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Strut Chem Cite

Strut Chem Cite

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Published by Punitha Mohan
about thermochemistry
about thermochemistry

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Published by: Punitha Mohan on Mar 15, 2013
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REVIEW ARTICLE
Interplay of thermochemistry and
Structural Chemistry
,the journal (volume 21, 2010) and the discipline
Maja Ponikvar-Svet
Joel F. Liebman
Received: 24 January 2011/Accepted: 16 February 2011/Published online: 5 March 2011
Ó
Springer Science+Business Media, LLC 2011
Abstract
In the current review the content of the journal
Structural Chemistry
for the calendar year 2010 is relatedto thermochemistry. To a short summary of each article inthis volume of the journal a thermochemical comment isadded.
Keywords
Structural Chemistry
Á
Thermodynamics
Á
Physical Chemistry
Á
Thermochemistry
Á
Enthalpy of formation
Á
Chemical reactions
Á
Phase transitions
Introduction
The current review of 
Structural Chemistry
for the calendaryear 2010 has become tradition as this is already the 10threview and as such, constitutes a ‘‘jubilee’’ review. Let usadd that we have been told that these reviews in which anattempt is made to link experiments and theory of all of thearticles in a given chemistry/physics/material scienceperiodical, represents a unique and appreciated approach.This adds to our enthusiasm to continue with this annualproject.This review is conceptually and organizationally verymuch the same as the reviews of previous volumes of this journal [110] in which each article has been reviewed and summarized by us from our personal perspectives as wellas knowledge, facilitated wherever possible by the originalauthors’ choice of key words. Of course, our perspectivesare often very much different as is also our basic scientificeducation—it is interesting to observe how scientistsworking in different areas consider the same subject.Therefore, it is perhaps also educational how we handle thesame area of investigation from our perspectives of theo-retical and analytical chemistry and then combine thecomments into a logical unit. The review is supplementedby adding thermochemical comments. Occasionally, it isfound that the investigations presented in the articles doc-ument inadequacy of current knowledge by the scientificcommunity and that additional studies enlightening theinvestigated area would be highly desirable. As such, hints,suggestions, and encouragement for possible futureresearch are often given.Thermochemical data are occasionally given as part of our added material as well. All data for inorganic com-pounds with otherwise unreferenced enthalpies of forma-tion will be assumed to be taken from ‘the Wagmancompendium[11], while corresponding unreferencedenthalpies of formation of organic compounds will beassumed to be taken from ‘‘the Pedley compendium’’ [12].
Issue 1
Volume 21 begins with the editorial by Hargittai [13] onLinus Pauling and his work on the structure of proteins andeventual discovery of the alpha-helix. Pauling postulatedthat the amino acid units are linked to each other in thefolded protein molecule not only by the normal peptidebond but also by hydrogen bonding that is facilitated bythis folding of the protein. His quantum chemical theory of 
M. Ponikvar-Svet (
&
)Department of Inorganic Chemistry and Technology, Jozˇef Stefan Institute, Jamova 39, 1000 Ljubljana, Sloveniae-mail: maja.ponikvar-svet@ijs.siJ. F. Liebman (
&
)Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250, USAe-mail: jliebman@umbc.edu
 123
Struct Chem (2011) 22:717–740DOI 10.1007/s11224-011-9769-0
 
resonance contributed to his understanding of other scien-tific phenomena, although at the same time, this theory wasattacked in Soviet Union as an ideological aberration.In the first of the theoretical papers that follow Xu andChen [14] described use of density functional theory (DFT)to predict the structural parameters, IR spectra, and ther-modynamic properties of tetrazole derivatives. The totalenergies, heats of formation, and enthalpies of combustionindicate the following order of stability: 5-(2,4,6-trinitro-phenyl)-2
 H 
-tetrazole
[
[5-(2,4,6-trinitrophenyl)-1
 H 
-tetra-zole
[
[5-(2,4,6-trinitrophenyl)-5
 H 
-tetrazole. A similarresult is found for the corresponding three isomers of 5-(2,4,6-trinitrobenzyl)-tetrazole. While there is a consid-erable body of experimental data that allow for the com-parisonofthe stabilityof1
 H 
and2
 H 
-tetrazoles,weknowof no corresponding study for 5
 H 
-tetrazoles. Indeed, we knowof but few thermochemically relevant studies of specieswith a –N=N–N=N– substructure. One was the study of species [15] of the type Ar–N=N–N=N–Ar as part of thecomparison of the dimerization of, and N
2
loss by, tran-sientlyformedArN
2
radicals.Anotheristhesuggestionthat5-nickelatetrazoles may enjoy significant stability [16].Liu et al. [17] then used DFT to study the correlationbetween regioselectivity and site charge in propene poly-merization by single-site metallocene catalysts such as[Cp
2
ZrMe]
?
. The activation energy for 1,2-insertion wasshown to be lower than that for 2,1-insertion in agreementwith the experimental data. Let us ask now if there is anysteric repulsion between the methyl group of the propeneand the cyclopentadienyl rings that contributes to the reg-ioselective addition? How different are the activationenergies for
- and
-2-butene from that of propenewherein this methyl/cyclopentadienyl repulsion in these4-carbon olefins is unavoidable?Chapkanov [18] studied 2-aminopyridinium tetrachlo-rocuprate (II) salt both in solution and in the solid-stateusing IR and UV–Vis spectroscopy
1
H-NMR, TGV, andDSC methods. A change of aromatic character wasexplained by the N
py
protonation that leads to weak chargeredistribution in the pyridinium ring and thereby changes ingeometrical parameters. Thermodynamically, the stabilityof the aminopyridines decreases in the order 2-
[
4-
[
3- and span a 25 kJ mol
-
1
range. The proton affinities [19]of the aminopyridines decrease in the order 4-
[
3-
[
2-and span a 33 kJ mol
-
1
range. From these data we find thatthe stability of the aminopyridinium ions decreases in theorder 2-
[
4-
[
3-. Is this change in enthalpy of formation,and presumably aromaticity, reflected in the properties of the corresponding aminopyridinium salts such as the abovecuprates?For typical concentrations found in solutions the numberthe solvent molecules outnumber the solute moleculeswhich makes the analysis of solute molecular structuredifficult. Lee and Ihee [20] used time-resolved X-raysolution scattering for determining structures of smallmolecules and proteins in solution. The difference scat-tering curves generally exhibit much higher structuralsensitivity to the solute structure than the original scatter-ing curves. The authors discuss solutions of iodine inmethanol and dissociation to form atomic iodine. We notethat the enthalpy of solution of gaseous I
2
in methanol is54 kJ mol
-
1
; we know of no corresponding data for theatomic iodine as solute.Stem and Ellzey [21] studied organotin(IV) moleculesusing computational optimization modeling (COM) whichenables the prediction of molecular properties and struc-tures. The data were compared to the experimental data asobtained by X-ray crystallography and solid-state NMR.Hyperconjugation-derived stabilization is suggested to bean important force in these molecules. The lack of vali-dation of computational optimization treatments for manyorganotin(IV) molecules remains a limiting factor againstgenerating accurate COMs. These authors explicitlyinvestigated species with Sn–S bonds. The enthalpy of formation of the simplest condensed phase species of tin(IV) with sulfur, namely the binary sulfide and inorganicmaterial, SnS
2
has been reported [22] but comparison withorganotin sulfides remains unexplored.Su¨leymanog˘lu et al. [23] describe synthesis and char-acterization, including crystal structure analysis, of 2-pro-pylamino-5-[4-(2-hydroxy-3,5-dichlorobenzylideneamino)phenyl]-1,3,4-thiadiazole. The experimentally determinedmolecular geometry was compared to the geometryobtained by DFT calculations. The results showed that theSchiff base, which contains a thiadiazole ring, prefers the
-configuration. A thermochemical comparison of 1,2,3-,1,2,4-, and 1,3,4-thiadiazole, their amino analogs andderived Schiff bases is welcomed.Six new salicylic acid derivatives were prepared byDjurendic´et al. using conventional heating or microwave-assisted synthesis [24]. Comparison of structures obtainedfrom X-ray analysis and molecular mechanics calculationsfor three of these synthesized compounds,
-(2-hydrox-ybenzoyl)-2,2
0
-bis(2-hydroxybenzoyloxy)diethylamine,2,2
0
,2
00
-tris(2-hydroxybenzoyloxy)triethylamine and
-phenyl-2,2
0
-bis(2-hydroxybenzoyloxy)diethylamine revealed thatthe intramolecular hydrogen bonds play an important role instabilizing the conformation of the molecules. The antioxi-dant activity and cytotoxicity tests showed strong activityagainst hydroxyl radical, as well as exhibiting promisinglipid peroxidation inhibition. Comparison with the 3- and4-hydroxybenzoic acid isomers is welcomed: it is to benoted that the enthalpies of formation of the three isomerichydroxybenzoic acids spans but 6 kJ mol
-
1
in the solidstate.DoesthismeantheeffectoftheOHgroupsonstabilityand conformation is rather negligible?
718 Struct Chem (2011) 22:717740
 123
 
In the experimental paper by Zhang et al. [25] the syn-thesis and characterization of complex [Co(Imazameth)
3
]
Á
0.5DMF
Á
4H
2
O(Imazameth
=
(
±
)-2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1
 H 
-imidazol-2-yl)-5-methyl-3-pyridinecarboxylic acid) by IR spectroscopy, elementalanalysis, thermal gravimetric analysis, fluorescence prop-erties, and single crystal X-ray structureanalysisisreported.Octameric water clusters were observed. We know of nodirect measurement as to the enthalpy of formation differ-ence of the tautomeric 4,5-dihydro-4(5)-oxo-imidazole andimidazole-4(5)-ol or even between their methylated deriva-tives [26]: synthetic chemists [27,28] have provided useful information.In the following experimental study by Kruszynski [29],2,2
0
-bipyridine complexation properties of the dichloroac-etates of zinc and cadmium is reported. [Zn(C
10
H
8
N
2
)(CHCl
2
COO)(H
2
O)
3
]
Á
[Zn(C
10
H
8
N
2
)(CHCl
2
COO)
3
]
?
and[Cd(C
10
H
8
N
2
)
2
(CHCl
2
COO)
2
] were synthesized and char-acterized by elemental and thermal analyses, IR andUV–VIS spectroscopy, and crystal X-ray structure analysis.The zinc compound is a rare example of a salt containingcomplex anions and complex cations in which the sameorganic ligands and anions are in the inner coordinationspheres. Consider now Zn(C
10
H
8
N
2
)(CHCl
2
COO)
2
(H
2
O)
2
[30]. Forgetting now the differences of Zn and Cd, do thethree compounds in this paragraph compose a homologousseries of hydrates with regards to nearly constant enthalpyof formation differences, cf. [31]?Using the MP2 method Qiu et al. [32] studied hydrogenbonding patterns of the base pairs between 4-thiouracil,analogue of uracil and four RNA bases, adenine, uracil,guanine, and cytosine. The order of stability is s
4
U : guan-ine
[
s
4
U : adenine
[
s
4
U : uracil
*
s
4
U : cytosine andthe calculated interaction energies for the complexes varyfrom
-
7.4 to
-
13.3 kcal mol
-
1
. What about the differenceoftheir interactionenergieswith othernucleobases? What isthe enthalpy of formation difference of 4-thiouracil and theisomeric 2-thiouracil?Tomura and Yamashita [33] successfully synthesized the2:1co-crystal of1,2,5-thiadiazole-3,4-dicarboxylic acidand4,4
0
-bipyridine, which has been widely used as a ligand insupramoleculararchitectureincrystalengineering.Auniquetwo-dimensional ladder-type molecular network in theco-crystal is built using intermolecular O–H
ÁÁÁ
N hydrogenbonds and S
ÁÁÁ
O heteroatom interactions. The 1,2,5-thiadia-zoleringisexpectedtobearomaticbythecriterionofhaving6
p
electrons. Comparison of the aromaticity of its ringannelated qunoxaline and dihydroquinoxaline derivativeshas recently been reported [34]. How do these speciescompare with the parent 1-ring heterocycle?Gossypol is a polyphenolic terpene that is found in thecotton plant. Four new solid-state forms, two polymorphicand two solvated, of the likewise naturally occurringderivative, 6,6
0
-dimethoxygossypol were synthesized andtheir structures determined by X-ray diffraction by Zelayaet al. [35]. We note that gossypol and its dimethoxyderivative may be recognized as 2,8-dihydroxy-1-napthal-dehydes. What is the enthalpy of formation differencebetween the aldehyde hydrogen-bonded species involvingthe 2-hydroxy group and the ring closed lactol isomerformed with the 8-hydroxy?In the following study, Qi et al. [36] studied the silyle-noid 2-NH
2
CH
2
C
6
H
4
(CH
3
)SiLiF using DFT to get moreinsight into the structures, and properties and solutionphase reactions of pentacoordinate silylenoids. 2-NH
2
CH
2
C
6
H
4
(CH
3
)SiLiF is more stable than corresponding silyl-ene NH
2
CH
2
C
6
H
4
(CH
3
)Si. The insertion of 2-NH
2
CH
2
C
6
H
4
(CH
3
)SiLiF into C–F bonds is similar to that of NH
2
CH
2
C
6
H
4
(CH
3
)Si. The activation barrier for the for-mer is 62.9 kJ mol
-
1
higher than that for the latter. Whatare the corresponding values for the 3- and 4-isomers of NH
2
CH
2
C
6
H
4
(CH
3
)SiLiF and the corresponding silylene,and what are the differences of enthalpies of formationwithin sets of isomers?Trzesowska-Kruszynska [37] synthesized, characterizedby spectroscopic and thermogravimetric analyses, anddetermined the crystal and molecular structures of 
 N 
-(2-carboxyphenyl)-4-dimethylaminebenzylideneiminepenta-hydrate, which is an example of Schiff base compoundexisting as the zwitterion, stabilized by the intramolecularN
?
–H
ÁÁÁ
O
-
hydrogen bond. As shown by NBO analysis thisformisenergeticallyunfavorableforthefreemoleculebutinthe solid and solution states the intermolecular interactionssupport the presence of the zwitterionic form. How manywaters are needed to stabilize the zwitterion—is it neces-sarily at least five?In the theoretical study by Macaveiu et al. [38] theeffects of NO
2
groups on intramolecular interactions werestudied using chloromethane, Cl–CH
3
. NO
2
groups weresuccessively introduced to form chloronitromethanes.Corresponding CN and F derivatives were also checked.Shortening of the carbon–chlorine bond in chloronitrome-thanes was explained by the changes in the attractive Cl
ÁÁÁ
Oelectrostatic interactions. Following up on this investiga-tion of chlorotrinitromethane, Klapo¨tke and Liebman [39]studied the energetics of chlorotrinitromethane and othertrinitromethyl derivatives.Ghosh et al. [40] synthesized mononuclear nickel(II)and copper(II) complexes with the tetradentate Schiff basebiacetyl bis(benzoylhydrazone) (H
2
babh) with the generalformula [M(babh)] and characterized them by microanal-ysis, magnetic susceptibility, spectroscopically, and X-raycrystal structure analysis. Both compounds form one-dimensional self-assemblies via
p
p
interaction andhydrogen bonding. Considering the partial double bondcharacter of amides, the above species are seen to have four
Struct Chem (2011) 22:717740 719
 123

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