ C1N#\ 0598 sh "C1C#[ 0H NMR "169 MHz\
CDCl2#] dꢁ7[29 ðd 2Jꢁ09[1 Hz\ 0H\ N1CHŁ\ 5[87Ð5[97
2[21[ Complex of 7 with ð"Et2P#"Cl#Pt"m!Cl#Ł1 28
2
"m\ 5H\ Hol#\ 4[13 ðCH1Cl1Ł\ 2[49 ðd\ Jꢁ8[4 Hz\ 0H\ a!
Red powder[ IR"KBr#] nꢁ0478 vs "C1N#\ 0464s\ 0449
½
CHŁ\ 1[96 ðm\ 0H\ CH"CH2#1Ł\ 1[97:0[85:0[55 "each s\
each 2H\ CH2#\ 0[50 ðs\ 04H\ C4"CH2#4Ł\ 0[58Ð0[24 "m\
5H\ CH1#\ 0[08:9[81 ðeach d\ 2Jꢁ5[6 Hz\ 2Jꢁ5[6 Hz\ each
2H\ CH"CH2#1Ł\ 9[86 ðs\ 5H\ C"CH2#1Ł[ 02C NMR
"099 MHz\ CDCl2#] dꢁ067[49 "CO1#\ 052[24 "C1N#\
040[19\ 030[96\ 026[45\ 025[85\ 023[18\ 020[57\ 029[32\
018[46\ 018[49\ 016[83 "Col#\ 74[03 ðC4"CH2#4Ł\ 71[75 "a!
C#\ 28[44 ðCH1C"CH2#1Ł\ 23[06 ðCH"CH2#1Ł\ 22[96
ðCH"CH2#1Ł\ 20[20 ðCH1C"CH2#ꢁŁ\ 17[76 ðCH"CH2#1Ł\
19[21 ðCH1"CH1#1Ł\ 08[36:08[97 ðCH"CH2#1Ł\ 08[97
ð"CH1#1Ł\ 10[53:03[91:01[80 "CH2#\ 8[18 ðC4"CH2#4Ł[
UV:Vis "MeOH\ nm\ lg o#] lmaxꢁ315 "3[13#\ "toluene\ nm\
lg o#] lmaxꢁ303 "3[35#[ C24H40ClIrNO1=9[4CH1Cl1 "676[8#]
calcd[ C 43[00\ H 5[54\ N 0[67^ found C 43[93\ H 5[67\ N
0[70[
0
vs[ H NMR "399 MHz\ CDCl2#] dꢁ7[66Ð7[53 "m\ 1H\
CH1N\ Hol#\ 6[43 "d\ 1H\ 2Jꢁ7[7 Hz\ Me1NC5H3#\ 6[13
2
2
"d\ 0H\ Jꢁ7[9 Hz\ Har#\ 6[02 "d\ 0H\ Jꢁ03[3 Hz\ Hol#\
5[83 "t\ 0H\ 2Jꢁ6[0 Hz\ Har#[ 5[63Ð5[56 "m\ 2H\ Har\
2
Me1NC5H3#\ 5[38 "t\ 0H\ Jꢁ5[8 Hz\ Hol#\ 2[95 ðs\ 5H\
N"CH2#1Ł\ 0[87Ð0[77 "m\ 5H\ PCH1CH2#\ 0[20Ð0[08 "m\
8H\ PCH1CH2#[ 20P NMR "098 MHz\ CDCl2#] dꢁ2[08 s
"64)#\ 0[29 s "14)#[ UV:Vis] "CH1Cl1\ nm\ lg o#]
lmaxꢁ317 "3[53#\ 383 "3[49#[ C12H21ClN1OPPt "502[1#]
calcd[ C 33[88\ H 4[14\ N 3[45^ found C 33[56\ H 4[05\ N
3[38[
2[22[ Complex of 7 with ð"h4!C4Me4#"Cl#Ir"m!Cl#Ł1 39
Red powder[ IR"KBr#] nꢁ0480 vs "C1N#\ 0469 s\
½
0438 s[ 0H NMR "399 MHz\ CDCl2# dꢁ7[21 "d\ 2J
ꢁ8[4 Hz\ HC1N#\ 6[33 "d\ 1H\ 2Jꢁ7[8 Hz\ Me1NC5H3#\
2[29[ General procedure for the synthesis of the complexes
27Ð34 with the Schiff bases 7Ð09
2
6[14Ð6[07 "m\ 1H\ Hol\ Har#\ 6[94 "d\ 0H\ Jꢁ04[4 Hz\
Hol#\ 5[86 "t\ 0H\ 2Jꢁ6[4 Hz\ Har#\ 5[89 "d\ 0H\ 2J
ꢁ7[2 Hz\ Har#\ 5[69 "d\ 1H\ 2Jꢁ8[9 Hz\ Me1NC5H3#\ 5[39
9[0 mmol of Schi} base 7Ð09 was stirred in 09 ml of
methanol\ and 9[0 mmol of NaOMe in methanol was
added[ To the resulting solution 9[94 mmol of
ð"Et2P#"Cl#Pd"m!Cl#Ł1\ ð"Et2P#"Cl#Pt"m!Cl#Ł1\ ð"h4!C4Me4#
"Cl#Ir"m!Cl#Ł1 or ð"h5!p!cymene#"Cl#Ru"m!Cl#Ł1 were
added in one portion[ After stirring the mixture for 1 h
at room temperature the solvent was evaporated in vacuo\
and 09 ml of dichloromethane were added[ Further stir!
ring for 1 h and then centrifugation yields a deep coloured
solution of the product\ which was puri_ed by pre!
cipitation from dichloromethane with n!pentane and
additional washing with n!pentane for the complexes 31Ð
34 and chromatography on cellulose::CH1Cl1:n!pentane
for complexes 27Ð30[
2
"t\ 0H\ Jꢁ7[1 Hz\ Har#\ 2[94 ðs\ 5H\ N"CH2#1Ł\ 0[55 ðs\
04H\ C4"CH2#4Ł[ 02C NMR "56[7 MHz\ CDCl2#] dꢁ
057[36 "HC1N#\ 047[42:040[55:035[87:018[87:018[36:
013[02:012[25:008[13:004[04:003[17:000[74 "Col\ Car#\
73[64 "C4Me4#\ 39[01 ðN"CH2#1Ł\ 7[80 ðC4"CH2#4Ł[ UV:Vis]
"CH1Cl1\ nm\ lg o#] lmaxꢁ338 "3[35#\ 385 "3[32#[
C16H21ClIrN1OÐH1O "535[1#] calcd[ C 49[07\ H 4[29\ N
3[22^ found C 38[56\ H 4[43\ N 3[12[
2[23[ Complex of 7 with ð"h5!C09H09#"Cl#Ru"m!Cl#Ł1
30
Red powder[ IR"KBr#] nꢁ0480 vs "C1N#\ 0460 s\
½
0
2
0449 s[ H NMR "399 MHz\ CDCl2#] dꢁ7[24 "d\ Jꢁ

139
O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
2
8[7 Hz\ HC1N#\ 6[34 "d\ 1H\ Jꢁ7[8 Hz\ Me1NC5H3#\
6[26 "dd\ 0H 2Jꢁ04[5 Hz\ 2Jꢁ8[3 Hz\ Hol#\ 6[13 "d\ 0H\
lmaxꢁ330 "3[57#\ 430 "3[46#\ "MeOH\ nm\ lg o#] lmaxꢁ328
"3[54#\ 418 "3[32#[ C22H30ClNOPPtÐH1O"791[6#] calcd C\
38[26^ H\ 4[16^ N\ 0[63^ found C\ 38[31^ H\ 4[28^ N\ 0[63[
2Jꢁ6[2 Hz\ Har#\ 6[01 "d\ 0H\ Jꢁ04[3 Hz\ Hol#\ 5[84 "t\
2
0H\ 2Jꢁ6[3 Hz\ Har#\ 5[76 "d\ 0H\ 2Jꢁ8[9 Hz\ Har#\ 5[63
"d\ 1H\ 2Jꢁ8[6 Hz\ Me1NC5H3#\ 5[39 "t\ 0H\ 2Jꢁ6[3 Hz\
2[26[ Complex of 09 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 33
Har#\ 4[45 "d\ 0H\ Jꢁ4[4 Hz\ h5!C5H3#\ 4[49 "d\ 0H\ J
ꢁ5[2 Hz\ h5!C5H3#\ 4[33 "d\ 0H\ 2Jꢁ4[7 Hz\ h5!C5H3#\
4[11 "d\ 0H\ 2Jꢁ4[5 Hz\ h5!C5H3#\ 2[97 ðs\ 5H\ N"CH2#1Ł\
1[62 ðsep\ 0H\ 2Jꢁ6[9 Hz\ CH"CH2#1Ł\ 1[26 "s\ 2H\ CH2#\
0[02 ðdd\ 5H\ CH"CH2#1Ł[ UV:Vis] "CH1Cl1\ nm\ lg o#]
lmaxꢁ320 "3[31#\ 385 "3[39#[ ! C16H20ClN1ORuÐ9[4H1O
"434[0#] calcd[ C 48[38\ H 4[81\ N 4[03^ found C 48[27\ H
5[05\ N 3[86[
2
2
Black powder\ soluble in all polar organic solvents\
in solution purple!black[ Two isomers "cis:trans# were
obtained which could not be separated but gave di}erent
NMR shifts[ IR"KBr#] nꢁ0593 s "C1N#\ 0450 s\ 0419
½
0
vs "C1C#[ H NMR "399 MHz\ CDCl2#] dꢁ7[17:7[91
ðeach d\ 3JHPꢁ02[9 Hz\3JHPꢁ5[6 Hz\ 0H\ CH1N\ "5]3#Ł\
6[25 "d\ 1H\ 2Jꢁ8[0 Hz\ C5H3#\ 6[08 "d\ 0H\ 2Jꢁ6[4 Hz\
H3#\ 6[99Ð5[78 "m\ 2H\ Har\ Holef#\ 5[79Ð5[53 "m\ 4H\ C5H3\
Har\ Hol#\ 5[38 "t\ 2Jꢁ6[7 Hz\ Har#\ 5[28Ð5[20 "m\0H\ Hol#\
2[9 "s\ 5H\ N"CH2#1#\ 1[42:0[71 ðeach s\ 2H\ CH2!cis\ CH2!
trans\ "2]1#Ł\ 1[96 "s\ 2H\ CH2#\ 0[83Ð0[74 "m\ 5H\ PCH1#\
0[23Ð0[13 "m\ 8H\ PCH1CH2#[ 20P NMR "098 MHz\
CH1Cl1#] dꢁ24[28 s "39)#\ 21[81 s "59)#[ UV:Vis]
"CH1Cl1\ nm\ lg o#] lmaxꢁ383 "3[65#[ C20H31ClN1OPPdÐ
H1O"538[3#] calcd[ C 46[22\ H 5[71\ N 3[20^ found C
45[69\ H 5[89\ N 3[11[
2[24[ Complex of 8 with ð"Et2P#"Cl#Pd"m!Cl#Ł1 31
Black powder\ soluble in all polar organic solvents\
in solution purple!black[ Two isomers "cis:trans# were
obtained which could not be separated but gave di}erent
NMR shifts[ IR"KBr#] nꢁ0503 "C1N#\ 0472\ 0459\ 860\
½
657\ 630[ 0H NMR "399 MHz\ CDCl2#] dꢁ7[16:7[90
ðeach d\ 3JHPꢁ02[3 Hz\ 3JHPꢁ5[4 Hz\ 0H\ CH1N\ "3]5#Ł\
6[12 "m\ 0H\ Har#\ 5[85Ð5[15 "m\ 8H\ Hol\ Har#\ 3[31 "m\
1H\ C4H3#\ 3[20 "m\ 1H\ C4H3#\ 3[01 "s\ 4H\ C4H4#\
1[49:0[79 ðs\ 2H\ CH2!cis\ CH2!trans "3]5#Ł\ 1[93 "s\ 2H\
CH2#\ 0[81Ð0[74 "m\ 5H\ PCH1#\ 0[22Ð0[13 "m\ 8H\
2[27[ Complex of 09 with ð"Et2P#"Cl#Pt"m!Cl#Ł1 34
Black powder\ soluble in all polar organic solvents
purple black[ Two isomers "cis:trans# were obtained
which could not be separated but gave di}erent NMR
signals[ 0H NMR "169 MHz\ CDCl2#] dꢁ7[41:7[13 ðeach
d\ 3JHPꢁ02[3 Hz\ 3JHPꢁ4[8 Hz\ 2H\ CH1N\ "0]8#Ł\ 6[26
PCH1CH2#[
02C
NMR
"099 MHz\
CDCl2#]
dꢁ053[25:052[09 "C1N cis:trans#\ 034[69\ 039[67\
028[91\ 025[50\ 029[71\ 018[59\ 018[28\ 018[05\ 016[00\
012[23\ 006[70\ 005[99\ 004[62\ 002[69 "Car\ Col#\ 72[05\
58[34\ 56[92\ 04[80\ 03[60\ 03[30\ 01[73\ 6[64\ 6[61[ 20P
NMR "098 MHz\ CH1Cl1#] dꢁ23[58 s "39)#\ 21[11 s
"59)#[ UV:Vis] "CH1Cl1\ nm\ lg o#] lmaxꢁ328 "3[91#\ 417
"2[67#\ "MeOH\ nm#] lmaxꢁ401\ 317^ C22H30ClFeN!
OPPd=9[4H1O "694[2#] calcd[ C 45[07\ H 5[99\ N 0[88^
found C 44[53\ H 4[62\ N 1[96[
2
"d\ 1H\ Jꢁ7[6 Hz\ C5H3#\ 6[90Ð5[77 "m\ 3H\ Har\ Holef#\
2
5[67Ð5[43 "m\ 5H\ C5H3\ Har\ Holef#\ 5[39 "t\ Jꢁ5[8 Hz\
H1#\ 5[23 "d\ 2Jꢁ00[7 Hz\ H4#\ 2[9 "s\ 5H\ N"CH2#1#\
1[43:0[73 ðeach s\ 2H\ CH2!cis\ CH2!trans\ "0]8#Ł\ 1[96 "s\
2H\ CH2#\ 0[86Ð0[78 "m\ 5H\ PCH1#\ 0[17Ð0[19 "m\ 8H\
PCH1CH2#^ 02C NMR "099 MHz\ CDCl2#] dꢁ069[75
"C1N#\ 049[25\ 035[57\ 030[89\ 027[80\ 026[28\ 029[71\
029[96\ 018[27\ 017[67\ 016[87\ 015[83\ 014[48\ 006[27\
003[25\ 001[27 "Car\ Col#\ 39[15 ðN"CH2#1Ł\ 03[52:01[81
2[25[ Complex of 8 with ð"Et2P#"Cl#Pt"m!Cl#Ł1 32
0
Black powder\ soluble in all polar organic solvents
purple black[ Two isomers "cis:trans# were obtained
which could not be separated but gave di}erent NMR
"CH2#\ 02[54 ðd\ JCPꢁ26 Hz\ P"CH1CH2#2Ł\ 6[31
ðP"CH1CH2#2Ł[ 20P NMR] dꢁ3[03 s ð0JPtPꢁ2596 Hz\
89)Ł\ 2[98 s "09)#[ UV:Vis] "CH1Cl1\ nm\ lg o#]
lmaxꢁ317 "3[83#[ C20H31ClN1OPPtÐH1O"627[0#] calcd[ C
49[33\ H 5[99\ N 2[68^ found C 38[30\ H 4[73\ N 2[40[
signals[ IR"KBr#] nꢁ0503\ 0475\ 0452 "C1N\ C1C#\
½
860\ 374 "PtÐN#\ 235 "PtÐCl#[ 0H NMR "399 MHz\
3
3
CDCl2#] dꢁ7[42:7[14 ðeach d\ JHPꢁ02[3 Hz\ JHP
ꢁ
4[7 Hz\ 0H\ CH1N"0]8#Ł\ 6[22Ð5[27 "m\ 09H\ Hol\ Har#\
3[33 "ct\ 2Jꢁ1 Hz\ 1H\ C4H3#\ 3[22 "ct\ 2Jꢁ0[8 Hz\ 1H\
C4H3#\ 3[02 "s\ 4H\ C4H4#\ 1[42:0[73 ðeach s\ 2H\ CH2\
"0]4#Ł\ 1[94 "s\ 2H\ CH2#\ 1[9Ð0[78 "m\ 5H\ PCH1#\ 0[21Ð
0[08 "m\ 8H\ PCH1CH2#[ 02C NMR "56MHz\ CDCl2#]
dꢁ069[73 "C1N#\ 052[16 "C1N#\ 035[30:030[11:027[72:
026[13 : 029[51 : 029[42 : 018[47 : 018[32 : 016[96 : 012[59:
006[34:003[26 "Col\ Car#\ 72[02\ 58[40\ 56[97\ 03[69:01[89
2[28[ 8!Ferrocenyl!1\6!dimethylnonatetraen!0!ð"h5!ben!
zenechromiumtricarbonyl#!imineŁ 35
58[4 mg
"9[1 mmol#
of
8!ferrocenyl!1\6!dime!
thylnonatetraenal ð65Ł and 33[4 mg of ðh5!aminobenzeneŁ!
chromiumtricarbonyl were stirred in 09 ml of dichlo!
romethane with Na1SO3 for 2 d[ After centrifugation the
solvent was removed in vacuo[ The crude product was
washed with n!pentane:Et1O "4]0#[ 59 mg "39)#[ Single
crystals were obtained by di}usion of n!pentane into a
0
"CH2#\ 02[68 ðd\ JCPꢁ22 Hz\ P"CH1CH2#2Ł\ 6[37
ðP"CH1CH2#2Ł[ 20P NMR] dꢁ3[09 s ð0JPtPꢁ2599 Hz\
"76)#Ł\ 2[96 s "02)#[ UV:Vis] "CH1Cl1\ nm\ lg o#]
dichloromethane solution[ IR"KBr#] nꢁ0850\ 0783\
½

O[ Briel et al[:Polyhedron 07 "0888# 114Ð131
130
0762[ 0H NMR "399 MHz\ CDCl2#] dꢁ7[94 "s\ 0H\
CH1N#\ 5[87Ð5[56 "m\ 2H\ Hol#\ 5[42Ð5[38 "m\ 1H\ FcÐ
CH1CH#\ 5[29 "d\ 2Jꢁ01[1 Hz\ HC1C"CH2#CH1N#\
4[38 "t\ 2Jꢁ5[4 Hz\ 1H\ Hmetaar#\ 4[15 "d\ 2Jꢁ4[8 Hz\ 1H\
Horthoar#\ 4[19 "t\ Jꢁ5[2 Hz\ 0H\ Hparaar#\ 3[33 "m\ 1H\
C4H3#\ 3[21 "m\ 1H\ C4H3#\ 3[02 "s\ 4H\ C4H4#\ 1[94:1[92
"each s\ each 2H\ CH2#[
ð19Ł Sato M\ Shintate H\ Kawate Y\ Sekino M\ Katada M\ Kawata S[
Organometallics 0883^02]0845[
ð10Ł Colbert MCB\ Ingham SL\ Lewis J\ Long NJ\ Raithby PR[ J[
Chem[ Soc[\ Dalton[ Trans[ 0883^1104[
ð11Ł Colbert MCB\ Edwards AJ\ Lewis J\ Long NJ\ Page NA\ Parker
DG\ Raithby PR[ J[ Chem[ Soc[\ Dalton Trans[ 0883^1478[
ð12Ł Behrens U\ Brussaard H\ Hagenau U\ Heck J\ Hendrick E\ Kor!
Ã
2
nich J\ van der Linden JGM\ Persoons A\ Spek AL\ Veldman N\
Voss B\ Wong H[ Chem[ Eur[ J[ 0885^1]87[
ð13Ł Brady M\ Weng W\ Gladysz JA[ J[ Chem Soc[\ Chem[ Commun[
0883^1544[
ð14Ł Zhou Y\ Seyler JW\ Weng W\ Arif AM\ Gladysz JA[ J[ Am[ Chem[
Soc[ 0882^004]7498[
Acknowledgements
Generous
support
by
Deutsche
For!
ð15Ł Brady M\ Weng W\ Zhou Y\ Seyler JW\ Amoroso AJ\ Arif AM\
schungsgemeinschaft and Fonds der Chemischen Indu!
strie is gratefully acknowledged[ We thank BASF AG\
Ludwigshafen\ and F[!Ho}mann!LaRoche AG\ Basel\
for generous gifts of carotenoid dialdehydes and Pro!
Bohme M\ Frenking G\ Gladysz JA[ J[ Am[ Chem[ Soc[
Ã
0886^008]664[
ð16Ł Gladysz JA\ Bartik TA\ Bartik B\ Brady M\ Dembinski R[ Angew[
Chem[ 0885^097]356[
ð17Ł Seyler JW\ Weng W\ Zhou Y\ Gladysz JA[ Organometallics
0882^01]2791[
fessor Karlheinz Sunkel\ Munich\ for helpful discussions[
Ã
Further details for the X!ray structure determinations
can be obtained from the Cambridge Crystallographic
Data Centre[
ð18Ł Bunz UHF[ Angew[ Chem[ 0885^097]0936[
ð29Ł Bunz UHF[ Angew[ Chem[ Int[ Ed[ Engl[ 0885^24]857[
ð20Ł Le Narvor N\ Toupet L\ Lapinte C[ J[ Am[ Chem[ Soc[
0884^006]6018[
ð21Ł Schimanke H\ Gleiter R[ Organometallics 0887^06]164[
ð22Ł Lavastre O\ Plass J\ Bachmann P\ Guesmi S\ Moinet C\ Dixneuf
PH[ Organometallics 0886^05]073[
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