Zinc and cadmium

1

Coordination Chemistry Reviews, 62 (1985) l-35 Elsevier Science Publishers B.V., Amsterdam

1.

ZINC

AND

-Printed

in The Netherlands

CADMIUM

D. DAKTERNIEKS

CONTENTS

Introduction

ZINC

1.1

Zinc(I1) 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5 1.1.6 1.1.7

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Halide and pseudohalide complexes ............. Complexes with oxygen donor ligands ............ Complexes with sulphur donor ligands ........... Complexes with nitrogen donor ligands ........... Complexes with phosphorus, arsenic. ............ and carbon donor ligands Complexes with transition metal complexes ......... as donor ligands Macrocyclic complexes ...................

2 2 2 5 7 15 16 17

CADMIUM

1.2

Cadmium(I1) ........................ 1.2.1 Halide and pseudohalide complexes ......... 1.2.2 Complexes with oxygen donor ligands ........ 1.2.3 Complexes with sulphur donor ligands ....... 1.2.4 Complexes with nitrogen donor ligands ........ 1.2.5 Complexes with phosphorus and arsenic donor ligands 1.2.6 Macrocyclic complexes ............... 1.2.7 Cadmium-113 NMR spectroscopy ...........

References

...........................

OOlO-8545/85/$12.25

0 1985 Elsevier Science Publishers B.V.

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21 21 21 22 23 24 25 25

. . . . 26

3

Simple organic Zigands

1.1.2.2

High resolution

electron

study the interaction of the CO stretching strengthening

Reaction

chain

Various

described

L21.221.

octahedral

reactions

in isopropanol

analysis

bridging

environment

forming an infinite

of CM(OS~N~)~ICASF~I~

in complexes

(M = Zn.Cd)

Lewis acid with a variety

of phosphine

Octahedral

of Zn *+ with embelin

has been isolated

with

L in the

with zinc salts have been

about the central M atom [231.

is also implied

Zn(S02)2(AsF6)2

L molecules

to zinc

of ZnLZClZ

bipyramidal

of triethanolamine

X-ray structures

O6 environments

coordination

trigonal

due to a between

coordinated

atoms and an oxygen atom of a monodentate

plane and two bidentate

CZO].

moieties

structural

shows Zn in a distorted

coupling

and potassium

two Al(O'Pr)4

A crystal

cl91.

The increase

of CO to ZnO is mostly

of ZnClZ with Al(OzPr)3

to two chlorine

compound

upon adsorption

which contains

OiPr ligands

(L = 1,4-dioxane)

equatorial

(HREELS) was used to

of CO with the (1010) surface of ZnO C181. frequency

gives Zn[Al(OiPr)4)1,

bonding

loss spectroscopy

of the CO bond and not solely to a mechanical

oscillations.

by bridging

energy

[241.

show O8 The

from liquid SO2 1251 and acts as a

oxides.

sulphides

and selenides

C26-281.

CarboxgZic acids and reZated Zigands

2.1.2.3

An X-ray structural tetrahydrate

and neutron-diffraction

Zn(C404H3)2(H20)4

monodentate

maleates

shows octahedral

and four equatorial

study of zinc maleate coordination

water molecules

by two axial

[291.

The zinc atom

in zinc citrate citrates

Zn(C H 0 ) is octahedrally coordinated by two equivalent 6572 via a central hydroxyl, central carboxyl and one terminal carboxyl

oxygen atom from each citrate recorded

for zinc acetate

[301. Electron impact mass spectra have been

[311.

Glycine

group in a number of its complexes

coordinates

with ZnC12 C321.

bis(N-benzoylglycinato)triaquazinc(II)dihydrate atom of the carboxyl

compound

ZnL2 where LH is (I) has been prepared

(LH =

structure

o-aminobenzoic

through

substituted

environment

of [Zn(edta)12+

structure

shows the metal

acid) 1361.

The interactions

acids with Zn 2+ have been described

carboxylic

C481. substituted

acids

derived

C461. salicylic

anthranilic

giving a The

[34].

to possess

an

ion in ZnL

2 of a variety

[37-431.

of monohydroxamine

data for zinc complexes

of

by an oxygen

about zinc [33].

and characterised

[351 as does the metal

the oxygen atom in a variety

Thermodynamic

acids

trigonal bipyramidal

04J/S environment

dicarboxylic

The crystal

group of each anion and by three water molecules

distorted

The crystal

the carboxylate

shows coordination

slightly

octahedral

through

of substituted

Coordination

complexes

from hydroxamic

occurs

of zinc c441.

acids [45].

acid [471. acetic and levulinic

acid c491 and substituted

picolinic

acid

\ /”

CH2.N-CH,

0’

\

I I

CH2iN'CH,

Cl)

CO,H Thermodynamic parameters for the interaction t5Oj have been reported. 2+ and L-3,4_dihydroxyphenylalanine (L-dopa) [Sl] and

between

Zn

C521 are also reported.

2-amino-2(hydroxymethyl)-1,3-propandiol structure-reactivity

which predicts

relationship

largely on the structure

formation

constants

ligand has been presented

of the organic

The electrosynthesis Addition

of cyanogen

of Zn(acac)2

in methanol

to dipivaloylmethane

has been reported

Zn(acac)2

[551.

Solvent extraction

2-thenoyltrifluoroacetone bidentate

continue

studies

in the distribution

ratio while higher ratio [56].

concentrations

Formation

with a variety

characterised

Various mixed-ligand

have been investigated

[59-611.

gives only a mononuclear (LH = 2-acetylcoordinated

in various mixed aqueous have been measured

of zinc involving

ZnL2 (2) C621.

The compounds

are tetrahedral

complexes

of pyridoxine

oxygen donors

C651.

MLC12

ZnL2

have been reported constants

02CZ2 environments

to contain

for zinc(II)

8-formyl-7-hydroxy-4-methyl-2H-l-benzopyran-2-one 4-hydroxy-3-aldehydrobiphenyl Zn2LC14

in a bridging

moiety

(M = Zn.Hg and LH =

have tetrahedral

Stability

(HL)

with the ligands

through one acyl oxygen and one oxygen of the indandione

Coordination

and

diketones

The ligand 1,8_dihydroxyanthraquinone

compound

[571.

bases have been prepared

complexes

and 2-benzoyl-1.3-indandione)

3-amino-2-benzoylbenzofuran) complexes

of nitrogenous

of

improvement

of amine cause a lowering

constants

complex with dibenzoylmethane

Adducts of Zn(acac)2

by

of zinc with

(<10-5M) causes a remarkable

of the distribution

C581.

is catalysed

and it has been found that addition

amines at low concentration

solvents of the zinc(I1)

[541.

to give

2,2.6.6-tetramethyl-4-(aminocyanomethylene)-3,5-heptanedione

complex

based

[53].

Diketone and other ligands

1.1.2.4

C631.

A

Zinc

complexes

with

[66] and

C671 have been determined.

(L = N.N'-bis(anti pyrylmethyl)piperazine)

oxygen role [681. The mixed-ligand

C641.

the ligand as bidentate

compound

A homobinuclear contains

zinc

the ligand

of zinc with

0 o-hydroxypropiophenone The crystal

and quinoline

structures

of ZnX2L2

L = triphenylphosphineoxide) Organophosphoric

have been studied

of simple zinc(I1)

LG9J

(X = C1,Br and

show the zinc to be in a 08X2 environment

acids as complexons

zinc and cadmium, formation

has been reported

for a variety c711.

complexes

of metal

Thermodynamic

[701.

ions. including

parameters

for

with adenosine-5-triphosphate

(H4ATP)

show that the equilibrium

zn2++ is enthalpically

disfavoured

ATP4-

-_c

CZ~(ATP)~~-

but entropically

stabilised

[72].

CompZexes with sulphur donor Zigands

1.1.3

Simple organic ligands

1.1.3.1

Thiophenol [M(SPh)4121.3-dithio studies

1.1.3.2

compounds

continue

to be of interest

(M = Zn,Cd) have been described ligands have been prepared

involving

phosphine

sulphides

[731.

and the preparations

Zinc(II)

and characterised

of

complexes

with some

by ESCA [741.

Only two

as ligands have appeared

C75.761.

Thioacids, thioomidss and related compounds

The synthesis monothio+-diketonate monothiocarbamates

and characterisatfon complexes

of some alkyl substituted

have been described

and their reactions

with pyridine

C77.781.

Complexes

have been reported

of [79].

6 The zinc(I1) p_ethoxyphenyl molecular in which between

complexes

of 4-aminophenazone

structure

study of zinc(I1)

each zinc is coordinated 2.3398 and 2.846x

and their reactions Complexes

Zinc(I1) contain

Bimetallic

1831.

MX2L

voltametry

alkylxanthogenates The crystal [Zn(S2PPh2)31tetrahedral

tetradentate MZnL4

bridging

ranging of

ligands and appear

(M = Co,Cu and LH = HS2CNEt2)

have been described

disulphide)

of some zinc(II)

C841.

have been reported

and cadmium(I1)

and nitrogen-containing structures

are almost

about

complexes

(M = Zn,Cd; X = C1,Br,NCS,0Ac,N03;

L = N,N,N'N'-tetramethylthiuram extraction

shows a dimer

atoms at distances

and cadmium(II)

complexes

with pyridine

C801 and

A crystal and

bis(diallyldithiocarbamate)

by five sulphur

1821.

piperazinebis(dithiocarbamate) to be polymeric

dithiocarbamate

C811have been described.

dithiocarbamate

The

with

ligands has been investigated

of the anions

identical

C851.

complexes

[Zn(S2P{OC6H4Me12)3]-

C871.

[86].

and

Both anions are distorted

zinc with one bidentate

ligand having

somewhat

larger Zn-S

The polarographic

distances

than those of each of the two unidentate

ligands.

behaviour

of zinc(I1) with diethyldithiophosphoric

acid and nitrogen-bases

as pyridine

was studied and in all cases the electroreduction

was observed

[SS].

r.inc(II) complexes for zinc(I1) reported

Electron

[90].

impact mass spectra were recorded

of dialkyldithiophosphoric

complexes

with thiodiacetic

The zinc(I1)

Sulphur

1.1.3.3

(X = halide)

bidentate

donors

through nitrogen stability

acid contain

and its methyl

towards

zinc(I1)

from thiazole

of these complexes

data

acids have been

of

the ligands as a bidentate

analog give complexes

is through

and sulphur

Formation

act as

with coordination

from thiourea

Complexes

c931.

occuring

The thermal

ZnL2X2

X = N03,0Ac,C1)

ring and nitrogen

constants

ZnL2X2 and ZnLX2

the sulphur atom of the

and cadmium(II)

is Zn
through sulphur of the thiazole 1941.

for some

Thermodynamic

The ligands N-benzothiazoyl;N'-alkylthioureas

(L = benzothiazolesulphonamidmorpholide;

described

such Zn(O)

heterocycZes

in which coordination [92].

complexes

-)

[911.

Imidazoline-2-thione

heterocycle

acid C891.

and dithioacetic

and cadmium(II)

2-aminocyclopentene-1-dithiocarboxylic through the CS2 group

Zn(I1)

with L being bidentate

of the sulphonamide

have been

for [ZnLl+ and ZnL2

(HL = N-~2,3-dimethyl-l-phenyl-5-oxo-3-pyrazoline-4-yl~-N'-benzoylthiourea~ were measured octahedral sulphur.

in 70% EtOH-H20

with coordination The stability

[951 and the metal complexes through

constant

benzoyl

for interaction

2-hydroxy-l-naphthalidenesulphamethoxasole

are thought

to be

carbonyl

oxygen and thiocarbonyl 2+ of Zn with

has been measured

1961,

Complexes

contain bidentate

ZnL2 and CdL2 (HL = N-a-dib enzoylthioacetamlde) coordinated

1.1.4

1.1.4.1

through

Complexes

thio and car-bony1 groups

with nitrogen donor Zigands

Amines

The complex dmf solution

Zn(OAc)2.2NH3

of Zn(OAc)2_2H20

has been obtained [981.

Stability

Zn',+ with N-(Z-hydroxy-5-phenylbenzylidene)aniline crystal (L

ligands

[97].

structure

determination

constants

for the interaction

have been measured

shows tetrahedral

[99].

NSBr2

-CH,

I/

/

H2N\,,/N\t_B”

Br’’ structure

contains

a tetrahedral

symmetry

related

aryl complexes

through

(3) about zinc [lOOI.

Ph ‘CH -CH

The crystal

ammonia

of ZnLBr

2 = o-(l-tert-butyl-2-aziridinyl)bensylamine

coordination

by passing

C3)

Br

of ZnL2 (L = N-(2-p yrrolylmethylene)-tert-butylamine) zinc atom coordinated

bidentate

ligands

ClOll.

(4,s) have been described

M =Zn,Cd

to four nitrogen

atoms of two

Some chelate-supported [1021.

alkyl and

a of A

8 The zinc atom in [ZnL2(lactate)l[lactatel (L = N-isopropyl-2-methyl-1.2-propanediamine) bipyramidalN40

environment

series of tris-chelate T = triflate)

(Meg-tren

[Zn(LL)31(T)2

has been described

solvent exchange

p-toluidene,

of a

(LL = (R.S)-l-amino-2-propanol;

compound

[Zn(Me6-tren)(dmf)12+

-tris(N.N-dimethylamino)triethylamine)

(p-anisidine.

trigonal

and characterisation

Proton NMR has been used to study dmf

[1041.

on the five coordinate

= 2.2'.2"

of arylamine

compounds

has a distorted

The synthesis

[1031.

[1051.

aniline, p-chloroaniline)

Dissociation complexes

and ZnI 2 in acetonitrile was studied by following -NH2 proton 2 Cl061 which are linear functions of the fraction of coordinated amine. 2+ with Formation constants for the interaction of Zn

with ZnBr

2-hydroxy-1-naphthalidene-o-fluoroaniline constants glycine

of quaternary

have been measured

Zn(II) complexes

as a second and ethylenediamine

potentiometrically

[1081.

comprising

The ligand in (ZnClL)20

atom and one hydroxy

six-membered

chelate rings

oxygen

[1091.

is coordinated

atom resulting

square planar with a N4 environment

Schiff

bases,

The Schiff base derived

of two

is tetrahedral

whereas

ZnL is

about the zinc atom [UO].

hydrasones

and oximes

from salicylaldehyde

reacts with Zn2+ as a monobasic

through one

in formation

The adduct ZnC12(LH2)

(LH2 = N.N'-(dipicolyl)-1.8-naphthylenediamine)

1.1.4.2

Formation

as a first.

as a third ligand were determined

(L = N.N'-bis(o-hydroxybenzyl)ethylenediamine nitrogen

[107].

pyridoximine

shifts

tridentate

and 2-hydrazinobenzoxazole

ligand with phenolic

oxygen and both

azomethinyl nitrogen atoms as donors [llll. The ligand formed from ~ AL__. II I ___.___L1__ ~I c E. coneensatron or 2.~ -mernyreneois~salicylaldehyde) and diaminopropane gives a 2+ polymeric Schiff base complex with Zn C1121. Schiff bases derived from substituted the ligands.

salicylaldehydes

and o-hydroxybenzylamine

L. behave as tridentate

of salicylaldehyde pseudo-tetrahedral ON donors giving

ON0 donors

and o-mercaptobenzaldehyde zinc compounds tetrahedral

[1141.

give complexes

[1131.

ZnL where

Schiff base complexes

with bulky amines give

The ligands in ZnL2 (HL = (6)) act as

coordination

about the zinc atom [1151. Mixed-

ligand complexes

of N-6-methylbenzothiazol-2-yl-salicylaldimine and 2+ 2-methylbenzimidazole with Zn are octahedral with coordination of the ligands through phenolic derived

oxygen and exocyclic

from salicoylhydrazine

nitrogen

atoms C1161.

and biacetylmonoxime

with Zn2+ and Cd2+ [1171. Pyridoxal-5'-phosphate-e-amino complexes

and their salicylaldehyde

analogues

borate buffer at pH 9.5 [1181. Zinc(I1) zwitterionic

behaviour

of non-ionised

rlracrihd

compounds

acid zinc(I1)

show photochromic

complexes

forms of Schiff bases have hnnn

The Schiff base (7)

gives octahedral

[119.12Oj.

and of

in

(6)

0 *

C-LN=N-Me I

HO-NN=C-Me OH

a 0

\ I

10

Stability

constants

complexes

CuLMX2

condensation

have been determined X = Cl,Br,I)

(8) (M = Zn,Cd;

Binuclear

have been described

of ethanolamine with benzil biacetyl 2+ In ZnLC12 with Zn and Cd 2+ C1231.

(L = 2-pyridylaldehyde-2-pyridylcarboxylic the 2-pyridyl

and imino nitrogens

other ZnL2 Schiff base complexes ZnLC12,

CdLC12

acting as a bidentate atoms

c1211.

product

ligand complexes

complexes

of Zn 2+ with Schiff bases of

for the interaction

3-formyl-4-hydroxybiphenyl

(L = benzidine

bridging

the chlorines

to zinc C1241.

are also tetrahedral acetylacetone)

[1221.

The

gives tetradentate

acid hydraride)

are coordinated

metal

[125-1291.

and

A number of Schiff base

are dimeric with L

ligand with coordination

through

the nitrogen

C1303. Methyl pyruvate

form neutral tridentates

aroylhydrazones

hexacoordinated through carbonyl

(9) undergo

1:2 complexes

deprotonation

with Zn(OAc)2

ZnL2 with the ligands acting as

oxygen atoms and the azomethine

ii

nitrogen

[131].

R = Ph, o-C4H40H

R/C\N/N\\C/C\oMe H A2

The X-ray structure

(9)

of

bis(2,6-diacetylpyridinebis(2-thenoylhydrazonato)(2-))dizinc(II) pyridine

ring unusually

highly distorted

bridging

octahedral

(LH2 = (10)) are probably

two zinc atoms

environments

C1321.

penta-coordinated

contains

(Zn-Zn = 3.552) which have The complexes

dimers

(11) [1331.

ZnL2, CdL2

a

to

The preparation

and characterisation

of a variety

with Zn 2+ have been described

complexes

derivatives

of substituted

as have a number

hydrazone

of oxime

[139-1411.

Zinc complexes been described

of benzalacetone

[142].

X = Cl.NCS.ClO4)

Complexes

are apparently

coordinated

through oxygen

containing

ZnLX2 and ZnL2X2

[1451.

benzoin

Complexes

have

(L = benzil semicarbazone; [143].

thiosemicarbazone)

and imino nitrogen

tridentate

have been described

and dibenzalacetone-semicarbazone

also tetrahedral

(LH = 2-hydroxy-1.4-naphthaquinone

complexes

[134-1381

atoms

The zinc complex ZnL2

contains [144].

semicarbasone

the ligands

Zinc and cadmium

and thiosemicarbasone

ZnLX2

(LH2 = 4-benzamido-l-diacetylmonoxime-3-thiosemicarbazone

(12); X = Cl,Br)

contain

halides

tridentate

NpS coordinated

ligand and coordinated

C1461.

Ph-

’

I ‘:, -rN=C--Me N=C-Me

Hid--C-S

(12)

HO’ Stability

constants

for zinc complexes

have been reported

hydrazides

amides,

1.1.4.3

The preparation ZnX2(dmf)l.2

and related

of N.N-dimethylformamide

has been described

zinc lactam complexes

have been reported acetamides

configurations

cl511.

contain bidentate

terminal nitrogen

C1521.

c1531.

constant

The compound

is octahedral

Zinc and cadmium been reported tridentate

complexes

p-hydroxyphenylthiohydrazide and cadmium

11571.

complexes

of (13) has been

complexes

through carbonyl

ZnL, oxygen and

whilst

ZnL2(H20j2

appears

to

Zn(tmc)Cl2 is monomeric

and tetrahedral

acid hydraside

aroyl hydraside

zinc and cadmium behaves

of

Some

Zn(HL)C12

of 3-nitrobenzoic

towards

stability

octahedral

in the solid state but dissociates

cl551. Salicylidene

behaviour

Zinc mixed-ligand

for formation

is octahedral

The compound

adducts

cadmium adducts.

Zinc formylhydrazide

(tmc = 1.1.5.5-tetramethylcarbohydrazide) Zn(tmcj2C12

[1491.

ligands coordinated

(HL = Z-furanthiocarboxyhydrazide) be square planar

The thermal

and amines have distorted

The stability

Cl501.

potentiometrically

(n = 1.2.3)

[1481.

is less than that of the corresponding

with some substituted

measured

diphenylcarbasones

compounds

and thermochemistry

(X = Cl.Br.1)

the zinc adducts

with some substituted

[1471.

whilst

in solution

[1541.

(L). !dL4(N03)2 have

ligands show dibasic

C1561.

The ligand

as a sulphur-nitrogen

donor towards

zinc

12

complexes CZII(ATPTS)X~~CI (x = Cl,Br, ~s04,~A~,NOj) are thought to have structure

(14) [158]. Coordination

polymers

I

of zinc and cadmium with

Me3-N--CH2-~=Y

(14)

s

1

a tetradentate

II

“7/NH-cNH-

/Zn\X

1-isonicotinoyl-4-allyl-3-thiosemicarbazide contain

I

ligand.

have been described

Zinc and cadmium

complexes

[1591 and

with

1-isovaleryl-4-phenyl-3-thiosemicarbazide

are monomeric

through oxygen and nitrogen

The ligand 1-acetylpyridium

atoms [160].

chloride-4-phenyl-3-thiosemicarbazide cadmium

C1611.

Polymeric

octahedral

acts as a nitrogen

structure

of zinc(II)

[1631.

A variety

of tetrahedral

dithizonate

zinc and

has been described

C1621.

The

shows a N s environment about zinc 22 complexes of vanillin azine

zinc and cadmium

complexes

have been reported

complexes

with phenylhydrazoacetoacetanilide

C1651.

donor towards

ZnL.ZHZO

(LHZ = 5,5*-(p-phenylenebisazo)diquinolin-8-01) crystal

with ligand donation

C1641.

Stability

constants

for zinc and cadmium

ligands have been determined

13

Amino acids

1.1.4.4

A polarographic the existence

study of L-4-hydroxyproline Zn(LHP)2

of [Zn(LHP)I+,

ligand coordinates

through

the nitrogen

oxygen atom of the carboxylate complexes

[167].

complexes

been studied

[1691.

of zinc shows

[166]. In Zn(LHP)2 the

atom of the pyrroline

of zinc and cadmium with L-lysine

Mixed-ligand

Stability

ring and an

constants

for 1:2

have been determined

C1681.

of zinc with anions of erotic acid and amino acids have

Heterocyczes

1.1.4.5

Solvent extraction

measurements

constants

for mixed-ligand

pyridines

[1701.

octahedral studied

group

(LHP) complexes

and [Zn(LHP)31-

Some substituted Crystal

[1731.

Zn(N03)2(quin)2

of zinc with chloride

pyridine

structures

of the nitrate

with some benzoylpyridines

formates

and pyridine

adducts of zinc halides

for Zn(N03)2(py)2,

show &s-coordination

degrees of involvement

zinc ascorbate

ligands

[174]. [175].

shows a distorted adducts

have been described

In [Zn2L(bipy)2](PF6)2 two metal centres,

C1781.

Synthetic

chelated

evidence

bipyridine

Stability

constants

for ternary mixed-ligand

for zinc complexes

N4

the ligand acts as a bridge

of zinc has been presented

phen and N-(thiobenzoyl)-N-phenylhydroxylamine Stability

tetrahedral

of

of

each zinc is in a N 0 tetrahedral environment 22 for a monodentate intermediate in the formation

complexes

constants

structure

(15) [1771.

(LH2 = naphthazarin)

between

and

of Zn(NCSj2

The crystal

bis(l,4-dihydro-1-pyridyl)bispyridinezinc(II)

bis(3-nortricyclyl)zinc

have been

bases with various

Complexes

environment

Two bipyridine

are has been

Zn(N03)2(2-Mepy)2

of the heterocyclic

have been described

about zinc C1761.

formation

and some substituted

adducts with zinc and cadmium

The 1:2 adduct between

[1711.

C1721.

described

complexes

Aminopyridine

have been used to determine

of

[1791.

complexes

of zinc with bipy,

have been determined

C1801.

with Tiron and phen have also been

14 determined

Various

ClSll.

adducts

synthesised

and characterised

Zn(terpy)C12

shows discrete

almost

trigonal

of Zn(CN)2 with bipy and phen have been

by IR C1821.

monomeric

bipyramidal

NSCZS

The crystal

molecules

environment

C1831.

his-bidentate coordination

1:l complexes

forming

(16) forms

with zinc in which the ligand acts as a

five or six-coordinate

through pyridyl

nitrogen

polymeric

complexes

and amide oxygen

involving

atoms [184].

/(? j. //“-“\_/“- ‘N

of

the zinc atoms have an

The ligand

N-methyl-N.N'-bis(2'-pyridinecarboxamide)-l.Z-ethane non-deprotonated

structure

in which

N’- \

Ye

?

H

(16)

0

Some heterobinuclear

complexes

involving

N.N'-bis(antipyrylmethyl)piperazine ZnL(NCS)2 [1861.

(L = bis(methylaminoantipyryl)ethane)

Substituted

Imidazole

pyrimidine

and substituted The crystal

zinc and cadmium. [Zn(imidH)61C12.4H20 imidazole

zinc and the tetradentate

have been described

has also been characterised

adducts with ZnC12 have been reported imidazoles structure

Thermodynamic

continue

to be popular

of the imidazole

shows a zinc atom octahedrally

coordinates

by six planar

parameters Cl891.

in the range 2.183-2.1962 [188]. 2+ for the interaction of Zn with 1-methylimidazole The zinc complex

through

ZnL2 (LH = 4-(3'.3'.3'-trifluoro-

the oxygen atom of the hydroxy

imine group has been described

c1901.

ligands and substituted

The crystal

structure

Zinc complexes

phenols

where the ligand

group and the N atom of the with substituted

as anions have been reported

[1911.

of

bis(4.4'.5.5'-tetramethyl-2.2'-biimidazole)zinc(II)O

pyramidal

C1871.

ligands with

complex

coordinated

2'-oxopropylidene)-2.2.5.5-tetramethylimidazolidine-l-oxyl)

consists

ligand

The compound

rings with Zn-N distances

have been measured

imidazole

Cl851.

gocopper

10dinitrate

[Zn(Me bim) ONOl+ cations giving an approximately square 4 2 NdO environment about zinc [192]. The crystal structure of the

of discrete

imidazole-bridged

bimetallic

center

in the copper-zinc

superoxide

dimutase

has

15 been described

[193] as has the structure

cyclo(L-methionyl-L-histidyl) of Zn2+ with 2,4-dimethyl [195]. Zinc and cadmium have been reported

of the zinc complex with

Stability

[1941.

complexes

with benzimidazole

Formation

C1961.

constants

((lH-benzimidazol-2-ylmethylene)amino)phenol zinc complex with 5-nitrobenzimidazole 2-methyl-5-nitrobenzimidazole be tetrahedral [2001.

1,2,4-triazole

and substituted

[202-2041.

The crystal

(L = 4-ethyl-1,2,4-triazole) with the central

complexes

to

of 2-aminobenzothiazole

The synthesis

complexes

and structures

of some

with zinc have been described

coordinated

trinuclear

by six nitrogen

cations atoms and

atoms and three oxygen atoms of water

The ligand

1,4,7-trizacyclononane-N,N',N" set in its zinc complex via deprotonated

The

adducts of ZnC12 are thought

shows linear ligand bridged

zinc atom octahedrally

C2051.

of

of [Zn3L6(H20)6](CF3S03)6

zincs by three nitrogen

the terminal molecules

[201].

triazole

structure

C1981.

chelates

cl971 and the

(L = 6-methyl-2_aminobenzothiazole,

ZnL2X2 and ZnL4X2

have been described

and 2-methylbenzimidazole

for zinc and cadmium

reported

and metronidazole

X = I,NCS,OAc)

for the interaction

have been determined

have been measured

cl991 as are zinc and cadmium

Some complexes

constants

and 2,7_dimethylbenzimidazole

-tris(2_ethanesulphonate)

12061.

nitrogen

Compiexes

of (17) appear

provides

a N 0 donor 33 the ligand

to involve

[2071.

07)

Zinc halide C2081.

complexes

The complexes

with bridging

ligands

aminoalkyltetrazole pyrazine

complexes

pz bridges

[2111.

with 4,6-dimethylpyrimidine_2(1H)-one Zn(LH)2C12 [?091.

complexes

Complexes

for a number of 12101.

show these compounds

spectroscopic

ESR studies on zinc to be polymeric

study of the pyrazole

arsenic and carbon donor Zigands

Raman and phosphorus-31

with

adduct of

[212].

with phosphors,

The far infra-red,

constants

have been determined

doped with Mn(II)

ZnS04 has been reported

1.1.5

Stability

An infra-red

have been described

and ZnL2 (LH = 5- am ino te trazole) are polymeric

NMR spectra of 1:l and 1:2

16 adducts of zinc and cadmium halides Zinc and cadmium

with tricyclohexylphosphine

complexes

studied

[2131.

contain

the ligands as oxygen-arsenic

Gas-phase dipropylzinc orbital

electron

structure

studies on dimethyl-.

on dimethylzinc

indicate

been described

zincacyclohexane

[2161 and appear

complexes

structure

neopentylidyne

of a trimetallic

G2C&Tnvironment

C2191.

structure

trigonal-planar

The synthesis

has been reported described

complex

as dimers [217].

and

have

in thf solution. The crystal

shows zinc in a tetrahedral

compZexes as donor Zigands

of the [Zn(Fe(cp)(C0)2)31zinc complex

anion is the first for a

and shows Zn-Fe distances

of a series of zinc(transition-metal

and the crystal

structure

of Lewis bases

to give the kinetically

and cadmium halides scission.

The synthesis

of 2.5418

carbonyl)

of [ZnFe(cp)(C0)20Me]4

alkoxides (18)

[220].

In the presence reduction

[2151.

of zinc are

[218].

The crystal tetrametal

and

~b ivlit{o molecular

has been reported

Complexes with transition meta

1.1.6

acids

and zincacycloheptane

to exist exclusively

A study of dinorbornylzinc

diethyl-

that the 3d electrons

and that the Zn-C bonds are pure o-bonds

of zincacyclopentane.

arsinobenzoic

[2141.

show C-Zn-C angles of about 114O C2151.

calcultions

non-bonding

diffraction

of Z-tertiary

donors

have been

react with

or both 12221.

ethers with Zn{Co(C04)}2 {Zn(cp))2Co(Cp)P(C

H ) 653

[ZnFe(CO)41n stable

complexes

[Zn{Fe(CO)4}212-

CF~~(C~)~(CO~)(CNM~)~

Reactions

of allylic

have been studied has been determined

undergo mild stepwise anion C2211.

to give adducts.

and propargylic

C2231.

The crystal

Zinc dimer

amines and structure

of

C2241 as has been the structure

for

17

(CH3)2~(~~2)3Zn~(~~)(~~)~ [Zn4Ni2(cp)61 ZnPt(th)C13 platinum

The structure

C2251.

has also been described (th = thiamine)

contains

12261.

a two coordinate

compound

zinc atom bonded

to

C2271. MacrocycZic

1.1.7

Formation

complexes

constants

for zinc complexes

of tetramethylcyclam

N,N1,N"-tris(2-hydroxyethyl)-l,4,7-triazacyclononane The synthesis

of a mono-N-functionalised

been described

ligand

(both I) are described

(Cl,Br,I,py

C2281 and

[2291 have been measured.

tetraazamacrocycle

Axial ligand derivatives

C2301.

of zinc with one axial ligands

compound

of the metal-cluster

The dinuclear

zinc complex

of the macrocyclic

or Me2benzimidazole)

has

complex

(19)

or two axial

C2311.

(19)

U

The imine carbon-13 coordination

chemical

shifts of these complexes

are affected most

number

and to a lesser extent by the axial ligand. 2+ data for the interaction of Zn with

Equilibrium

N,N',N"-tris(2-(N-hydroxycarbamoyl)ethyl)-1,3,5-benzenetricarboxamide

have

been determined

C2321.

Reversible

films of zinc phthalocyanines

oxidation

and re-reduction

has been observed

C2331.

of entire

by

thin

An electrochemical

study of Zn(Pc-CN8) existence

(PC-CN8 = octacyanophthalocyanine) has established the /. of a stable tetraanion [Zn(Pc-CN8)]4- in non-aqueous solution C2341.

The physical

and chemical

properties

it to be aromatic

similar

crystal

of zinc and cadmium

structure

macrocycles

show that systematic

lead to a dramatic complexes

of a zinc complex

to porphyrins

dislocation

minor

and corroles

complexes

of a sapphyrin

C2351.

Stability

(20) show data and

of a series of 0 N donor 23 of ligand structure can

perturbations

in geometry

at one point along a series of metal

C.2361.

Zinc complexes through oxygen

atoms

of some cyclic urethanes 12371.

(21) appear

to be coordinated

only

18

Me

HN

NH I (yH2)6

I n-1,2

T6 (21)

The synthesis described

and characterisation

c2381. Equilibrium

and dinuclear

macrocyclic

[2391 as have stability The ligand

of some soluble

constants

complexes constants

(24) forms pentadentate

bimetallones

for the formation

of zinc with

of some mononuclear

(23) have been determined

for some polyaza-crown complexes

(22) have been

ether complexes

with zinc and cadmium

[241].

[240].

RS

ys\,“/‘yyR

NI .N/ \o/ lNRN I

I

c ‘o-’ tl-Bu

Carbon-13

(233

(22)

and proton

NMR spectra of some porphyrin

quality of the spectra

improves with the addition

been described

Photophysical

porphyrins porphyrin

[2421.

have been studied derivatives

base complexes

of zinc tetraphenylporphyrin [247].

spectrophotometrically

Coordination

have

zinc

Equilibrium

by adsorbed kinetics

studies of

poly(4-vinylpyridine)

of

in pyridine

have been studied

metalloporphyrins

oxidase models

Zn(hp)(H20),

(hpH2 = (26)) have been reported

Schiff

A full pH study of incorporation

C2461.

Some imidazolato

of zinc complexes

the

spectra of zinc porphyrin

with Zn(OAc)2

and studied as cytochrome

characterisation Zn(hp)(HBr)

C2481.

of some water soluble

C2451.

has been made

tetra(5,6-dimethylbenzo)porphine

synthesised

The IR and mass

(25) have been reported

have been reported

where

Proton NMR was used to study some capped

[2431.

C2441.

of Zn2+ into uroporphyrin complexation

properties

complexes

of excess pyrrrolidine

C2491.

Zn(hp)(HCl),

C2501.

have been

The synthesis Zn(hp)(HC1)2

and and

20

(25)

(26)

The decrease partially

in rate constants

ether cavities 2,6-lutidine

12511.

investigated Spectroscopic

C2531.

zinc-carbon

Complexation

porphyrins

into fully and in the presence

films prepared Polyvalent

by UV-visible

porphyrins

by C2521.

12551.

Some

have been

of zinc have been studied

of superoxide

have been reported

and zinc-sulphur

spectroscopy

by electro-oxidation

of

ability of the crown

of zinc tetraphenylporphyrin

studies on the reaction

tetraphenylporphyrin

incorporation

in terms of cation complexation

and dmso has been studied

metalloprotoporphyrin

2+

meso-substituted

benzo-15-crown-5,

cations has been explained

of Zn

[2541.

ion with zinc

The photochemical

bonds in zinc porphyrins

activation

has been studied

C2561.

of

21

CADMIUM 1.2

Cacihiwn (III

1.2.1

Halide and pseudohaZide complexes

The preparation

of some phosphorus-quaternary

compounds

have been

described

C2571and IR bands proposed for [CdC1,12-, [CdBr41 2- and [Cd2C161

species.

An infra-red

the existence

study of some thiosemicarbazide

of a [Cd3C1,12-

adducts

C2581. The vibrational

species

soLid pyridinetrihalocadmiate

complexes

have been described

constants

complexes

have been measured

for cadmium

bromide

of Cd 2+ from thiocyanate

extraction

solutions

2-

of CdC12 shows spectra of some

c41.

Equilibrium

12591.

has been studied

Solvent

[260].

Complexes with oxygen donor ligands

1.2.2

1.2.2.1

Inorganic

The crystal

structure

of Cd(OH)(N03)

cadmium by three hydroxyl method

and ions

moZecuZes

and three nitrate

has been used to study formation

[262].

Stability

solubility structure

constants

of Cd(OHj2

for [Cd(OH)31-

oxygen donor in compounds

1.2.2.2

Simple organic

the

The crystal

Chlorosulphate

(L = py,CH3CN)

acts as a

[17].

Zigands

structure

of the 1,2-ethanediol

[CdC12(C2H4(OH)213-C2H4(0H)2 cadmium

by determining

C2631.

[264].

CdL4(S03C1j2

about

C2611. A competing ligand 2+ hydroxy complexes Cd

were obtained

has been redetermined

unidentate

complex

shows a chlorine-bridged

in a 02CZq environment

Cd[Al(OiPr)314

groups

of monomeric

in LiOH. NaOH and KOH solutions

of Cd4Na(V04j3

The crystal

shows a hexa-coordination

C2651.

has been described

The bimetallic

[191.

endless

chain with

isopropoxide

A polarographic

study of complexes

between mono-.

di- and tri-ethanolamines has been reported 1211 as has a study 2+ of mixed-ligand complexes of Cd with some carboxylic acids and 2+ ethylenediamine C2661. Formation constants for Cd with some monocarboxylic acids have been reported

C2671.

dichloro(L-proline)cadmium(II) chlorine

atoms and a carboxyl

each cadmium formates

hydrate group

atom is in a distorted

being bidentate

Antimicrobial

The structure

activity

is a one dimensional

C2681.

and bridging

polymer

In the structure

octahedral

of mixed-ligand

of

environment

to other cadmium complexes

bridged

by

of NH4CCd(HC00)31

with all the

atoms [269].

with HO-8-quin

and

22 various

salicylic

mixed-ligand tetraionic

acids have been studied

complexes species

monocarboxylates

complexes

have been measured

with hydroxamic

The crystal

octahedral

Cd12L2

1.2.3

Complexes

with

The structure

irregularly

donor

of a distorted

distorted SE octahedron

along which cadmium environments

its l-methyl

analogue

Potentiometric

acid

A variety of cadmium

of the complex

tetrahedralS202 structure

anion consists Cd4 tetrahedron

[2771.

mixed complexes

C2851.

Polarographic

complexes

dithiocarbamate

complexes

complexes

and

of

linear chains

and dodecahedral

complexes acid

complexes

consists

thiourea

with

have been described

[2821 whereas the cadmium

Thermodynamic

or thiosulphate

studies of mixed-ligand

[75. 761.

possesses

a for

ions have been reported

of cadmium thiolactate

thiocyanate

in the

parameters

have been described and glutamate

C286, 2871 as has been a polarogaphic

of thioacetamide.

The

of an approximately

C2831.

complexes

and

C921.

C2801 have been

with phosphinesulphides

Sq environment

have been reported

mixed-ligand

structure

tetrahedralSq

studies of cadmium

with tu and nitrite

Some disubstituted

and a highly

halide adducts with imidasoline-2-thione

(L = N.N'-dimethylthiourea)

[2841.

The

with the ligand

of infinite

about the cadmium atom

tetrahedral

ligand Cd 2+ C2751.

of an adamantane-like

The crystal consists

Cd(tmtu)2(N03)2

environment

of CdL4(N03j2

very distorted

The anionic donor towards

C2791 and dithiopropionic

C81, 84. 2811 as have cadmium structure

has been reported

shows a distorted

the ligand as simple sulphur donors

and polarographic

2-mercaptopropionic described.

Cadmium

contain

[47] and an anthranilic

is tetrahedral

atoms are in alternating

C2781.

for cadmium

Zigands

bis(carbethoxymethanethiolato)cadmium(II)

S404

CdL2.7H2Q

C2761.

of the [Cd4(SPh)lo12-

cage composed

Cd4(p-S16

acids

of Cd(acac)2

12741.

acid amide)

suZphur

structure

constants

of Cd(acac)2(phen)

about cadmium

acting as a simple oxygen donor

of some cadmium

Formation

- acts as a phosphineoxide

(2, = isobutyric

of

complex with cadmium atoms in a 050'2 2+ for the interaction of Cd with

1411.

structure

study of

shows the presence

The crystal

[451. salicylic

acids

04N2 environment

[(cp)Co{P(0)(OMe)2}31 complex

adducts

The electrosynthesis

acid 1491 are reported. [54, 2741.

constants

A polarographic

and oxalate

C2721.

shows a dimeric

Stability

C2731.

~Y-~,~-(CO~H)~

Trimethylamine

C2711.

have been described

(L = p-hydroxybenzoate) environment

C2701.

with mercaptobenzoate

study on

and nicotinamide

C2881.

23

CompZexes with nitrogen donor Zigands

1.2.4

Amines

1.2.4.1

Both the compounds nitrogen

environment

about cadmium

in a distorted

cooordinated Stability

C2891.

The cadmium atoms environment

has an infinite

of protonated,

en have been measured diaminopropane

C2921.

Cd(N03j2

Mixed-ligand

C2911.

The crystal

chains

structure

with

of the

coordinated

cadmium

0 1 environment and the other has a 222 The structure of the hydrated adduct of

in which cadmium

and are linked by bridging

atoms have an 0 0' fl 2 22 C2951.

hmta groups

Sehiff bases, hydrasones and related donors

1.2.4.2

The cadmium in the section

analogues

of many of the zinc Schiff base complexes

on zinc have been reported

117. 119. 120. 122, 123, 126-128. metals.

The cadmium

diaminopropane

is thought

Cadmium

complexes

N.N-dimethylglycine through aNSO

thiocarbazone

to be tetrahedral

C300, 3011.

of both

from benzoin

and

CdLX2

have been described

12991.

and

to be coordinated

complexes

of some

Many hydrazone

and

in the section on zinc and furfural

with the ligands being either

constants

thiosemicarbazone

with substituted

The structure

are thought

with acetone

or bidentate

Stability

complexes

[116.

product of biacetylmonoxime

been described

have been described

through selenium

p-nitrobenzaldehyde complexes

have already

reported

references

Complexes

The cadmium

Cadmium complexes

selenosemicarbazones

nitrogen

hydrochloride

have been investigated

complexes

12961.

X = C1.Br.I.N03.SCN.C104)

with the condensation

hydrazide

C137. 138. 142-1461.

monodentate

130. 133, 1361 describe

ligand donor set [2981.

salicylaldoximates

and in particular

complex with the Schiff base derived

(L = N.N'-bis(acetoacetanillde):

consists

atoms

chelated complexes 2+ of Cd with en and

complexes

C2931.

7V1S environment.

with hmta comprises

environment

C2971.

with each cadmium

and two amine nitrogen

have been investigated

tetrahedral

are

non-, and partially

[294], one is in an octahedralN

distorted

four coplanar

The compound

adduct of Cd12 with hmta shows two differently

hydrated

contain

in Cd12(p-toluidinej2

C2901.

layer structure

by four cyano nitrogen

constants

and Cd(NH3)4(1.12)2

iodide ions with form a QUasi-octahedral

tetrahedralN212

[Cd(NH3)2Ni(CN)4]

atoms

Cd(NH3)412.12

atoms and two axial

through

selenium

for cadmium

have been determined

salicylhydrazines

appear

and the hydrazine

complexes

with

[302].

Some

to be oxygen-bonded

c3031.

of dichloroiodo(methylisothiocarbonohydrazidi~)cadmium(II)

of polymeric

a NCz41 environment

chains of edge-shared

[304].

The crystal

octahedra

structure

with the cadmium atom in

of potassium

cadmium

aside

24 K2Cd(N3j4 somewhat

shows cadmium octahedrally similar structure

surrounded

by six aside groups

is found in T18Cd3(N3)14

[305].

Heterocycks

1.2.4.3

Many cadmium corresponding 200-203,

complexes

solutions

anionic

13101.

complexes

resemble

in pyridine-hexane

as a function identified

the

The coordination have been studied

of CdC12 with a variety

[3091 as have mixed-ligand

and in

of solvent composition

[3071.

of N-(pyrid-2-yljthiobenzamide complexes

have been characterised pyridines

of Cd(OAc)2

were determined

properties

Mixed-ligand

closely

C171, 173, 175, 180, 182, 186. 187, 196-198.

Solubilities

a number of mixed-solvate extraction

with heterocycles

zinc complexes

207-2101.

dmf-benzene

of substituted

complexes

C3081. pyridines

with oxime and

The ligand bis(2-(picolinoylamino)ethyl)sulphide

acts as a

without involvement of sulphur [3111. The complexing ability 2+ bipy towards Cd has been studied polarographically in aqueous-ethanol mixtures

and characterised

CdC12L2

(L = 5-amino-1.2,3,4-thiatrazole)

[313].

The structure

octahedrally

coordinated

groups giving a N4S2 environment

structure

C3143.

xanthine

complexes

(LH = 2-thiobarbituric and not sulphur

have been described

have been reported

acid) contains

of Cd12P(C2H5)3

a tetrahedral

is tetrameric

described

with phosphorus ad

The structure

13151.

NCS

CdC12 and The crystal

[317] and the physical

[3181.

The complex

the ligand coordinated

in

properties

CdL2 through nitrogen

arsenic

donor tigands

is dimeric with iodide bridges

PI3 environment

whereas

the structure

giving

of CdC12P(e-C6H11)3

with two cadmium atoms each having

Vibrational

and phosphorus-31

with tricyclohexylphosphine (SV)has been synthesised

C3221.

ligands and four bridging

Some 1:l adducts between

C3191.

CompZexes

[3211.

shows

L (H 0) (L = dimethyltriazolopyrimidine) shows cadmium 22 2 2 octahedral N 2N 2'02 environment C3161. Thermal studies of some

of a CdC12 adduct with adenine

C3201.

has been prepared

(L = triazole)

of Cd(NCS)

a distorted

cadmium

of CdL2(NCSj2

by two triazole

CdBr2 with 2-(2'-pyridyl)imidazoline

1.2.5

of

C3121.

The compound

cadmium

and

and

tetradentate

cadmium

A

C3061.

Various

PC1 and PCZ environments 4 3 spectra of 1:l adducts of cadmium halides

are described

and characterised

cadmium halide

complexes

[2131.

The heterobimetallic

by phosphorus-31 with arylarsolanes

complex

NMH spectroscopy have been reported

25

Ph2 P

,cR .C@ I *Pi’

PPh2 1 Cd 12

4,C Rc

1.2.6

Macrocyclic

Some macrocyclic

described

I P Ph2

complexes

complexes

to in the corresponding preparation

I Ph2P

<27>

containing

cadmium have already

been referred

section on zinc C228. 236, 241, 248. 2551.

and electrochemistry

of the cadmium

The

complex with (28) have been

[323].

Ph

c28)

The crystal in a distorted Mn(II)

structure

of the 1:l compound

square pyramidal

into tsppH2

(30)

of Cd12 with

NSIS environment

is catalytically

assisted

(29) shows cadmium

c32.41. Incorporation of 2+ at concentrations by Cd

as

low as 10-7mol.dm -3 [3251.

1.2.7

Cadmiwn-113

NMR spectroscopy

The '13 Cd NMR shifts for.a number of CdX2L (L = 2,6-diacetylpyridine(bls(imine)); measured

and show a dependence

X = Cl,NCS.I.OAc)

on the coordination

number

complexes

have been

of the cadmium

[326].

26

(29)

The solid state

113

has been measured

Cd NMR spectrum of [CdL41(N03)2

C2831 as has been the spectrum

(L = 1,1,3,3-tetramethyl-2-thiourea) spectrum

of Cd(N0

symmetry

C3271.

number of cadmium

c2821.

(I, = N,N'-dimethylthiourea)

for [CdL2(N03)21

The single crystal cadmium-113

NMR

) .4H 0 shows that shielding tensors do not exhibit axial 32 2 Carbon-13 and IL'3Cd NMR spectra have been re-recorded for a amino acid complexes

chelate rings involving

cadmium

and imply formation

of five-membered

C3281.

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