, O ) Ligands Potentiometric Study of Transition Metal Ions Complexes of Hexadentate(N

Printed in the Republic of Korea

-      

  

*
 ^†


 


† 


(2000. 1. 24 )

Potentiometric Study of Transition Metal Ions Complexes of Hexadentate(N

, O

) Ligands

Sun-Deuk Kim
, Jun-Kwang Kim, and Woo-Sik Lee^† Department of Chemistry, Taegu University, Kyonsan 712-714, Korea

†Department of Environment Engineering, Kyungwon College, Sungnam 461-702, Korea (Received January 1, 2000)

.    -    1,13-bis(2-hydroxybenzyl)-2,5,9,12-tetraaza- tridecane-tetrahydrochloride(BSATD!4HCl)" 1,14-bis(2-hydroxybenzyl)-2,6,9,12-tetraazatetradecanetetrahyd- rochloride(BSATED!4HCl)# $ % &&'( )*+ ,-, ./0 ,12, 3 4 52 6

789:;'( )*# <=+>?. )*@  A  BCD(logK^nH) Cu(II), Ni(II), Co(II) 6 Zn(II)E
F GHI C D(logK^ML)# JK .H2'( +, LMN OP  A QRE E ST4" U(V4W XY+Z  A [R \E ]^  BC _* 6 R`aE
F G HICDE bcZ de# f+>?. g [Cu(BSATD)]ClO⁴" [Cu(BSATED)](ClO⁴)2(II)hi

# )*+ g *# jOkl?.

ABSTRACT. The open-chain hexadentate N4, O2 ligands 1,13-bis(2-hydroxybenzyl)-2,5,9,12-tetraaza- tridecane-tetrahydrochloride (BSATD!4HCl) and 1,14-bis (2-hydroxybenzyl)-2,6,9,12-tetraazatetradecane-tet- rahydrochloride (BSATED!4HCl) have been synthesized as their tetrahydrochloride salt and characterized by EA, IR, NMR and Mass. Their proton dissociation constants(logKⁿH) and stability constants(logKML) for Cu(II), Ni(II), Co(II), and Zn(II) ions were determined in aqueous solution by potentiometry and compared with those of analogous N4,O2 ligands contain ethylenic spacers or propylenic spacers, which make six-membered chelate rings between the aliphatic nitrogen atoms. Synthesis and characterization of [Cu(BSATD)]ClO4 and [Cu (BSATED)](ClO4)2 complexes are described.

LMN OPmE no4W XY+Z p  qU

&4  Ar    `a hi( )*s tu 4 ., ,1. 6 v _*R k

stu w?.^1-8qU&4 Z xK OP aldehyde

" yz+ , { RP(C=N)|)# *F?. RP

 R}|)r g ~ €GH+ ,R ‚r pH dƒE„Z ,BsZ eR …t  †

, t‡ˆ ‰( `a h )i(„ )*stu w?.⁹ Š‹ Kim ŒE B  &'( Ž

pHW v+ qU&4  &&'( ,+

70%-dioxane ‘Ž’E„ “J E ]^ 

A  BC" R`aR” GHICD#

‘ kF •…?.¹⁰F– R qU&4  Z 

 —c ˜Z NaBH4( RP4W + ™(š

 W )*›  …, RA -  Z

œr  ‰% W L …t RP4W XY+

Z qU&4  "  RP4(C=N) R}|) R žx |)'( (C-N)st ,{ Ÿ*#

 q¡ `a hi GHI CD# ¢x £†

O¤¥ ŽE„ JK .H2 ,11I2 _

¦# jO§  …Z —¨R …?.^9,11-13

© E„Z k¹⁴E„ k@  { LMN OP QªR EST4(† |@ N,N'-bis(2-hyd- roxybenzyl)-triethylenetetraamine-tetrahydrochloride (BHTT!4HCl)# )*+, LMN OPA QRE … Z « EST4" U(V4( |@ ™(š

 1,14-bis(2-hydroxybenzyl)-2,6,9,12-tetraazate- tradecane-tetrahydrochloride(BSATED!4HCl)" 1,13- bis(2-hydroxybenzyl)-2,5,9,12-tetraazatridecane-tetra- hydrochloride(BSATD!4HCl)# )*+ «

[R \E ]^ BHTT, BSATD 6 BSATED  B

CD(lognH) _* R`a(II) GHI CD (logKML)D# ‘ ¬­+>, [Cu(BSATD)]ClO⁴"

[Cu(BSATED)](ClO4)2 hi# ®t ./0 ¯

89:;, ,-, ¯89:;, ° II 6 FAB-7,-'(±² <=+>?.

  . ³  A )*E QŽF triethylenetetramine, N,N-bis(2-aminoethyl)-1,3-propane- diamine, N,N-bis(3-aminopropyl)ethylenediamine6 2- hydroxybenzaldhydeZ aldrich´ _µq¶# H´+L

· g
( QŽ+>?. &4Z KOHW QŽ+>, LLB 6 ¸¹Ž# † Zº QŽ@ q¶r

Merck´ ˜Z Junsei´ _µq¶# QŽ+>?. ./

0 89:;r ShimadzuQ FT-IR 8201 ./0 , 11IW RŽ+ |W ®»'¼, C.H.N , -r Carlo ErbaQ ,-4 1106# RŽ+>, NMR 89:;r BrukerQ AM300 FT-NMR Spec- trometerW QŽ+ ®»'¼, 789:;r Kratos Q GC-Mass Spectrometer# QŽ+ |W ®»

?. )*@  A ½* BC 6 hi G HI CZ Metrohm 665 Dosimat¾.H4"

Metrohm 682 pH b²W RŽ+ JK .H2'(

pHW ¿H+>'¼, À”r Metrohm À”Á Jeio TechQ RC-10VÀ”vW QŽ+ ¿HŽ ”I W 25^oCÂ0.1( Hq¡ ¿H+>?.

   

1,13-bis(2-hydroxybenzyl)-2,5,9,12-tetraazatridecane- tetrahydrochloride(BSATD
4HCl). ÃÄ«Å(25 ml)E N,N-bis(2-aminoethyl)-1,3-propanediamine(1.72 g, 0.01 mole)# Ær ?Ç  4m+E„ 2-hydroxy- benzaldhyde(2.21 g, 0.02 mole)# „„È ÆZ?. R

Ž# 6q m qÉÊ ËÌÍ Î)iR ®tÏ

?. R ËÌÍ Î)i# Ä«Å(50 ml)E Ð-qÑ Ò NaBH4(1.51 g, 0.04 mole)W Ó³qÉʄ v`Ô ÆZ?. 12q ¾G yzqÑ Ò &'( pH 7Õ8 ÖL }qÉÊ ×Í ØiR Ù*@?. RW 

+ E ?q ÏF &'( pH 1R sIÚ +

 4^oCR+ +Û ÜÝ# +Ê ×Í,Þ BSATD!

4HClR Ù*@?. R Ù*i# Ä«ÅE ß à áâ+

 Ϻqã² aE ävqå?.

Yield: 3.14 g, 68% Anal. Calcd for C21H36N4O2Cl4: C, 48.74; H, 6.96; N, 10.83%. Found: C, 48.38; H, 7.30; N, 10.65%.¹H-NMR(D2O/DMSO-d6): 6.93, 7.31 ppm (phenol), 4.23 ppm(phenol-CH2-N), 3.40 ppm(N-(CH2)2- N), 2.34, 3.14 ppm(N-(CH2)3-N).¹³C-NMR(D2O/DMSO- d6): 112.88, 114.05, 117.92, 128.54, 129.11, 152.46 ppm (phenol), 44.65 ppm(phenol-CH2-N), 40.36, 42.05 ppm (N-(CH2)2-N), 19.87, 39.66 ppm(N-(CH2)3-N), Mass sp- ectrum(m/e): 372 [Mw-4HCl],ΛM,Ω⁻¹M⁻¹cm⁻²: 513 (H2O). IR(KBr) vN-H 3380 cm⁻¹, vC-N 1180 cm⁻¹, vC=C 1610 cm⁻¹.

1,14-bis(2-hydroxybenzyl)-2,6,9,12-tetraazatetradecane- tetrahydrochloride(BSATED
4HCl). Ä«Å(25 ml)E N,N'-bis(3-aminopropyl)ethylenediamine(1.95 g, 0.01 Scheme 1.

mole)W Ær ?Ç  4m+E„ 2-hydroxybenz- aldhyde(2.21 g, 0.02 mole)# yzq¡ BSATD!4HCl

 )* œr M2'( )*+>?.

Yield: 3.21 g, 68%. Anal. Calcd for C22H38N4O2Cl4: C, 49.64; H, 7.14; N, 10.53%. Found: C, 48.28; H, 7.35; N, 10.25%. ¹H-NMR(D2O-DMSO-d6): 6.79, 7.10 ppm (Phenol), 3.97 ppm(Phenol-CH2-N), 2.91, 3.17 ppm(N- (CH2)3-N), 1.87 ppm(N-(CH2)2-N).^{1 3}C-NMR(D2O- DMSO-d6):112.80, 114.32, 117.82, 128.85, 129.02, 152.28 ppm.

(phenol), 44.12 ppm(Phenol-CH2-N), 42.31 ppm(N- (CH2)2-N), 19.70, 40.30, 40.84 ppm(N-(CH2)3-N). Mass spectrum(m/e): 386[Mw-4HCl]. Λ^M,Ω⁻¹M⁻¹cm⁻²: 494(H2O).

IR(KBr): vN-H 3420 cm⁻¹, vC-N 1190 cm⁻¹, vC=C 1610 cm⁻¹.

[Cu(BSATD)]ClO4. BSATD!4HCl(0.51 g, 1 mmole)

# æ= ÃÄ«Å Ž(30 ml)E sodium acetate trihydrate(0.55 g, 4 mmole)W Æ 1q y F?.

R Î) ŽE Cu(OAc)²!H²O(0.18 g. 1 mmole)W æ= Ò 7 NaClO4W + 2q y +Ê

Ž Íçr èÍR @?. R Î) ŽE KOH' ( pH 10'( v+Ê ÏF éÍR @?. R Ž

 Øi# êp {  # ë”E +Û Mc +Ê èÍ |HR Ù*@?. R |H# + Ä«

Å-Oá­¤:ì Î) ŽE í|H+>?. ®r èÍ

|Hr 0.11 g'( [Cu(BSATD)]ClO4(Fw:530.44)W

‹î( F ïðr 28%R»?.

Anal. Calcd: C, 48.09; H, 5.78; N, 10.38. Found:

C, 47.28; H, 5.63; N, 10.51. IR(KBr): vN-H 3195 cm⁻¹, vClO4 1100 cm⁻¹. UV/vis(acetonitril): λmax, nm (ε, M⁻¹cm⁻¹); 587(77).Λ^M,Ω⁻¹M⁻¹cm⁻²(acetonitril):

160. Mass spectrum(P-PAN): 434[Cu(BSATD)]²⁺, 534 [Cu(BSATD)]ClO4.

[Cu(BSATED)](ClO4)2.ÃÄ«Å(50 mL)E N,N- bis(3-aminopropyl)-ethylenediamine(1.95 ml, 0.01 mole)

# Æ  4m +E„ 2-hydroxybenzaldhyde(2.21 g, 0.02 mol)# „„È Ær ?Ç R Ž# 6q m qÑ?. Ó³ y—cW RŽ+ NaBH4(1.51 g, 0.04 mole)W p àE êñ v`Ô ÆZ?. R Î)

ŽE Cu(OAc)²!H²O(2.49 g. 0.01 mole)W F ? Ç 1q m qÑ?. R Î) ŽE 7 NaClO4

W + ë”E +Û ÜÝ# +Ê .Í |HR Ù

*@?. R |H# Ä«Å-Oá­¤:ì Î) ŽE

í|H QŽ+>?. Ù*i |Hr 1.49g( [Cu(BSATED)]

(ClO4)2 (Fw: 649.04)W ‹î( F ïðr 23%

R»?.

Anal. Calcd: C, 40.96; H, 4.65; N, 8.68. Found:

C, 41.54; H, 4.29; N, 8.42. IR(KBr): vN-H 3150 cm⁻¹, vClO4 1100 cm⁻¹. UV/vis(acetonitril): λ^max, nm(ε, M⁻¹cm⁻¹); 569(190).ΛM,Ω⁻¹M⁻¹cm⁻²(acetonitril): 292.

Mass spectrum(P-PAN): 448[Cu(BSATED)]²⁺, 548[Cu (BSATD)]ClO4.

N,N'-bis(2-hydroxybenzyl)-triethylenetetraamine- tetrahydrochloride(BHTT!4HCl)Z k" œR )*

+ QŽ+>?.¹⁴

 
    

JK .H2'( ½* BC 6 GHIC

W ¿H+4 J+ 1.0ò10⁻²M BSATD!4HCl 6 BSATED!4HCl   óIW QŽ+>, Rô Q

Ž@ õö&4 óIZ 9.67ò10⁻²M# QŽ+ .H

 pHW ¿H+>?. .H R”á4(µ)Z KNO3'( 0.1R sã +>, Ž{±E ÷í+Z O2" CO² de# øR4 JB„  4m+E„

.H+>?. ¿H@ pHD# PUKAS U(gù# QŽ

+ B žú? ½* B CD# +>, hi GHI CDr  óI, `aR” óI 6 KOH &4 óI(±² pH û D# ¿H+

BESTA U(gù'( +>?.^15-17

  

LMN OP N,N'-bis(2-aminoethyl)-1,3-propanedia- mine" N,N'-bis(3-aminopropyl)-ethylenediamineE é

% no4W XY+Z -   

BSATD" BSATEDZ yz*R ü xKOPE 2- hydroxybenzaldhydeW yzq¡ no é , |) F qU&4W ®r Ò )i# ]( ,+L ·

qU&4 RP(C=N) |)# NaBH⁴( žx |)

( qå?. R )iE ÏF &# + L MN OP E $ % &&'( ,+ QŽ

+>?. gp BHTTZ triethylenetetramine F ,

" á , 2-hydroxybenzaldhyde yz+ L

  sal3trien'( )*@?Z QëR j‡ u …?.⁹ L   Oý xK OP E„† é

% noR |)F
þ v qU&4W ®4 J

B„ Kim Œr Oá: &# + pH 4.5H I( vY'( BHTT ÿ~ )i= BSTT!4HCl

)i )*R 
+ã s»?.⁶]¥„ BSTT!4HCl qU&4W && („ ,+ Ä«ÅE æ

` *« ’ +E„  # + BHTT!4HCl

)i# ®»?.¹⁰

BSATD!4HCl ,- |Z RcD ë

cDR  xc+>, ŽE„ ° IIDr $

% &&R @ D 513#  {»?. 7 8 9:;E„ $ % &&r ¬sL ·l 

 ,R”(M⁺)  372E„   236E B+Z 4öZ phenol-CH²-NH-CH2 tu

 ¥E B@?. ./0 89:;E„Z qU

&4 RP4(C=N) 1645 cm⁻¹ϾR Q¥L

( RP4 (C-N)s»Ç# j  …»?.

BSATD!4HCl NMR89:;r Fig. 1E  {»?.

1H-NMRE„  { no Z 7.31, 6.93 ppm E„  , no xKOP | Z 4.23, LMN OP { Z 2.34, 3.14 ppmE„

<=+>?. ¹³C-NMRE„Z no4  % «

Fig. 1.¹H-NMR and ¹³C-NMR spectra of BSATD
4HCl.

Table 1. Ligand protonation constants at 25^oC in 0.10 M KNO3

Ligand logK¹H logK²H logK³H logK⁴H logK⁵H logK⁶H logβ Reference

BHTT 9.00 8.96 8.45 7.55 5.90 3.11 42.9742.97 14

BSATD 9.19 8.93 8.73 7.78 6.24 5.22 46.0946.09 This work

BSATED 9.31 9.15 8.89 8.04 7.34 5.81 48.5448.54 This work

*Calculated by Fortran program PUKAS.¹⁵

W 112.88Õ152.46 ppmE„ <=+> LMN { ? % «Z 19.87Õ44.65 ppmE„    { «"  xcY# j  …?.

BSATED!4HCl ,-, ° II, NMR, IR 6 Mass)* <=r ë±,E µ +>Z  œR

 xc+>?.

&&'( ®tÏ  A  BCDr &

4 .E ]¥ xtZ ½* BžW  JK2'( ¿H+>?. ž BCD K^nH= [HnL]/[H]Z Table 1E  {»?.

 Ar é % no4" LMN RK OPE

@ $ % ½*W XYF?. ]¥„ RA &

&  A 4 R” óIZ pH 2Õ3D'(

*#  {,   Z  &4I"

no4 _*E B„ pH 9 RCR @?.

Fig. 2Z Ligand!4HCl H6L, H5L, H4L, H3L, H2L, HL 6 L E
F pH ,X0'(„

H6L H⁵L r no 4E B+, H4L, H3L, H2L, HL r LMN OP E

@ ½*E B@?. Lr  E @ ÿ

½* B @ # õF R?.  A

~. ,X 0# kÊ H6LÕH3L Ar pH 2E„ 8ÖLE„ &4" ¸†F },XW L …

'ʄ  { LMN OP _*#  {…

Z yÊE no* 4 XYsZ H2L, HL 

Ar pH8E„ 10QR ‘F pH dƒE„  F ,Xð# L …?.

 AE
F H6L# !"kÊ BSATD"

BSATEDZ pH 6E„ ÖL ,Xst…L† BHTT

Z pH 4ÖL ,Xst …?. RZ OPA "

½* GHIW  {Z OP &4I âI(„ 

@ ½* B +4EZ BHTT — ŽR +?

Z # j  … BHTT logK^6HDI — ‚r D

#  { …?. g # à$ ½* B ž

H5L ƒq BHTTZ pH 2E„ q%st pH 7E„ &

sZ yÊE ?^ é  Z pH 4E„ q%st pH 8E„ ,X &s …?. ]¥„ BSATD 6

BSATED OP ½* GHI BHTTk? '„

v` ( ¢r pH dƒE„ H⁵LR ÷íY# j

 …?.

BSATDE„Z ?^  A k? ÿ AR

‘. ^ ,Xð( pH 4E„ 10ÖL ÷í+ …

?. RZ OP E @ ½* ž.'(

R +(¥I , v.= GH# ŸL+ …Ç#

)%›  …, yÊE BSATEDZ H4L±² HL 

ÖL  F ,Xð Y* ½* R( =F ,


þR ?^  k? +t)# Ù³›  …?. ]¥„  A BC _*# |H+Z ,

=r   { no* 4 k?Z LMN OP

# |+Z « _*E L“.-# j  …?.

Fig. 2. Distribution diagram for the species in equilibrium as function of pH in the systems (a) BHTT
4HCl, (b) BSATD

4HCl, (c) BSATED
4HCl.

™( )*@ BSATD pH9E„ ³  , Xð# kÊ ½* ÿé B@ LR 5%, HLR 20%, H2LR 55%, H³LR 30% ÷í+, H4L

H5Lr ÷í+ …L ·?. Table 1E„" œR ž

 BCDr logK^nH=9.19, 8.93, 8.73, 7.78, 6.24, 5.22D# ®»?. 4„ LMN OP N,N-bis(3- aminopropyl)ethylenediamineE B+Z Dr logKⁿH

=8.73, 7.78, 6.24, 5.22E B+ logK^nH=9.19, 8.93r no 4E B+Z DE BF?.

BCDE
F  A _*r LMN OP

# |+Z «  ›Ú   ~ &

4IDR  Y# j  …?. LMN OPE é %

 U(V4W LZ BSATEDZ F %W LZ BSATD 6 EST4( |@ BHTTk? — ü logβ(overall proton dissociation constant)# Ï?.

RZ «[R [t)'( OP4A QRE 

y.# /q¡ @ ½* GHIW ¢RZ

'( Ù³@?.^18,19 ]¥„ , {   «

|E„ EST4 6 U(V4 Qª " JcE ]¥  A _¦R LˆÏ?.

³  A R`a hi GHICDr &

&   " `aR” ŽE õö&4 KOHW .Y'( ®tLZ }0'(±² s tÏ?. Fig. 3r BSATD!4HCl" R`a(II)R”

Î)i q&W &4 õöŽ'( JK .HF |

R?. 4„ qDr &4W . +># ô ½*

}sZ &4 7#  { &4 . E ]¥ BSATD" R`a R” hiR Ù*#

bF?. BHTT, BSATEDhi GHI CD#

Table 2E Ú+>?.

R |" œR no# XY+Z - 

   R`a(II)R”E
F GHI CD 04Z BHTT<BSATED<BSATD 1„(  +>?.

 A hi GHI CD _¦# kÊ Table 1E„ k2R  " `aR”A R”|)*# 

{Z no* 4 &4I k?Z “J|)*#

LZ LMN OP ÷*#  { … xy.

'( logβ ü R `a hi GHI 3  R¥ 4Cs»' logβ %r BSATD BSATED k? GHIDR ÿ `aE
B„ 0?. ]¥„ h iE
F GHIZ OP «[RE ]^ `aR”

 04 6 5~—6 deE L“.-# j  …

?. `a ( ³  AE
F 04Z `a ´ 2R” E7L 04 1„" xcF?. Table 2 |

E„ R`a hi GHICD 04 1„W

‘+ kÊ d 8I    1„" œR Co(II)<Ni(II)<Cu(II)>Zn(II)1„ R»?. R" œr |

Table 2. Stability constants for Ni(II), Co(II), Zn(II) and Cu(II) complexes of ligands at 25^oC in 0.10 M KNO3

Ligands Ni(II) Co(II) Zn(II) Cu(II) Reference

BHTT 19.27 17.50 14.00 24.90 14

BSATD 22.08 19.79 17.34 28.87 This work

BSATED 20.61 18.27 16.84 25.07 This work

*Calculated by Fortran program BESTA¹⁵

Fig. 3. Potentiometric equilibrium curves for BASTD
4HCl and 1:1 complexes of Cu(II), Ni(II), Co(II) and Zn(II) in H2O.

q=mole of base(KOH)added/mole of ligand percent.

Z Irving-Williams „  xcF?.²⁰

[Cu(BSATD)]ClO4hir  BSATD!4HCl

Ä«Å Ž’E Cu(OAc)²!H²OW yzqÉÊ 9^Í

 : “JhiR Ù*s, NaClO4W + F ,

 ClO⁴⁻& ( ®»?. )*@ hi  ,-r Rc" ëcD  xc+>, ./0 8 9:;E„Z `a R”E “J@ RKOP N-H

ϾR 3195 cm⁻¹ ‹;E„  '¼, ÇR”=

ClO4− <R0Z 1100 cm⁻¹‹;E„ =+ >㠁 ?. Oá­¤:ì ŽE„ °IID(ΛM, Ω⁻¹ M⁻¹cm⁻²)r 160'(„ 1:1 R” )iE B+Z D#  ?,  ¯ 89:; d-d RZ 587 nm(ε=77 M⁻¹cm⁻¹)E„  ?. hi 7 8 9:;r Fig. 4" œ?. [Cu(BSATD)]²⁺ ½R”E BsZ Z 434E„  , BSATD 

 Z 371E„, ,7E B+Z <R0Z 534E„  ?. [Cu(BSATED)](ClO⁴)2 hir BSATED ’«Å Ž’E Cu(OAc)²!H²OW yzq¡

é , ClO4−& ( ®»'¼ ,-, 

¯89:;, °II 6 789:; <=r ë

±,E  {»?.

   

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