Stabilization of diazene in Fe(II)–sulfur model complexes relevant for nitrogenase activity. I. A new approach to the evaluation of intramolecular ... View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2001-11

AUTHORS

Markus Reiher, Dieter Sellmann, Bernd Artur Hess

ABSTRACT

. A key step in the biological nitrogen fixation problem is the transfer of protons and electrons onto inert molecular nitrogen. A first intermediate will then be diazene (diimide), N2H2, which is thermodynamically unstable with respect to dissociation into N2 and H2 in the gas phase. Thus, diazene must be stabilized such that the reduction of a complex binding an activated nitrogen becomes energetically feasible. A considerable contribution to this stabilization has been attributed to hydrogen bonds of the type N–H···S. We investigate the strength of these hydrogen bonds in two model compounds. Since the contribution of an intramolecular hydrogen bridge to the total binding energy of a molecule is not a well-defined concept, it is necessary to define a suitable descriptor for this quantity. We present a new approach of estimating hydrogen-bond energies from two-center shared-electron numbers obtained from density functional calculations. Our approach is particularly designed for highly complex systems such as transition-metal complexes with large coordination spheres. More... »

PAGES

379-392

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/s002140100287

DOI

http://dx.doi.org/10.1007/s002140100287

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1023352617


Indexing Status Check whether this publication has been indexed by Scopus and Web Of Science using the SN Indexing Status Tool
Incoming Citations Browse incoming citations for this publication using opencitations.net

JSON-LD is the canonical representation for SciGraph data.

TIP: You can open this SciGraph record using an external JSON-LD service: JSON-LD Playground Google SDTT

[
  {
    "@context": "https://springernature.github.io/scigraph/jsonld/sgcontext.json", 
    "about": [
      {
        "id": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/03", 
        "inDefinedTermSet": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/", 
        "name": "Chemical Sciences", 
        "type": "DefinedTerm"
      }, 
      {
        "id": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/0302", 
        "inDefinedTermSet": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/", 
        "name": "Inorganic Chemistry", 
        "type": "DefinedTerm"
      }
    ], 
    "author": [
      {
        "affiliation": {
          "alternateName": "Lehrstuhl f\u00fcr Theoretische Chemie, Universit\u00e4t Erlangen-N\u00fcrnberg, Egerlandstrasse 3, 91058 Erlangen, Germany, DE", 
          "id": "http://www.grid.ac/institutes/grid.5330.5", 
          "name": [
            "Lehrstuhl f\u00fcr Theoretische Chemie, Universit\u00e4t Erlangen-N\u00fcrnberg, Egerlandstrasse 3, 91058 Erlangen, Germany, DE"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Reiher", 
        "givenName": "Markus", 
        "id": "sg:person.01265561117.03", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01265561117.03"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Lehrstuhl f\u00fcr Anorganische und Allgemeine Chemie, Universit\u00e4t Erlangen-N\u00fcrnberg, Egerlandstrasse 1, 91058 Erlangen, Germany, DE", 
          "id": "http://www.grid.ac/institutes/grid.5330.5", 
          "name": [
            "Lehrstuhl f\u00fcr Anorganische und Allgemeine Chemie, Universit\u00e4t Erlangen-N\u00fcrnberg, Egerlandstrasse 1, 91058 Erlangen, Germany, DE"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Sellmann", 
        "givenName": "Dieter", 
        "id": "sg:person.0656560346.48", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.0656560346.48"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Lehrstuhl f\u00fcr Theoretische Chemie, Universit\u00e4t Erlangen-N\u00fcrnberg, Egerlandstrasse 3, 91058 Erlangen, Germany, DE", 
          "id": "http://www.grid.ac/institutes/grid.5330.5", 
          "name": [
            "Lehrstuhl f\u00fcr Theoretische Chemie, Universit\u00e4t Erlangen-N\u00fcrnberg, Egerlandstrasse 3, 91058 Erlangen, Germany, DE"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Hess", 
        "givenName": "Bernd Artur", 
        "id": "sg:person.0715672344.54", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.0715672344.54"
        ], 
        "type": "Person"
      }
    ], 
    "datePublished": "2001-11", 
    "datePublishedReg": "2001-11-01", 
    "description": "Abstract. A key step in the biological nitrogen fixation problem is the transfer of protons and electrons onto inert molecular nitrogen. A first intermediate will then be diazene (diimide), N2H2, which is thermodynamically unstable with respect to dissociation into N2 and H2 in the gas phase. Thus, diazene must be stabilized such that the reduction of a complex binding an activated nitrogen becomes energetically feasible. A considerable contribution to this stabilization has been attributed to hydrogen bonds of the type N\u2013H\u00b7\u00b7\u00b7S. We investigate the strength of these hydrogen bonds in two model compounds. Since the contribution of an intramolecular hydrogen bridge to the total binding energy of a molecule is not a well-defined concept, it is necessary to define a suitable descriptor for this quantity. We present a new approach of estimating hydrogen-bond energies from two-center shared-electron numbers obtained from density functional calculations. Our approach is particularly designed for highly complex systems such as transition-metal complexes with large coordination spheres.", 
    "genre": "article", 
    "id": "sg:pub.10.1007/s002140100287", 
    "inLanguage": "en", 
    "isAccessibleForFree": false, 
    "isPartOf": [
      {
        "id": "sg:journal.1134081", 
        "issn": [
          "1432-881X", 
          "1432-2234"
        ], 
        "name": "Theoretical Chemistry Accounts", 
        "publisher": "Springer Nature", 
        "type": "Periodical"
      }, 
      {
        "issueNumber": "6", 
        "type": "PublicationIssue"
      }, 
      {
        "type": "PublicationVolume", 
        "volumeNumber": "106"
      }
    ], 
    "keywords": [
      "hydrogen bond energy", 
      "hydrogen bonds", 
      "intramolecular hydrogen bond energy", 
      "transition metal complexes", 
      "intramolecular hydrogen bridge", 
      "transfer of protons", 
      "density functional calculations", 
      "coordination sphere", 
      "model complexes", 
      "hydrogen bridges", 
      "model compounds", 
      "bond energy", 
      "gas phase", 
      "activated nitrogen", 
      "functional calculations", 
      "diazene", 
      "molecular nitrogen", 
      "first intermediate", 
      "bonds", 
      "key step", 
      "type N", 
      "suitable descriptors", 
      "complexes", 
      "N2H2", 
      "nitrogen", 
      "intermediates", 
      "compounds", 
      "molecules", 
      "energy", 
      "protons", 
      "H2", 
      "dissociation", 
      "stabilization", 
      "N2", 
      "considerable contribution", 
      "electrons", 
      "calculations", 
      "new approach", 
      "transfer", 
      "bridge", 
      "phase", 
      "descriptors", 
      "sphere", 
      "step", 
      "complex systems", 
      "activity", 
      "reduction", 
      "strength", 
      "contribution", 
      "quantity", 
      "approach", 
      "fixation problems", 
      "respect", 
      "system", 
      "evaluation", 
      "nitrogenase activity", 
      "number", 
      "concept", 
      "problem"
    ], 
    "name": "Stabilization of diazene in Fe(II)\u2013sulfur model complexes relevant for nitrogenase activity. I. A new approach to the evaluation of intramolecular hydrogen bond energies", 
    "pagination": "379-392", 
    "productId": [
      {
        "name": "dimensions_id", 
        "type": "PropertyValue", 
        "value": [
          "pub.1023352617"
        ]
      }, 
      {
        "name": "doi", 
        "type": "PropertyValue", 
        "value": [
          "10.1007/s002140100287"
        ]
      }
    ], 
    "sameAs": [
      "https://doi.org/10.1007/s002140100287", 
      "https://app.dimensions.ai/details/publication/pub.1023352617"
    ], 
    "sdDataset": "articles", 
    "sdDatePublished": "2022-06-01T22:03", 
    "sdLicense": "https://scigraph.springernature.com/explorer/license/", 
    "sdPublisher": {
      "name": "Springer Nature - SN SciGraph project", 
      "type": "Organization"
    }, 
    "sdSource": "s3://com-springernature-scigraph/baseset/20220601/entities/gbq_results/article/article_311.jsonl", 
    "type": "ScholarlyArticle", 
    "url": "https://doi.org/10.1007/s002140100287"
  }
]
 

Download the RDF metadata as:  json-ld nt turtle xml License info

HOW TO GET THIS DATA PROGRAMMATICALLY:

JSON-LD is a popular format for linked data which is fully compatible with JSON.

curl -H 'Accept: application/ld+json' 'https://scigraph.springernature.com/pub.10.1007/s002140100287'

N-Triples is a line-based linked data format ideal for batch operations.

curl -H 'Accept: application/n-triples' 'https://scigraph.springernature.com/pub.10.1007/s002140100287'

Turtle is a human-readable linked data format.

curl -H 'Accept: text/turtle' 'https://scigraph.springernature.com/pub.10.1007/s002140100287'

RDF/XML is a standard XML format for linked data.

curl -H 'Accept: application/rdf+xml' 'https://scigraph.springernature.com/pub.10.1007/s002140100287'


 

This table displays all metadata directly associated to this object as RDF triples.

133 TRIPLES      21 PREDICATES      85 URIs      77 LITERALS      6 BLANK NODES

Subject Predicate Object
1 sg:pub.10.1007/s002140100287 schema:about anzsrc-for:03
2 anzsrc-for:0302
3 schema:author N77d6eeb51df24fe78828fea50f7b0274
4 schema:datePublished 2001-11
5 schema:datePublishedReg 2001-11-01
6 schema:description Abstract. A key step in the biological nitrogen fixation problem is the transfer of protons and electrons onto inert molecular nitrogen. A first intermediate will then be diazene (diimide), N2H2, which is thermodynamically unstable with respect to dissociation into N2 and H2 in the gas phase. Thus, diazene must be stabilized such that the reduction of a complex binding an activated nitrogen becomes energetically feasible. A considerable contribution to this stabilization has been attributed to hydrogen bonds of the type N–H···S. We investigate the strength of these hydrogen bonds in two model compounds. Since the contribution of an intramolecular hydrogen bridge to the total binding energy of a molecule is not a well-defined concept, it is necessary to define a suitable descriptor for this quantity. We present a new approach of estimating hydrogen-bond energies from two-center shared-electron numbers obtained from density functional calculations. Our approach is particularly designed for highly complex systems such as transition-metal complexes with large coordination spheres.
7 schema:genre article
8 schema:inLanguage en
9 schema:isAccessibleForFree false
10 schema:isPartOf N29c1cad18de74d97862bbdda66af7ff1
11 N4df172a1e13f46c88e472c29026e9ec5
12 sg:journal.1134081
13 schema:keywords H2
14 N2
15 N2H2
16 activated nitrogen
17 activity
18 approach
19 bond energy
20 bonds
21 bridge
22 calculations
23 complex systems
24 complexes
25 compounds
26 concept
27 considerable contribution
28 contribution
29 coordination sphere
30 density functional calculations
31 descriptors
32 diazene
33 dissociation
34 electrons
35 energy
36 evaluation
37 first intermediate
38 fixation problems
39 functional calculations
40 gas phase
41 hydrogen bond energy
42 hydrogen bonds
43 hydrogen bridges
44 intermediates
45 intramolecular hydrogen bond energy
46 intramolecular hydrogen bridge
47 key step
48 model complexes
49 model compounds
50 molecular nitrogen
51 molecules
52 new approach
53 nitrogen
54 nitrogenase activity
55 number
56 phase
57 problem
58 protons
59 quantity
60 reduction
61 respect
62 sphere
63 stabilization
64 step
65 strength
66 suitable descriptors
67 system
68 transfer
69 transfer of protons
70 transition metal complexes
71 type N
72 schema:name Stabilization of diazene in Fe(II)–sulfur model complexes relevant for nitrogenase activity. I. A new approach to the evaluation of intramolecular hydrogen bond energies
73 schema:pagination 379-392
74 schema:productId N8991d7d3c4624ac28fbb10372837a33b
75 Ned6c68938e614d949bdf08552420483d
76 schema:sameAs https://app.dimensions.ai/details/publication/pub.1023352617
77 https://doi.org/10.1007/s002140100287
78 schema:sdDatePublished 2022-06-01T22:03
79 schema:sdLicense https://scigraph.springernature.com/explorer/license/
80 schema:sdPublisher N8fe9f329c3084911b855d01ba942db75
81 schema:url https://doi.org/10.1007/s002140100287
82 sgo:license sg:explorer/license/
83 sgo:sdDataset articles
84 rdf:type schema:ScholarlyArticle
85 N29c1cad18de74d97862bbdda66af7ff1 schema:issueNumber 6
86 rdf:type schema:PublicationIssue
87 N4df172a1e13f46c88e472c29026e9ec5 schema:volumeNumber 106
88 rdf:type schema:PublicationVolume
89 N65b81070fc2b422cb6e1a67a35ee36bd rdf:first sg:person.0656560346.48
90 rdf:rest Ncf73d2dedd424ef0aeb3fa5a178dc977
91 N77d6eeb51df24fe78828fea50f7b0274 rdf:first sg:person.01265561117.03
92 rdf:rest N65b81070fc2b422cb6e1a67a35ee36bd
93 N8991d7d3c4624ac28fbb10372837a33b schema:name doi
94 schema:value 10.1007/s002140100287
95 rdf:type schema:PropertyValue
96 N8fe9f329c3084911b855d01ba942db75 schema:name Springer Nature - SN SciGraph project
97 rdf:type schema:Organization
98 Ncf73d2dedd424ef0aeb3fa5a178dc977 rdf:first sg:person.0715672344.54
99 rdf:rest rdf:nil
100 Ned6c68938e614d949bdf08552420483d schema:name dimensions_id
101 schema:value pub.1023352617
102 rdf:type schema:PropertyValue
103 anzsrc-for:03 schema:inDefinedTermSet anzsrc-for:
104 schema:name Chemical Sciences
105 rdf:type schema:DefinedTerm
106 anzsrc-for:0302 schema:inDefinedTermSet anzsrc-for:
107 schema:name Inorganic Chemistry
108 rdf:type schema:DefinedTerm
109 sg:journal.1134081 schema:issn 1432-2234
110 1432-881X
111 schema:name Theoretical Chemistry Accounts
112 schema:publisher Springer Nature
113 rdf:type schema:Periodical
114 sg:person.01265561117.03 schema:affiliation grid-institutes:grid.5330.5
115 schema:familyName Reiher
116 schema:givenName Markus
117 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01265561117.03
118 rdf:type schema:Person
119 sg:person.0656560346.48 schema:affiliation grid-institutes:grid.5330.5
120 schema:familyName Sellmann
121 schema:givenName Dieter
122 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.0656560346.48
123 rdf:type schema:Person
124 sg:person.0715672344.54 schema:affiliation grid-institutes:grid.5330.5
125 schema:familyName Hess
126 schema:givenName Bernd Artur
127 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.0715672344.54
128 rdf:type schema:Person
129 grid-institutes:grid.5330.5 schema:alternateName Lehrstuhl für Anorganische und Allgemeine Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany, DE
130 Lehrstuhl für Theoretische Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen, Germany, DE
131 schema:name Lehrstuhl für Anorganische und Allgemeine Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany, DE
132 Lehrstuhl für Theoretische Chemie, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen, Germany, DE
133 rdf:type schema:Organization
 




Preview window. Press ESC to close (or click here)


...