Identification and characterization of intramolecular γ-halo interaction in d0 complexes: a theoretical approach View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2017-06-24

AUTHORS

Tanay Debnath, Tamalika Ash, Subhendu Sarkar, Abhijit K. Das

ABSTRACT

A mechanistic investigation to detect intramolecular M⋯X–C type interactions in d0 neutral and cationic complexes was carried out through a benchmark study employing different density functional methods. As γ-halogen is involved in M⋯X–C type interactions, it is denoted as a γ-halo interaction and the respective conformers are designated as halo-conformers. By analyzing the geometrical parameters of halo-conformers, it was observed that, irrespective of the nature of the metal and the halogen, the Cγ–X bond distance increases compared to the usual C–X bond, which brings the M and X centers close enough to generate a weak interaction. Generation of the M⋯X–C interaction was confirmed by performing NBO, AIM and Wiberg bond index analyses, from which the persistence of γ-halo interaction was seen to be prominent. Moreover, for each neutral and cationic complex, the values of Wiberg bond order are in good agreement with the AIM results. The effect of the metal center, as well as γ-halogen substitution, on γ-halo interaction was also studied in the present work. To justify the practical subsistence of the halo-conformers, we checked the stability of the conformers with respect to their β-conformers by comparing the zero-point-corrected electronic energies. Therefore, the entire study was designed in such a way that it can provide evidence in support of intramolecular M⋯X–C interactions, where, instead of the C–H bond, the Cγ–X bond will interact with the central transition metal. More... »

PAGES

213

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/s00894-017-3387-8

DOI

http://dx.doi.org/10.1007/s00894-017-3387-8

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1086154588

PUBMED

https://www.ncbi.nlm.nih.gov/pubmed/28647872


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": "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India", 
          "id": "http://www.grid.ac/institutes/grid.417929.0", 
          "name": [
            "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Debnath", 
        "givenName": "Tanay", 
        "id": "sg:person.013616574672.33", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.013616574672.33"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India", 
          "id": "http://www.grid.ac/institutes/grid.417929.0", 
          "name": [
            "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Ash", 
        "givenName": "Tamalika", 
        "id": "sg:person.01230005433.50", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01230005433.50"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India", 
          "id": "http://www.grid.ac/institutes/grid.417929.0", 
          "name": [
            "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Sarkar", 
        "givenName": "Subhendu", 
        "id": "sg:person.010455461123.77", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.010455461123.77"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India", 
          "id": "http://www.grid.ac/institutes/grid.417929.0", 
          "name": [
            "Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Das", 
        "givenName": "Abhijit K.", 
        "id": "sg:person.01011272142.88", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01011272142.88"
        ], 
        "type": "Person"
      }
    ], 
    "citation": [
      {
        "id": "sg:pub.10.1007/s00214-015-1755-y", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1027528857", 
          "https://doi.org/10.1007/s00214-015-1755-y"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/s00214-007-0310-x", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1024437999", 
          "https://doi.org/10.1007/s00214-007-0310-x"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/s002140050249", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1051150138", 
          "https://doi.org/10.1007/s002140050249"
        ], 
        "type": "CreativeWork"
      }
    ], 
    "datePublished": "2017-06-24", 
    "datePublishedReg": "2017-06-24", 
    "description": "A mechanistic investigation to detect intramolecular M\u22efX\u2013C type interactions in d0 neutral and cationic complexes was carried out through a benchmark study employing different density functional methods. As \u03b3-halogen is involved in M\u22efX\u2013C type interactions, it is denoted as a \u03b3-halo interaction and the respective conformers are designated as halo-conformers. By analyzing the geometrical parameters of halo-conformers, it was observed that, irrespective of the nature of the metal and the halogen, the C\u03b3\u2013X bond distance increases compared to the usual C\u2013X bond, which brings the M and X centers close enough to generate a weak interaction. Generation of the M\u22efX\u2013C interaction was confirmed by performing NBO, AIM and Wiberg bond index analyses, from which the persistence of \u03b3-halo interaction was seen to be prominent. Moreover, for each neutral and cationic complex, the values of Wiberg bond order are in good agreement with the AIM results. The effect of the metal center, as well as \u03b3-halogen substitution, on \u03b3-halo interaction was also studied in the present work. To justify the practical subsistence of the halo-conformers, we checked the stability of the conformers with respect to their \u03b2-conformers by comparing the zero-point-corrected electronic energies. Therefore, the entire study was designed in such a way that it can provide evidence in support of intramolecular M\u22efX\u2013C interactions, where, instead of the C\u2013H bond, the C\u03b3\u2013X bond will interact with the central transition metal.", 
    "genre": "article", 
    "id": "sg:pub.10.1007/s00894-017-3387-8", 
    "inLanguage": "en", 
    "isAccessibleForFree": false, 
    "isPartOf": [
      {
        "id": "sg:journal.1118122", 
        "issn": [
          "1610-2940", 
          "0948-5023"
        ], 
        "name": "Journal of Molecular Modeling", 
        "publisher": "Springer Nature", 
        "type": "Periodical"
      }, 
      {
        "issueNumber": "7", 
        "type": "PublicationIssue"
      }, 
      {
        "type": "PublicationVolume", 
        "volumeNumber": "23"
      }
    ], 
    "keywords": [
      "cationic complexes", 
      "Wiberg bond index analysis", 
      "Wiberg bond orders", 
      "central transition metal", 
      "bond distance increases", 
      "different density functional methods", 
      "density functional method", 
      "metal center", 
      "type interaction", 
      "bond order", 
      "transition metals", 
      "d0 complexes", 
      "respective conformers", 
      "AIM results", 
      "Mechanistic investigations", 
      "bonds", 
      "weak interactions", 
      "halogen substitution", 
      "conformers", 
      "electronic energy", 
      "complexes", 
      "functional method", 
      "halogen", 
      "metals", 
      "NBO", 
      "present work", 
      "interaction", 
      "geometrical parameters", 
      "theoretical approach", 
      "C\u03b3", 
      "good agreement", 
      "index analysis", 
      "stability", 
      "characterization", 
      "distance increases", 
      "substitution", 
      "energy", 
      "benchmark study", 
      "investigation", 
      "nature", 
      "method", 
      "center", 
      "agreement", 
      "work", 
      "D0", 
      "study", 
      "parameters", 
      "generation", 
      "order", 
      "increase", 
      "analysis", 
      "values", 
      "effect", 
      "respect", 
      "results", 
      "support", 
      "identification", 
      "approach", 
      "way", 
      "aim", 
      "entire study", 
      "evidence", 
      "persistence", 
      "subsistence", 
      "halo interaction", 
      "halo-conformers", 
      "bond index analyses", 
      "practical subsistence", 
      "zero-point-corrected electronic energies"
    ], 
    "name": "Identification and characterization of intramolecular \u03b3-halo interaction in d0 complexes: a theoretical approach", 
    "pagination": "213", 
    "productId": [
      {
        "name": "dimensions_id", 
        "type": "PropertyValue", 
        "value": [
          "pub.1086154588"
        ]
      }, 
      {
        "name": "doi", 
        "type": "PropertyValue", 
        "value": [
          "10.1007/s00894-017-3387-8"
        ]
      }, 
      {
        "name": "pubmed_id", 
        "type": "PropertyValue", 
        "value": [
          "28647872"
        ]
      }
    ], 
    "sameAs": [
      "https://doi.org/10.1007/s00894-017-3387-8", 
      "https://app.dimensions.ai/details/publication/pub.1086154588"
    ], 
    "sdDataset": "articles", 
    "sdDatePublished": "2021-12-01T19:38", 
    "sdLicense": "https://scigraph.springernature.com/explorer/license/", 
    "sdPublisher": {
      "name": "Springer Nature - SN SciGraph project", 
      "type": "Organization"
    }, 
    "sdSource": "s3://com-springernature-scigraph/baseset/20211201/entities/gbq_results/article/article_734.jsonl", 
    "type": "ScholarlyArticle", 
    "url": "https://doi.org/10.1007/s00894-017-3387-8"
  }
]
 

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/s00894-017-3387-8'

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/s00894-017-3387-8'

Turtle is a human-readable linked data format.

curl -H 'Accept: text/turtle' 'https://scigraph.springernature.com/pub.10.1007/s00894-017-3387-8'

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

curl -H 'Accept: application/rdf+xml' 'https://scigraph.springernature.com/pub.10.1007/s00894-017-3387-8'


 

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

164 TRIPLES      22 PREDICATES      98 URIs      87 LITERALS      7 BLANK NODES

Subject Predicate Object
1 sg:pub.10.1007/s00894-017-3387-8 schema:about anzsrc-for:03
2 anzsrc-for:0302
3 schema:author N7fcc9e706d3845a699b2f7c312bdeff7
4 schema:citation sg:pub.10.1007/s00214-007-0310-x
5 sg:pub.10.1007/s00214-015-1755-y
6 sg:pub.10.1007/s002140050249
7 schema:datePublished 2017-06-24
8 schema:datePublishedReg 2017-06-24
9 schema:description A mechanistic investigation to detect intramolecular M⋯X–C type interactions in d0 neutral and cationic complexes was carried out through a benchmark study employing different density functional methods. As γ-halogen is involved in M⋯X–C type interactions, it is denoted as a γ-halo interaction and the respective conformers are designated as halo-conformers. By analyzing the geometrical parameters of halo-conformers, it was observed that, irrespective of the nature of the metal and the halogen, the Cγ–X bond distance increases compared to the usual C–X bond, which brings the M and X centers close enough to generate a weak interaction. Generation of the M⋯X–C interaction was confirmed by performing NBO, AIM and Wiberg bond index analyses, from which the persistence of γ-halo interaction was seen to be prominent. Moreover, for each neutral and cationic complex, the values of Wiberg bond order are in good agreement with the AIM results. The effect of the metal center, as well as γ-halogen substitution, on γ-halo interaction was also studied in the present work. To justify the practical subsistence of the halo-conformers, we checked the stability of the conformers with respect to their β-conformers by comparing the zero-point-corrected electronic energies. Therefore, the entire study was designed in such a way that it can provide evidence in support of intramolecular M⋯X–C interactions, where, instead of the C–H bond, the Cγ–X bond will interact with the central transition metal.
10 schema:genre article
11 schema:inLanguage en
12 schema:isAccessibleForFree false
13 schema:isPartOf N312bf195df3b41cca59b214118d22271
14 Nce6e4c33248e4dde9864f45076cebd1e
15 sg:journal.1118122
16 schema:keywords AIM results
17
18 D0
19 Mechanistic investigations
20 NBO
21 Wiberg bond index analysis
22 Wiberg bond orders
23 agreement
24 aim
25 analysis
26 approach
27 benchmark study
28 bond distance increases
29 bond index analyses
30 bond order
31 bonds
32 cationic complexes
33 center
34 central transition metal
35 characterization
36 complexes
37 conformers
38 d0 complexes
39 density functional method
40 different density functional methods
41 distance increases
42 effect
43 electronic energy
44 energy
45 entire study
46 evidence
47 functional method
48 generation
49 geometrical parameters
50 good agreement
51 halo interaction
52 halo-conformers
53 halogen
54 halogen substitution
55 identification
56 increase
57 index analysis
58 interaction
59 investigation
60 metal center
61 metals
62 method
63 nature
64 order
65 parameters
66 persistence
67 practical subsistence
68 present work
69 respect
70 respective conformers
71 results
72 stability
73 study
74 subsistence
75 substitution
76 support
77 theoretical approach
78 transition metals
79 type interaction
80 values
81 way
82 weak interactions
83 work
84 zero-point-corrected electronic energies
85 schema:name Identification and characterization of intramolecular γ-halo interaction in d0 complexes: a theoretical approach
86 schema:pagination 213
87 schema:productId N6a72008c988e4e9699af4351acfccbdf
88 Na39140b73b42468e9b8886b4a88cc82f
89 Nfa98f51300e044d79e6d9bfc6cd45e2e
90 schema:sameAs https://app.dimensions.ai/details/publication/pub.1086154588
91 https://doi.org/10.1007/s00894-017-3387-8
92 schema:sdDatePublished 2021-12-01T19:38
93 schema:sdLicense https://scigraph.springernature.com/explorer/license/
94 schema:sdPublisher N2c2dcde112554d70a3c34adcd9410956
95 schema:url https://doi.org/10.1007/s00894-017-3387-8
96 sgo:license sg:explorer/license/
97 sgo:sdDataset articles
98 rdf:type schema:ScholarlyArticle
99 N2c2dcde112554d70a3c34adcd9410956 schema:name Springer Nature - SN SciGraph project
100 rdf:type schema:Organization
101 N312bf195df3b41cca59b214118d22271 schema:issueNumber 7
102 rdf:type schema:PublicationIssue
103 N6a72008c988e4e9699af4351acfccbdf schema:name pubmed_id
104 schema:value 28647872
105 rdf:type schema:PropertyValue
106 N7fcc9e706d3845a699b2f7c312bdeff7 rdf:first sg:person.013616574672.33
107 rdf:rest Nafebe18dfadb44fab90f1e317bc08fa1
108 Na39140b73b42468e9b8886b4a88cc82f schema:name doi
109 schema:value 10.1007/s00894-017-3387-8
110 rdf:type schema:PropertyValue
111 Nafebe18dfadb44fab90f1e317bc08fa1 rdf:first sg:person.01230005433.50
112 rdf:rest Ne33fc022609746a5955a37e89d957cd2
113 Nc6e96a58af914f5185019d3ecefb0861 rdf:first sg:person.01011272142.88
114 rdf:rest rdf:nil
115 Nce6e4c33248e4dde9864f45076cebd1e schema:volumeNumber 23
116 rdf:type schema:PublicationVolume
117 Ne33fc022609746a5955a37e89d957cd2 rdf:first sg:person.010455461123.77
118 rdf:rest Nc6e96a58af914f5185019d3ecefb0861
119 Nfa98f51300e044d79e6d9bfc6cd45e2e schema:name dimensions_id
120 schema:value pub.1086154588
121 rdf:type schema:PropertyValue
122 anzsrc-for:03 schema:inDefinedTermSet anzsrc-for:
123 schema:name Chemical Sciences
124 rdf:type schema:DefinedTerm
125 anzsrc-for:0302 schema:inDefinedTermSet anzsrc-for:
126 schema:name Inorganic Chemistry
127 rdf:type schema:DefinedTerm
128 sg:journal.1118122 schema:issn 0948-5023
129 1610-2940
130 schema:name Journal of Molecular Modeling
131 schema:publisher Springer Nature
132 rdf:type schema:Periodical
133 sg:person.01011272142.88 schema:affiliation grid-institutes:grid.417929.0
134 schema:familyName Das
135 schema:givenName Abhijit K.
136 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01011272142.88
137 rdf:type schema:Person
138 sg:person.010455461123.77 schema:affiliation grid-institutes:grid.417929.0
139 schema:familyName Sarkar
140 schema:givenName Subhendu
141 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.010455461123.77
142 rdf:type schema:Person
143 sg:person.01230005433.50 schema:affiliation grid-institutes:grid.417929.0
144 schema:familyName Ash
145 schema:givenName Tamalika
146 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01230005433.50
147 rdf:type schema:Person
148 sg:person.013616574672.33 schema:affiliation grid-institutes:grid.417929.0
149 schema:familyName Debnath
150 schema:givenName Tanay
151 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.013616574672.33
152 rdf:type schema:Person
153 sg:pub.10.1007/s00214-007-0310-x schema:sameAs https://app.dimensions.ai/details/publication/pub.1024437999
154 https://doi.org/10.1007/s00214-007-0310-x
155 rdf:type schema:CreativeWork
156 sg:pub.10.1007/s00214-015-1755-y schema:sameAs https://app.dimensions.ai/details/publication/pub.1027528857
157 https://doi.org/10.1007/s00214-015-1755-y
158 rdf:type schema:CreativeWork
159 sg:pub.10.1007/s002140050249 schema:sameAs https://app.dimensions.ai/details/publication/pub.1051150138
160 https://doi.org/10.1007/s002140050249
161 rdf:type schema:CreativeWork
162 grid-institutes:grid.417929.0 schema:alternateName Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India
163 schema:name Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, 700032, Kolkata, India
164 rdf:type schema:Organization
 




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


...