The chemistry of heavy elements: a comparison
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Abschlussarbeit Buch |
| Sprache: | English |
| Veröffentlicht: |
1996
|
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | VIII, 253 S. graph. Darst. |
Internformat
MARC
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| 100 | 1 | |a Kapp, Jürgen |d 1967- |e Verfasser |0 (DE-588)115406611 |4 aut | |
| 245 | 1 | 0 | |a The chemistry of heavy elements |b a comparison |c vorgelegt von Jürgen Kapp |
| 264 | 1 | |c 1996 | |
| 300 | |a VIII, 253 S. |b graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 502 | |a Erlangen-Nürnberg, Univ., Diss., 1996 | ||
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Datensatz im Suchindex
| _version_ | 1807681961847685120 |
|---|---|
| adam_text |
CONTENTS
I.
SILICON
AND
ITS
CONGENERS
.
1
1.
INTRODUCTION
.
1
2.
METHODS
.
4
2.1
HOW
TO
CONSIDER
RELATIVITY
-
A
THROUGHOUT
APPROACH
.
4
2.2
ALL-ELECTRON
VS.
EFFECTIVE
CORE
POTENTIAL
CALCULATIONS
.
5
2.3
NON-RELATIVISTIC
THEORETICAL
METHODS
.
7
2.4
ANALYSIS
OF
THE
ELECTRONIC
STRUCTURE
.
8
3.
THE
NATURE
OF
THE
CHEMICAL
BOND
-
BETWEEN
HEAVY
ELEMENTS
.
8
3.1
THE
MOST
IMPORTANT
FACTORS:
HYBRIDIZATION
AND
ELECTRONEGATIVITY
.
8
3.2
WHAT
"ARE"
RELATIVISTIC
EFFECTS?
.
13
4.
MOLECULAR
CALCULATIONS
.
14
4.1
MH4
AND
OTHER
"TRIVIAL"
MH
N
SYSTEMS
.
14
A)
TETRAHYDRIDES
.
14
B)
OTHER
MH
N
SPECIES
.
21
4.2
EVEN
MORE
TRIVIAL?
DIVALENT
GROUP
14
COMPOUNDS
MO,
MH2,
AND
MX2
.
A)
MONOXIDES
AND
CHALCOGENIDES
.
B)
MH2
AND
MX2
(X
=
HALOGEN)
.
C)
CLUSTERS
.
4.3
CARBENES,
SILYLENES,
AND
CONGENERS
.
4.4
THE
M=M
DOUBLE
BONDS
.
A)
HISTORICAL
DEVELOPMENT
.
B)
TRANS-BENT
STRUCTURES
.
C)
DOUBLE
BOND
STRENGTH
.
D)
EMPIRICAL
RULES
.
4.5
"H
2
M=MH
2
"
NO
LONGER
.
4.6
HALOGEN
BRIDGES
.
4.7
EVEN
FEWER
HYDROGENS.
4.8
THE
EFFECT
OF
CONJUGATION
.
4.9
M2HG
+
AND
M2H6
.
4.10
CLASSICAL
MN
H
M
SPECIES
.
4.11
LARGER
SYSTEMS:
ARE
THEY
CLASSICAL?
.
A)
THE
ISOLOBAL
ANALOGY
.
B)
RINGS
AND
CAGES:
"STRAIN"
AND
GROUP
14
.
C)
BOND-STRETCH
ISOMERISM
.
K
38
8
FE
FE
FC
S
3
88S28
8
13
SSJB
S
3
4.12
SMALL
RINGS:
A
GLANCE
ON
THEORY
.
58
A)
BONDING
IN
THREE-MEMBERED
RINGS
.
58
B)
THE
DEWAR-CHATT-DUNCANSON
MODEL
.
58
4.13
PROPELLANES
.
60
4.14
THE
BENZENE
CONGENERS
AND
ISOMERS
.
63
5.
APPLICATIONS
TO
GROUP
14
METAL
CHEMISTRY
.
65
5.1
SIMPLE
H3MR
COMPOUNDS
.
65
5.2
REACTIONS
.
67
5.3
CATIONS
IN
ORGANOMETALLIC
GROUP
14
CHEMISTRY
.
68
5.4
REVERSED
BOND
POLARITY.
.
70
6.
BONDING
THEORY:
AN
EXTENSION
.
72
6.1
THE
STABILITY
OF
THE
DIVALENT
STATE
.
72
6.2
THE
OVERLAP
PROBLEM.
73
6.3
CONSEQUENCES
OF
THE
HYBRIDIZATION
TRENDS
.
76
7.
SUMMARY?
CONCLUSIONS?
OUTLOOK!
.
79
8.
REFERENCES
.
81
II.
CH3+
IS
THE
MOST
TRIVIAL
CARBOCATION,
BUT
ARE
ITS
HEAVIER
CONGENERS
JUST
LOOKALIKES?
.
98
1.
INTRODUCTION
.
98
2.
COMPUTATIONAL
DETAILS
.
99
3.
RESULTS
AND
DISCUSSION.
101
3.1
STATIONARY
POINTS
.
101
3.2
DIFFERENCES
IN
CARBON
VS.
THE
METALS
.
103
3.3
RELATIVE
ENERGIES
.
104
3.4
ELECTRONIC
STRUCTURE
.
105
3.5
ALTERNATIVE
DISSOCIATION
MECHANISMS
.
107
4.
SUMMARY
AND
CONCLUSIONS
.
107
5.
REFERENCES
.
109
III.
THE
SQUARE
PLANAR
STRUCTURE
OF
METHANE'S
HEAVIER
CONGENERS
IS
THE
INVERSION
TRANSITION
STATE
-
BUT
IT
CAN
NOT
BE
PASSED!
.
113
1.
INTRODUCTION
.
113
2.
METHODS
.
115
3.
RESULTS
AND
DISCUSSION.
117
3.1
THE
GEH4
PES
.
117
3.2
SIHI
-
COMPARISON
WITH
THE
GEH*
PES
.
123
3.3SNH4
.
123
3.4
IGNORING
RELATIVISTIC
AND
SOC
EFFECTS:
THE
PBHI
LIMIT
.
125
3.5
RELATIVISTIC
EFFECTS
AND
PBH4
.
126
3.6
MH4
COMPARISONS
.
127
4.
CONCLUSIONS
.
127
5.
REFERENCES
.
129
IV.
GROUP
14
ANALOGS
OF
THE
CYCLOPROPENIUM
ION
-
DO
THEY
FAVOR
CLASSICAL
AROMATIC
STRUCTURES?
.
132
REFERENCES
.
138
V.
H2XO
AND
(CH
3
)2XO
COMPOUNDS
(X
=
C,
SI,
GE,
SN,
PB):
DOUBLE
BONDS
VS.
CARBENE-LIKE
STRUCTURES
-
CAN
THE
METAL
COMPOUNDS
EXIST
AT
ALL?
.
140
1.
INTRODUCTION
.
140
2.
COMPUTATIONAL
DETAILS
.
142
3.
RESULTS
AND
DISCUSSION.
143
3.1
RELATIVE
ENERGIES
.
143
3.2
STABILITIES
.
145
3.3
GEOMETRIES.
148
3.4
ELECTRONIC
STRUCTURES
.
148
4.
CONCLUSIONS
.
153
5.
SUPPLEMETARY
MATERIAL
.
154
6.
REFERENCES
.
156
VI.
FROM
ANOMERIC
TO
RELATIVISTIC
EFFECTS
-
STARTLING
DIFFERENCES
OF
GROUP
14
MH3
SUBSTITUENTS
ON
OXYGEN,
NITROGEN,
AND
PHOSPHORUS
.
161
1.
INTRODUCTION
.
161
2.
COMPUTATIONAL
DETAILS
.
162
3.
RESULTS
AND
DISCUSSION.
165
3.1
THE
BARRIERS
.
165
3.2
THE
ZIGZAG
COURSE
.
166
3,3
HYPERCONJUGATION
.
170
3.4
INTERMOLECULAR
EFFECTS
.
172
3.5
RELATIVISTIC
EFFECTS
IN
THE
LEAD
COMPOUNDS
.
172
3.
CONCLUSIONS
.
173
4.
REFERENCES
.
175
VH.
HYPERMETALLATION
IS
UBIQUITOUS:
MXG
MOLECULES
(M
=
C
-
PB,
X
=
LI-K)
.
179
VARIATION
OF
THE
CENTRAL
ATOM
.
181
VARIATION
OF
THE
LIGAND
.
182
REFERENCES
.
184
VM.
M(CN 2
SPECIES
(M
=
BE,
MG,
CA,
SR,
BA)
-
CYANIDES,
NITRILES,
OR
NEITHER?
.
186
1.
INTRODUCTION
.
186
2.
COMPUTATIONAL
DETAILS
.
187
3.
RESULTS
.
188
3.1
BAC2N2
AND
S1C2N2
.
188
3.2
CAC2N2
AND
MGC2N2
.
190
3.3BEC2N
2
.
192
4.
DISCUSSION
.
194
5.
CONCLUSIONS
.
197
6.
REFERENCES
.
198
DC
HEAVY
ELEMENT
IT
DONATION
IS
NOT
LESS
EFFECTIVE
.
200
REFERENCES
.
208
X.
METHYL
CATIONS
WITH
LITHIUM
THROUGH
IODINE
MAIN
GROUP
SUBSTITUENTS
-
STRUCTURES,
STABILIZATION
ENERGIES,
AND
ISOMERS
.
210
1.
INTRODUCTION
.
210
2.
COMPUTATIONAL
DETAILS
.
211
3.
RESULTS
.
211
§
S9OS
199
,999IL
S
M
H
4.
DISCUSSION
.
4.1
SUBSTITUENT
STABILIZATION
ENERGIES
.
A)
O
DONORS
.
B)
HYPERCONJUGATION
.
C)
"LONE
PAIR"
SUBSTITUENTS
(GROUPS
15-17)
.
D)
REARRANGED
AND
BRIDGED
STRUCTURES
.
4.2
GEOMETRIES.
4.3
BONDING
.
A)
O
DONORS
.
B)
GROUP
1
AND
2
COMPOUNDS:
CARBENE
-
METAL
(
COMPLEXES
.
C)
HYPERCONJUGATION
.
D)
(SEMI-)BRIDGED
COMPOUNDS
.
E)
HYDRIDE
TRANSFER
.
5.
ADDITIONAL
OBSERVATIONS
WITHIN
SOME
GROUPS
.
A)
BEH
TROUGH
SRH
.
B)
BH2
THROUGH
I11H2
.
C)
CH3
THROUGH
S11H3
.
6.
SUMMARY
AND
CONCLUSIONS
.
7.
REFERENCES
.
XI.
ZUSAMMENFASSUNG:
DIE
CHEMIE
DER
SCHWEREN
ELEMENTE
-
EIN
VERGLEICH
.
244 |
| any_adam_object | 1 |
| author | Kapp, Jürgen 1967- |
| author_GND | (DE-588)115406611 |
| author_facet | Kapp, Jürgen 1967- |
| author_role | aut |
| author_sort | Kapp, Jürgen 1967- |
| author_variant | j k jk |
| building | Verbundindex |
| bvnumber | BV011105539 |
| classification_rvk | VC 6100 VH 7900 |
| ctrlnum | (OCoLC)258513390 (DE-599)BVBBV011105539 |
| discipline | Chemie / Pharmazie |
| format | Thesis Book |
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| owner_facet | DE-29 DE-29T DE-12 DE-703 DE-83 DE-188 DE-355 DE-BY-UBR |
| physical | VIII, 253 S. graph. Darst. |
| publishDate | 1996 |
| publishDateSearch | 1996 |
| publishDateSort | 1996 |
| record_format | marc |
| spelling | Kapp, Jürgen 1967- Verfasser (DE-588)115406611 aut The chemistry of heavy elements a comparison vorgelegt von Jürgen Kapp 1996 VIII, 253 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Erlangen-Nürnberg, Univ., Diss., 1996 Dichtefunktionalformalismus (DE-588)4258514-4 gnd rswk-swf Kohlenstoffgruppe (DE-588)4258859-5 gnd rswk-swf Schwermetallverbindungen (DE-588)4385735-8 gnd rswk-swf Chemische Bindung (DE-588)4009843-6 gnd rswk-swf Schwerer Atomkern (DE-588)4381820-1 gnd rswk-swf Ab-initio-Rechnung (DE-588)4141062-2 gnd rswk-swf Computational chemistry (DE-588)4290091-8 gnd rswk-swf Relativistische Korrektur (DE-588)4310201-3 gnd rswk-swf (DE-588)4113937-9 Hochschulschrift gnd-content Schwermetallverbindungen (DE-588)4385735-8 s Computational chemistry (DE-588)4290091-8 s DE-604 Kohlenstoffgruppe (DE-588)4258859-5 s Schwerer Atomkern (DE-588)4381820-1 s Chemische Bindung (DE-588)4009843-6 s Dichtefunktionalformalismus (DE-588)4258514-4 s Ab-initio-Rechnung (DE-588)4141062-2 s Relativistische Korrektur (DE-588)4310201-3 s DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=007440644&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Kapp, Jürgen 1967- The chemistry of heavy elements a comparison Dichtefunktionalformalismus (DE-588)4258514-4 gnd Kohlenstoffgruppe (DE-588)4258859-5 gnd Schwermetallverbindungen (DE-588)4385735-8 gnd Chemische Bindung (DE-588)4009843-6 gnd Schwerer Atomkern (DE-588)4381820-1 gnd Ab-initio-Rechnung (DE-588)4141062-2 gnd Computational chemistry (DE-588)4290091-8 gnd Relativistische Korrektur (DE-588)4310201-3 gnd |
| subject_GND | (DE-588)4258514-4 (DE-588)4258859-5 (DE-588)4385735-8 (DE-588)4009843-6 (DE-588)4381820-1 (DE-588)4141062-2 (DE-588)4290091-8 (DE-588)4310201-3 (DE-588)4113937-9 |
| title | The chemistry of heavy elements a comparison |
| title_auth | The chemistry of heavy elements a comparison |
| title_exact_search | The chemistry of heavy elements a comparison |
| title_full | The chemistry of heavy elements a comparison vorgelegt von Jürgen Kapp |
| title_fullStr | The chemistry of heavy elements a comparison vorgelegt von Jürgen Kapp |
| title_full_unstemmed | The chemistry of heavy elements a comparison vorgelegt von Jürgen Kapp |
| title_short | The chemistry of heavy elements |
| title_sort | the chemistry of heavy elements a comparison |
| title_sub | a comparison |
| topic | Dichtefunktionalformalismus (DE-588)4258514-4 gnd Kohlenstoffgruppe (DE-588)4258859-5 gnd Schwermetallverbindungen (DE-588)4385735-8 gnd Chemische Bindung (DE-588)4009843-6 gnd Schwerer Atomkern (DE-588)4381820-1 gnd Ab-initio-Rechnung (DE-588)4141062-2 gnd Computational chemistry (DE-588)4290091-8 gnd Relativistische Korrektur (DE-588)4310201-3 gnd |
| topic_facet | Dichtefunktionalformalismus Kohlenstoffgruppe Schwermetallverbindungen Chemische Bindung Schwerer Atomkern Ab-initio-Rechnung Computational chemistry Relativistische Korrektur Hochschulschrift |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=007440644&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT kappjurgen thechemistryofheavyelementsacomparison |