Polymeric transition metal complexes of 1,4-bis- (4-pyridylsulfenylmethyl)benzene and of its 2-pyridyl analogue

Article abstract of DOI:10.1016/S0277-5387(98)00295-2

The preparations are reported of a range of complexes of Mn^II, Co^II, Ni^II and Cu^II with 1,4-bis- (4-pyridylsulfenylmethyl)benzene (B4PSB) and of complexes of Co^II, Ni^II and Cu^II with the 2-pyridyl analogue (B2PSB), together with relevant spectroscopic data. X-Ray crystallographic studies on Co (B2PSB) (NO₃)₂ show the presence of a chain structure in which five-coordinate cobalt centers are linked by bridging (B2PSB) ligands, with the remaining coordination sites about each metal atom being occupied by one very asymmetrically chelating nitrate group and an oxygen atom of a unidentate nitrate.

Full text of DOI:10.1016/S0277-5387(98)00295-2

\
Polyhedron 07 "0888# 162Ð168
PERGAMON
Polymeric transition metal complexes of 0\3!bis!"3!
pyridylsulfenylmethyl#benzene and of its 1!pyridyl analogue
Zeno Atherton\ David M[ L[ Goodgameꢀ\ Stephan Menzer\ David J[ Williams
Chemistry Department\ Imperial College of Science\ Technology and Medicine\ London SW6 1AY\ U[K[
Received 04 June 0887^ accepted 11 July 0887
Abstract
The preparations are reported of a range of complexes of MnII\ CoII\ NiII and CuII with 0\3!bis!"3!pyridylsulfenylmethyl#benzene
"B3PSB# and of complexes of CoII\ NiII and CuII with the 1!pyridyl analogue "B1PSB#\ together with relevant spectroscopic data[ X!
Ray crystallographic studies on Co"B1PSB#"NO2#1 show the presence of a chain structure in which _ve!coordinate cobalt centers are
linked by bridging "B1PSB# ligands\ with the remaining coordination sites about each metal atom being occupied by one very
asymmetrically chelating nitrate group and an oxygen atom of a unidentate nitrate[ Þ 0888 Elsevier Science Ltd[ All rights reserved[
Keywords] X!ray structure^ Polymeric complexes^ Bis"pyridine# ligands
0[ Introduction
There is currently appreciable interest in the types
of polymeric arrays which can be prepared by the inter!
action of metal salts with extended!reach ligands of type
I\ in which pairs of 3!pyridyl units are linked by an
appropriate spacer group\ and it has been shown that
variations in the linking unit in~uence the types of struc!
ture formed ð0Ð7Ł[ With a related aim\ we have been
exploring the network!forming ability of linked pyr!
rolidin!1!thione "e[g[ II# ð8Ł and pyridin!1!thione "e[g[ III#
ð09\00Ł ligands\ which can be obtained by the action of
Lawesson|s reagent on their bis"pyrrolidin!1!one# and
bis"pyridin!1!one# analogues[ Parallel studies\ using the
direct reaction between a\a?!0\3!dibromoxylene and the
sodium salts of 1! or 3!mercaptopyridine have a}orded
the complementary types of ligand\ IV "B1PSB# and V
"B3PSB# respectively\ in which the sulfur atoms are incor!
porated into the spacer group connecting pairs of 1!
or 3!pyridyl donor groups[ We report here some metal
complexes of IV and V and the results of an X!ray study
on Co"B1PSB#"NO2#1[
ꢀ Corresponding author[
9166!4276:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[
PII] S9166!4276 "87#99184!1

163
Z[ Atherton et al[ : Polyhedron 07 "0888# 162Ð168
1[ Experimental
cobalt"II# bromide hexahydrate "9[090 g\ 9[20 mmol#
respectively in ethanol "1 cm2# with a solution of B1PSB
"9[986 g\ 9[29 mmol# also in ethanol "4 cm2#[ IR] chloride
1[0[ Preparation of compounds
n"CoÐCl# 299\ 215 cm−0
^ bromide n"CoÐBr# 129\
1[0[0[ 0\3!Bis!"1!pyridylsulfenylmethyl# benzene
159 cm−0
[
Sodium "0[69 g\ 63 mmol# was dissolved in butan!0!ol
"049 cm2# in a ~ask _tted with a re~ux condenser and a
CaCl1 drying tube[ Pyridin!1!thione "4[9 g\ 34 mmol# and
a\a?!0\3!dibromoxylene "4[82 g\ 11[4 mmol# were added
and the mixture was re~uxed "graphite bath\ 019>C# for
4 h[ Upon cooling\ golden needle!like crystals separated[
The butan!0!ol was removed and then diethylether
"199 cm2# was added to the slightly damp solid\ and the
mixture stirred thoroughly[ The product was extracted
into dichloromethane\ dried over anhydrous magnesium
sulfate and crystallized by slow evaporation[ The tan!
colored crystals were dried in vacuo over P1O4 "yield 74)\
mp 64Ð65>C#[ Found] C\ 55[5] H\ 4[9^ N\ 7[5[ Calc[ for
C07H05N1S1] C\ 55[5^ H\ 4[9^ N\ 7[5)[ MS"EI# 213 "M¦#[
0H NMR "169 MHz\ CDCl2#] d 3[31 "3H\ s#\ 6[99 "1H\
m#\ 6[05 "1H\ m#\ 6[23 "3H\ s#\ 6[36 "1H\ m#\ 7[34 "1H\
d#[ The constitution of the ligand is also con_rmed by
the structure of the complex Co"B1PSB#"NO2#1[
1[1[1[ CoI1"B1PSB#
This was prepared as for the previous complexes\ and
on the same scale\ but with the cobalt"II# iodide in a
mixture of ethanol "1 cm2# and methanol "9[3 cm2#[
1[1[2[ M"NO2#1"B1PSB# "MꢀCo\ Ni#
A solution of the respective\ hydrated metal nitrate
"9[933 g\ 9[04 mmol# in ethanol "1 cm2# was added to one
of B1PSB "9[938 g\ 9[04 mmol# also in ethanol "4 cm2#[ In
the case of the cobalt complex the clear\ purple solution
was left to crystallize slowly\ until crystals of suitable
quality for X!ray study had formed[ After removal of
some of the crystals the remainder of the solution was
concentrated to ca 0 cm2\ treated with nitromethane
"4 cm2# and then re~uxed\ and a good yield of the purple
complex separated[ A similar procedure was used to
obtain the nickel complex\ but in that case crystals were
not grown[
1[0[1[ 0\3!Bis!"3!pyridylsulfenylmethyl#benzene
This was obtained by essentially the same procedure
and on the same scale\ but using pyridin!3!thione and
extracting the product into chloroform instead of dichlo!
romethane "yield 65)\ mp 076Ð089>C#[ Found] C\ 55[5]
H\ 3[8^ N\ 7[5[ Calc[ for C07H05N1S1] C\ 55[5^ H\ 4[9^ N\
1[1[3[ Cu"B1PSB#1"ClO3#1
This green complex precipitated on mixing ethanolic
solutions of hydrated copper"II# perchlorate "9[945 g\
9[04 mmol in 1 cm2# and B1PSB "9[986 g\ 9[29 mmol in
4 cm2#[ IR] n3"ClO−3# 512 cm−0
[
0
7[5)[ MS"EI# 213 "M¦#[ H NMR "169 MHz\ CDCl2#]
d 3[08 "3H\ s#\ 6[09 "3H\ d#\ 6[25 "3H\ s#\ 7[27 "3H\ d#[
1[1[4[ MnCl1"B3PSB#=H1O
This complex precipitated on addition of a solution of
B3PSB "9[938 g\ 9[04 mmol# in nitromethane "4 cm2# to
one of MnCl1=3H1O "9[929 g\ 9[04 mmol# in ethanol
"1 cm2#[
1[1[ Metal complexes
Analytical data "Microanalytical Laboratory\ Imperial
College#\ colors and yields of the complexes are given in
Table 0[ Preparative details are summarized below[ The
cobalt"II# and nickel"II# iodide and thiocyanate starting
reagents were prepared metathetically by mixing con!
centrated methanol solutions of the corresponding metal
nitrates and sodium iodide or potassium thiocyanate
respectively and removal of the precipitated alkali metal
nitrates[ Unless stated otherwise\ the metal complexes
were collected by _ltration\ washed with a small amount
of the solvent used for the preparation and then dried in
vacuo over P1O4[
Caution; Although we did not observe any explosive
behavior with the copper"II# perchlorate compounds
described below\ all metal perchlorates must be regarded
as potentially explosive and appropriate safety measures
taken[
1[1[5[ CoBr1"B3PSB#
Addition of a solution of CoBr1=5H1O "9[938 g\
9[04 mmol# in a mixture of ethanol "9[4 cm2# and nitro!
methane "0 cm2# to one of B3PSB "9[938 g\ 9[04 mmol# in
hot "79>C# nitromethane "4 cm2# gave the complex as a
_ne blue powder[
1[1[6[ CoI1"B3PSB#
This was obtained as for the previous complex\ and on
the same scale\ but using a solution of cobalt"II# iodide
in a mixture of methanol "9[1 cm2# and nitromethane
"0 cm2#[
1[1[7[ Co"NCS#1"B3PSB#1=1H1O
This pink complex precipitated on the addition of a
solution of cobalt"II# thiocyanate "9[04 mmol# in a mix!
ture of methanol "9[1 cm2# and nitromethane "0 cm2# to a
solution of B3PSB "9[986 g\ 9[2 mmol# in nitromethane
1[1[0[ CoX1"B1PSB# "XꢀCl\ Br#
These compounds precipitated on mixing a solution of
cobalt"II# chloride hexahydrate "9[963 g\ 9[20 mmol# or
"6 cm2#[ IR] n"CN# 1942 cm−0
[

Z[ Atherton et al[ : Polyhedron 07 "0888# 162Ð168
164
Table 0
Analytical data\ colors and yields of the complexes formed by ligands IV and V
Complex
Color
Analysis ")#a
C
Yield")#
H
N
Ligand IV "ꢁL#
CoCl1L
CoBr1L
blue
blue
green
purple
green
green
36[7 "36[5#
28[8 "28[7#
23[4 "22[8#
31[6 "31[5#
31[5 "31[5#
36[5 "36[4#
2[4 "2[5#
1[8 "2[9#
1[4 "1[4#
2[9 "2[1#
2[9 "2[1#
2[7 "2[4#
5[1 "5[1#
4[0 "4[1#
3[3 "3[3#
00[9 "00[9#
09[8 "00[0#
4[7 "5[1#
50
45
59
70
68
55
CoI1L
Co"NO2#1L
Ni"NO2#1L
ðCuL1Ł"ClO3#1
Ligand V "ꢁL?#
MnCl1L?=H1O
CoBr1L?
cream
blue
green
pink
yellow
tan
35[4 "35[1#
28[7 "28[7#
23[1 "22[8#
42[0 "42[0#
35[0 "34[7#
28[3 "28[7#
2[4 "2[8#
2[0 "2[9#
1[5 "1[4#
2[6 "3[1#
2[5 "2[7#
2[0 "2[9#
1[6 "1[4#
2[4 "2[3#
2[0 "2[4#
2[2 "2[1#
2[4 "2[4#
2[9 "1[8#
2[6 "2[7#
4[8 "5[9#
4[0 "4[1#
3[6 "3[3#
09[9 "8[7#
5[9 "4[8#
4[0 "4[1#
3[60 "3[3#
4[8 "4[7#
09[5 "09[6#
00[9 "00[1#
4[8 "5[0#
4[0 "4[0#
5[9 "4[8#
53
49
62
55
45
47
58
54
42
68
30
39
44
CoI1L?
Co"NCS#1L1?=1H1O
NiCl1L?=H1O
NiBr1L?
NiI1L?
NiI1L1?
Ni"NO2#1L?=H1O
Ni"NCS#1L?
CuCl1L?
CuBr1L?
CuL?1"ClO3#1=1H1O
orangeÐbrown 23[5 "22[8#
green
green
green
turquoise
green
purple
34[0 "34[9#
30[2 "30[1#
36[8 "37[0#
36[1 "36[0#
28[6 "28[4#
34[4 "34[5#
a Calculated values are given in parentheses[
1[1[8[ NiCl1"B3PSB#=H1O and NiBr1"B3PSB#
1[1[02[ Ni"NCS#1"B3PSB#
These compounds precipitated when solutions of nick!
el"II# chloride hexahydrate "9[925 g\ 9[904 mmol#\ or
nickel"II# bromide hexahydrate "9[925 g\ 9[904 mmol#
respectively\ in a mixture of ethanol "9[4 cm2# and nitro!
methane "0 cm2# were added to a hot solution of B3PSB
"9[938 g\ 9[04 mmol# in nitromethane "4 cm2#[
The same procedure was employed as for NiI1"B3PSB#\
and on the same scale\ but using nickel"II# thiocyanate
instead of nickel"II# iodide[ IR] n"CN# 1001 cm−0
[
1[1[03[ CuX1"B3PSB# "XꢀCl\ Br#
These compounds were obtained as for their nickel"II#
analogues\ and on the same scale\ but they separated as
very _ne powders and were collected by centrifuging[
1[1[09[ Ni"NO2#1"B3PSB#=H1O
This was prepared as for the previous complexes\ and
on the same scale\ but the solution of B3PSB was added
to the nickel nitrate solution[
1[1[04[ Cu"B3PSB#1"ClO3#1=1H1O
Addition of a solution of hydrated copper"II# per!
chlorate "9[915 g\ 9[96 mmol# in a mixture of ethanol
"0 cm2# and nitromethane "0 cm2# to a solution of B3PSB
"9[938 g\ 9[04 mmol# in nitromethane "4 cm2# gave a
cloudy purple solution\ from which a purple mic!
1[1[00[ NiI1"B3PSB#
A solution of nickel"II# iodide "9[04 mmol# in a mixture
of methanol "0 cm2# and nitromethane "0 cm2# was added
dropwise over a period of 1 min to a re~uxing solution of
B3PSB "9[938 g\ 9[04 mmol# in nitromethane "4 cm2#[ The
solution was momentarily brown in color\ but the _rst
few drops of the nickel iodide solution caused the for!
mation of a green solid[ As more nickel iodide was added
the brown color was maintained for longer periods
between the additions and the green solid _nally became
orangeÐbrown[
rocrystalline powder separated within 13 h[ IR] n3"ClO−
#
3
512 cm−0
[
1[2[ Spectroscopy
The EPR spectra were measured at room temperature
on a Varian E01 X!band "ca 8[4 GHz# spectrometer using
powdered samples[ Mass spectra "EI# were obtained on
a Varian Autospec Q mass spectrometer[ The other spec!
troscopic measurements were carried out as described
previously ð00Ł[
1[1[01[ NiI1"B3PSB#1
This was prepared by a similar method but using
9[2 mmol of B3PSB and 9[0 mmol of nickel"II# iodide\
when the formation of the green complex was sustained[

165
Z[ Atherton et al[ : Polyhedron 07 "0888# 162Ð168
1[3[ Crystallography
2[ Results and discussion
1[3[0[ Crystal data
Both B1PSB "IV# and B3PSB "V# gave solid complexes
with a range of _rst row transition metal ions Table 0[
The complexes were generally rather insoluble and\ as a
result\ crystals of suitable quality for single crystal X!
ray di}raction analysis were obtained in only one case\
Co"B1PSB#"NO2#1[ We shall discuss that X!ray result
_rst as it provides a basis for inferring the structures of
the other complexes from the spectroscopic studies[
For
Co"B1PSB#"NO2#1\
0]
C07H05CoN3O5S1\
Ä
¹
Mꢁ496[3\ triclinic\ space group P0\ aꢁ6[411"1# A\
Ä
Ä
bꢁ7[452"1# A\ cꢁ06[423"1# A\ aꢁ78[88"1#>\ bꢁ75[70
2
Ä
"1#>\ gꢁ57[62"1#>\ Uꢁ0949[6"1# A \ Zꢁ1\ Dcꢁ0[593 g
cm−2\ m"Mo Ka#ꢁ0[948 mm−0\ lꢁ9[60962 A\ F"999#
Ä
ꢁ407[ A dark red block of dimensions 9[39×9[22×
9[16 mm was used[
2[0[ Structure of Co"B1PSB#"NO2#1
1[4[ Data collection and processing
The X!ray study of the complex Co"B1PSB#"NO2#1
shows the compound to be polymeric\ the B1PSB ligand
adopting a bridging role between the cobalt centers\
bonding to them via the nitrogen atoms "Fig[ 0#[ Each
cobalt atom also has bonded to it one unidentate nitrate
and one asymmetric bidentate nitrate ion "Fig[ 1#[ The
coordination geometry at Co is very distorted[ It can
probably be best described as distorted tetrahedral
"involving N"0#\ N"11#\ O"092# and O"001## but with a
more loosely coordinated oxygen atom\ O"002#\ occu!
Data were collected on a Siemens P3:PC di}ractometer
with graphite monochromated Mo Ka radiation using v!
scans^ 2566 independent re~ections were measured
"6³1u³34># of which 2064 were considered observed
"=Fo=×3s"=Fo=##[ The data were corrected for Lorentz and
polarization factors^ no absorption correction was
applied[
1[5[ Structure analysis and re_nement
Ä
pying a _fth\ more distant "1[222"1# A# coordination site\
The structure was solved by direct methods[ The non!
hydrogen atoms were re_ned anisotropically[ The pos!
itions of the hydrogen atoms were idealized\ CÐ
without major perturbation of the tetrahedron[ The CoÐ
N"pyridyl# distances are asymmetric\ with that to N"0#\
in a pseudo!trans position to the loosely linked O"002#\
Ä
Ä
Hꢁ9[85 A\ assigned isotropic thermal parameters\
being slightly longer "1[970"1# A# than that to N"11#
Ä
U"H#ꢁ0[1Ueq"C#\ and allowed to ride on their parent
carbon atoms[ Re_nement was by full!matrix least!squa!
res\ based on F\ to give Rꢁ9[9214 and Rwꢁ9[9263
"w−0ꢁs1"F#¦9[9996F1#[ The mean and maximum shif!
t:error in the _nal re_nement were 9[999 and 9[990 respec!
tively and the maximum and minimum residual electron
"1[926"1# A#[ The solid state electronic spectrum of the
compound "Table 2# shows strong dÐd bands as expected
from the non!centrosymmetric coordination geometry[
The B1PSB ligand has Ci symmetry about the center
of the benzene ring\ thus producing an anti geometry for
the two terminal 1!mercaptopyridyl groups[ The pyridyl
and benzyl ring systems are steeply inclined to each other
"47># but with the C"5#ÐS"6#ÐC"7#ÐC"8# linkage being
essentially planar\ the principal torsional twist being
about the C"7#ÐC"8# bond "57>#[ Despite the potential for
−2
Ä
densities in the _nal DF map were 9[14 and −9[12 e A
\
respectively[ Computations were carried out using the
SHELXTL PLUS PC system ð01Ł[ Selected bond lengths
and angles are listed in Table 1[
Table 1
Ä
Selected bond lengths "A# and angles "># for Co"NO2#1"B1PSB#
Co"0#ÐN"0#
Co"0#ÐO"092#
Co"0#ÐO"002#
1[970"1#
1[915"1#
1[222"1#
Co"0#ÐN"11#
Co"0#ÐO"001#
1[951"1#
1[926"1#
N"0#ÐCo"0#ÐN"11#
N"0#ÐCo"0#ÐO"001#
N"11#ÐCo"0#ÐO"092#
N"11#ÐCo"0#ÐO"002#
O"092#ÐCo"0#ÐO"002#
Co"0#ÐN"0#ÐC"1#
Co"0#ÐN"11#ÐC"06#
Co"0#ÐO"092#ÐN"099#
Co"0#ÐO"002#ÐN"009#
095[1"0#
87[9"0#
85[2"0#
75[7"0#
74[6"0#
005[8"0#
007[8"0#
097[4"1#
75[7"0#
N"0#ÐCo"0#ÐO"092#
N"0#ÐCo"0#ÐO"002#
N"11#ÐCo"0#ÐO"001#
O"092#ÐCo"0#ÐO"001#
O"001#ÐCo"0#ÐO"002#
Co"0#ÐN"0#ÐC"5#
001[7"0#
044[2"0#
015[0"0#
006[3"0#
46[8"0#
014[1"0#
012[2"1#
099[1"0#
Co"0#ÐN"11#ÐC"10#
Co"0#ÐO"001#ÐN"009#

Z[ Atherton et al[ : Polyhedron 07 "0888# 162Ð168
166
Fig[ 0[ Part of the polymeric chain structure of Co"NO2#1"B1PSB#[
Fig[ 1[ The coordination geometry about Co in the structure of Co"NO2#1"B1PSB#[ The dashed line indicates the more loosely coordinated oxygen
atom\ O"002#[
interchain pÐp interactions\ a study of the packing of the
chains reveals a marked absence of either face!to!face or
edge!to!face interactions[
dination geometry\ both with respect to the band energies
and lower band intensities\ so it is probable that this
compound resembles its cobalt"II# analogue in having a
similar chain structure\ but in this case with six!coor!
dination at each nickel center by use of two bidentate
nitrates[
2[1[ Other complexes of B1PSB "IV#
Nickel nitrate also forms a complex of stoichiometry
Ni"B1PSB#"NO2#1 analogous to the cobalt complex
described above[ Its solid state electronic spectrum Table
2 is typical of nickel"II# in an essentially octahedral coor!
The solid state electronic spectra of the cobalt"II# hal!
ide complexes Co"B1PSB#X1 "XꢁCl\ Br\ I# are\ however
Table 2\ characteristic of essentially tetrahedral coor!
dination geometry about the Co center ð02Ł\ as they show

167
Z[ Atherton et al[ : Polyhedron 07 "0888# 162Ð168
Table 2
Electronic spectraa "cm−0# of some complexes formed by ligands IV and V
CoCl1"B1PSB#
CoBr1"B1PSB#
CoI1"B1PSB#
5499 sh\ 6199\ 7699 sh\ 05\699b
5199 sh\ 6999\ 7199 sh\ 05\499b
5899b\ 04\899b
Co"NO2#1"B1PSB#
Ni"NO2#1"B1PSB#
Cu"B1PSB#1"ClO3#1
CoBr1"B3PSB#
7699\ 02\799 sh\ 08\299
7699\ 04\399\ 13\099
06\699\ 14\399
5699\ 8099\ 05\499b
CoI1"B3PSB#
4899 sh\ 5499\ 8099\ 04\699b
8399\ 06\499 sh\ 19\999
5099\ 7499\ ca 01\999 sh\ 02\899\ ca 12\999 br
5999\ 7999\ 02\699\ ca 12\999 br
4899\ 7999\ 02\399c
Co"NCS#1"B3PSB#1=1H1O
NiCl1"B3PSB#=H1O
NiBr1"B3PSB#
NiI1"B3PSB#
NiI1"B3PSB#1
6399 br\ 01\999 sh\ 05\999c
03\399 br
CuCl1"B3PSB#
CuBr1"B3PSB#
04\999 br
Cu"B3PSB#1"ClO3#1=1H1O
06\699
a By re~ectance method[
b Center of strong multicomponent band[
c dÐd bands at higher energy obscured by strong electron transfer absorption[
strong\ overlapping bands in the range 5999Ð8999 cm−0
"transitions to components of 3T0"F## and a strong\ mul!
ticomponent band in the visible region "transitions to
the components of the n1 band system "transitions to
components of T0"F## in the near IR region\ indicative
of a greater distortion from strict Td symmetry at the
cobalt centers[
3
3
components of T0"P##[ Additional evidence ð03\ 04Ł for
tetrahedral coordination geometry for Co"B1PSB#Cl1 is
In contrast\ the corresponding nickel"II# halide com!
plexes Ni"B3PSB#X1 "XꢁBr\ I# have electronic spectra
characteristic of halide bridged six!coordinate nickel"II#\
as in e[g[ Ni"pyridine#1Br1 ð05Ł\ but in the present com!
pounds with concomitant bridging by the B3PSB ligands[
The electronic spectrum of the hydrated nickel chloride
complex Ni"B3PSB#Cl1=H1O is also of the halide!bridged
polymer type\ and this compound probably also contains
B3PSB cross!links\ but\ in the absence of direct X!ray
con_rmation\ the possibility that the water molecule is
coordinated cannot be ruled out[ Similar comments apply
to its manganese"II# analogue\ Mn"B3PSB#Cl1=H1O\ the
X!band EPR spectrum of which shows the single broad
gꢁ1 band characteristic ð06Ł of polymeric halide!bridged
ðMnL1X1Łn systems[
provided by the n"CoÐCl# bands at 299 and 215 cm−0
[
These results are consistent with these cobalt"II# halide
compounds also forming chains analogous to those in
Co"B1PSB#"NO2#1 but with the cobalt centers comprising
tetrahedral ðCoN1X1Ł units[
Reaction of B1PSB with hydrated copper"II# per!
chlorate in ethanol gave a complex of stoichiometry
Cu"B1PSB#1"ClO3#1\ the X!band powder EPR spectrum
of which was of the axial type with g_ꢁ1[949 and
g>ꢁ1[126 and with Cu hyper_ne splitting of 06[4 mT
on g>[ These results are consistent with a planar CuN3
coordination geometry about each copper center and
with negligible interaction between adjacent copper
centers[ The solid state electronic spectrum shows a broad
dÐd band at 06\699 cm−0 and a strong band\ probably of
electron!transfer origin\ at 14\399 cm−0[ Taken in con!
junction with the bridging capability of B1PSB dem!
onstrated for Co"B1PSB#"NO2#1\ these observations
suggest that the cations in ðCu"B1PSB#1Ł"ClO3#1 are
linked by B1PSB bridges so as to form a sheet array[
During the synthesis of the orangeÐbrown compound
Ni"B3PSB#I1 it was noticed that a solid green product
formed during the early stages of the addition of the
nickel"II# iodide solution[ Use of a 2]0 B3PSB]NiI1 ratio
of the reactants gave the green complex Ni"B3PSB#1I1\
the solid state electronic spectrum of which is typical of
six!coordinate NiL3X1 compounds where L is a nitrogen
donor heterocycle such as pyridine ð07Ł[ This implies the
formation of a sheet structure for this complex via the
bridging action of the B3PSB ligand and with a trans!
NiN3I1 coordination geometry at each nickel center[
The X!band powder EPR spectrum of CuCl1"B3PSB#
is of the axial type with g_ꢁ1[954 and g>ꢁ1[118[ This
observation and the solid state electronic spectrum
2[2[ Complexes of B3PSB "V#
The products of the reaction of B3PSB with cobalt"II#
bromide or iodide closely resemble those formed by the
1!pyridyl analogue as they have the stoichiometry
Co"B3PSB#X1 "XꢁBr\ I# and their electronic spectra
Table 2 show the presence of tetrahedrally coordinated
metal centers[ There is\ however a greater splitting of
"broad\ multicomponent band centered on 03\399 cm−0
#

Z[ Atherton et al[ : Polyhedron 07 "0888# 162Ð168
168
are consistent with trans!planar ðCuN1Cl1Ł coordination
References
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bonded via the nitrogen atom and the electronic spectrum
of the solid complex Table 2 is typical of an octahedral
ðCoIIN5Ł chromophore with an average ligand _eld
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the N atoms[ In contrast\ the anions in the nickel"II#
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Acknowledgements
ð19Ł Liehr AD[ J[ Phys[ Chem[ 0852^56]0203[
We thank the EPSRC for a Research Studentship "to
Z[A[#\ for a post!doctoral fellowship "to S[M[# and for
equipment[