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Spectral-structural correlations in high-spin cobalt(II) complexes

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Structures versus Special Properties

Part of the book series: Structure and Bonding ((STRUCTURE,volume 52))

Abstract

The spectral and magnetic properties of simple high spin cobalt(II) complexes are reviewed with the aim of showing how it is possible to relate the experimental data to the electronic structure and the coordination geometry of the complexes. It is hoped that this may be of help to all researchers who need to characterize cobalt(II) complexes or use cobalt(II) as a spectroscopic probe. The data relative to electronic, EPR, MCD, NMR spectra as well as to magnetic susceptibility measurements are interpreted within an Angular Overlap approach. Energy level diagrams are employed to calculate the electronic spectra and then, applying the relevant perturbation μ, g, A values are calculated for different chromophores in different coordination environments. The underlying theory is sketched paying in every case much attention to show the possibility of calculating the electronic properties in low symmetry environments. An extensive compilation of available experimental data is presented. The chromophores are classified according to the coordination number and according to the donor atom set.

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Abbreviations

AA:

acrylamide

ac:

acetylacetone

acac:

acetylacetonate

acpz:

N-acetylpyrazole

APDA:

2-amino-5 phenyl-1,3,4 oxadiazole

apy:

2,3 dimethyl-1-phenyl-3-pyrazolin-5-one

ATP:

adenosine-5′-triphosphate

bipy:

2,2′ bipyridine

BIz:

benzimidazole

C3H2S3 :

dithiole-1,2 thione-3

dabp:

2,2′ diamino biphenyl

dacoda:

1,5 diazacyclooctane-N,N′-diacetate

dan:

1,8 diaminonaphtalene

DEAP:

diethylacetylphosphonate

DEU:

N,N′-diethylurea

dienMe:

bis(2-dimethylaminoethyl)methylamine

dietu:

diethylthiourea

4 DMAP:

4-N,N′-dimethylaminopyridine

dpdmq:

6,7-dimethyl-2,3 di-(2-pyridyl)-quinoxaline

dpmq:

6-methyl-2,3 di-(2-pyridyl)-quinoxaline

DTMSO:

1,4 dithiane monosulfoxide

EG:

ethylene glycole

en:

ethylendiamine

epydo:

1-methyl-2-pyridone

ESU:

ethylselenourea

Et:

ethyl

Et3P:

triethylphosphine

Et3PO:

triethylphosphineoxide

Et4D:

tetraethyldithio oxamide

2-Et-py:

2-ethylpyridine

s-Et2en:

N-N′diethyletylenediamine

FUAenMe2 :

2-furylidene-2-iminoethyl-N,N diethylamine

HdMePyne:

2-hydrazino-4,6-dimethyl pyrimidine

H-SAL-DPT:

bis(salicylidene-3-iminopropyl) amine

5-ClSALenNet2 :

5-chlorosalicylidene-2-iminoethyl-N,N diethylamine

Iz:

imidazole

LE:

1,2-di(2′-pyridyl)ethane

L-Histidine:

L-histidinato

LS:

di-(2-pyridyl)disulfide

MABenz-NEt2 :

N-methyl-o-aminobenzilidene-2-imonoethyl-N,N diethylamine

Me:

methyl

Me(Cl-Ph)TazO:

1-methyl-3(2 chlorophenyl) triazene-1-oxide

Me4daes:

bis(2-dimethylaminoethyl)sulfide

Me4dipyMT:

3,3′4,4′-tetramethyldipyrromethane

Me4en:

N,N,N′,N′-tetrame thylethylenediamine

2MeIz:

2-methylimidazole

MeN-NAs:

1-(2′-pyridyl)-2-(o-dimethylarsinobenzene)-2 azaethane

MePh2AsO:

methyldiphenylarsineoxide

Me4pn:

N,N,N′,N′-tetramethyl-1,2-propylenediamine

Me2ppaz:

1,4-dimethylpiperazinium cation

Me3PSe:

trimethylphosphine selenide

2 Mepy:

2-methylpyridyne

1 MePyne-2-T:

1-methylpyrimidine-2-thione

1,4,6 MePyne-2-T:

1,4,6 trimethylpyrimidine-2-thione

6 Mequin:

6-methylquinoline

Me4tn:

N,N,N′,N′-tetramethyltrimethylenediamine

Me6tpt:

tris-(3-dimethylaminopropyl) amine

Me6tren:

tris(2-dimethylaminoethyl) amine

2-MIz:

2-methylimidazole

MOBenz-NEt2 :

o-methoxybenzilidene-2-iminoetyl-N,N-diethylamine

MSBenz-NEt2 :

o-methylthiobenzilidene-2-iminoethyl-N,N-diethylamine

NCNPh:

phenylcyanamide

N-EtdAZAO:

N-ethyl-1,4-diazabicyclo(2.2.2.)octonium cation

NMBuL:

N-methyl-γ-butyrolactame

N-N-N:

a,a′,a″-tri-imine-2,6-(dibenzothiazol-2-yl)pyridine

NN3 :

tris(2-diethylaminoethyl)amine

N3As:

bis(2-diethylaminoethyl)-2-diphenylarsinoethylamine

N,N′(4 ClB):

N,N′di-(4-Chlorobenzen)-pro-

PAI:

pene-1-iminato-3-imine

N3P:

bis(2-diethylaminoethyl)-2-diphenylphosphine ethylamine

N-NO2 :

2-diethylaminoethyl-bis-(2-methoxyethyl)amine

N-N2O:

bis(2-diethylaminoethyl)-2-methoxyethylamine

N2OP:

N-2-(diphenylphosphino)ethyl-N-(2-methoxyethyl)-N′,N′- diethylethylenediamine

NOP2 :

bis(2-diphenylphosphino-ethyl)-2-methoxyethylamine

N2P2 :

2-diethylaminoethyl-bis-(2-diphenylphosphinoethyl)amine

N-NS2 :

bis(2-methylthioethyl)-2-diethylaminoethylamine

N-N2S:

bis(2-deithylaminoethyl)-2-methylthioethylamine

N2SP:

N-2-(diphenylphosphino)ethyl-N-(2-methylthioethyl)-N′,N′-diethylethylenediamine

NP3 :

tris(2-diphenylphosphino-ethyl)amine

NS3 :

tris(2-t-butylthioethyl)amine

N-tBpyle-2-C:

N-t-butylpyrrole-2-carbaldimino

N-tBpyle-2-Aim:

N-t-butylpyrrole-2-aldimino

OAB:

o-aminobenzoate

OMPA:

octamethylpyrophosphoramide

OPD:

o-phenylenediamine

ox:

oxalate

PC4P:

1,4-bis(diphenylphosphino) butane

Ph:

phenyl

Ph3AsO:

triphenylarsino oxide

PhIPPh3 :

phenyliminotriphenylphosphorane

Ph3P:

triphenylphosphine

Ph3PO:

triphenylphosphineoxide

(Ph2PS)2N:

imidotetramethyldithiophosphino-S,S′

pic:

2-methylpyridinecarboxylate

PN′H+ :

2-(diphenylphosphinomethyl)-6-methylpiridinium ion

POP:

bis(diphenylphosphinoethyl) oxide

py:

pyridine

PyAenEt2 :

pyridine-2-carboxalidene-2-iminoethyl-N,N-diethylamine

py(Bus)2 :

2,6-diacetylpyridinebis(s-butylimine)

3 py(CO2):

pyridine-3-carboxilate

py(cy)2 :

2,6-diacetylpyridinebis(cyclohexylimine)

pyO:

pyridine-N-oxide

pz:

pyrazole

quin:

quinoline

SAL:

salicylaldeyde

SALen:

N,N′-ethylenebis-salicylaldiminato

SALiprp:

salicylidene-2-iminoisopropylamine

SU:

selenourea

TMPT:

1,4,6-trimethylpyrimidine-2-thione

tren:

2,2′,2″-triaminotriethylamine

trik:

1,5-diphenyl-1,3,5-pentanetrionato

tripyr:

1′,6-diethoxycarbonyl-1,2,3,4,5,6′-hexamethyltripyrrene

TTDA:

bis(N,N-dimethylacetoamido)-thioether

TU:

thiourea

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  1. General Chemistry Institute, Faculty of Pharmacy, University of Florence; I.S.S.E.C.C., C.N.R., Florence, Italy

    Lucia Banci, Alessandro Bencini, Cristiano Benelli, Dante Gatteschi & Claudia Zanchini

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  1. Lucia Banci
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Banci, L., Bencini, A., Benelli, C., Gatteschi, D., Zanchini, C. (1982). Spectral-structural correlations in high-spin cobalt(II) complexes. In: Structures versus Special Properties. Structure and Bonding, vol 52. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0111296

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