Alkyne insertion and coupling reactions of methyl propiolate with the heterometallic dimers CoRu(CO)7(μ-PPh2) and CoRu(CO)5[(Z)-Ph2PCH = CHPPh2](μ-PPh2): X-ray diffraction structures ... View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2005-03

AUTHORS

William H. Watson, Jie Liu, Michael G. Richmond

ABSTRACT

The reaction of the terminal alkyne methyl propiolate with the heterometallic dimers CoRu(CO)7(μ-PPh2) (1) and CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) (2) has been investigated at 65∘C in toluene. In the reaction of 1, chromatographic purification afforded a minor band, from which the two species RuCo(CO)4(μ-CO)[μ-PPh2C(O)CHC(CO2Me)] and RuCo(CO)4(μ-CO)[μ-PPh2CHC(CO2Me)] were observed by 1H NMR spectroscopy, and one major band, whose 1H NMR spectrum revealed the presence of multiple species. The identity of one of the compounds in the major component has been established as that of CoRu(CO)4(μ-CO)[μ-PPh2C(O)CH(CCO2Me)C(O)CHC(CO2Me)] (3) by X-ray diffraction analysis. The solid-state structure of 3 confirms the double insertion of CO and head-to-head coupling of the methyl propiolate that accompanies the formation of this product. Compound 3 crystallizes in the triclinic space group P-1, a = 8.4035(4), b = 9.6721(5), c = 17.678(1) Å, α = 94.135(2), β = 103.318(2), γ = 101.336(2)∘, V = 1360.5(1) Å3, Z = 2, Dcalc = 1.732 Mg/m3; R = 0.0300, Rw = 0.0760 for 8630 reflections with I > 2σ(I). The ruthenium-bound diphosphine ligand in 2 exerts a controlling influence on the reaction with added alkyne insomuch as only the mono-insertion product CoRu(CO)3(μ-CO)[(Z)-Ph2PCH=CHPPh2][μ-PPh2C(O)C(CO2Me)CH] (4) is formed as a single regioisomer. The molecular structure of 4 was established by X-ray diffraction analysis and 4 was found to crystallize in the monoclinic space group P21/c, a = 19.483(7), b = 11.905(4), c = 20.131(7) Å, β = 110.455(6)∘, V = 4375(3) Å3, Z = 4, Dcalc = 1.466 Mg/m3; R = 0.0961, Rw = 0.1683 for 6262 reflections with I > 2σ(I). The reactivity of methyl propiolate with 1 and 2 is compared with the known reactivity that has been reported for other alkynes. More... »

PAGES

249-258

References to SciGraph publications

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/s10870-005-2964-3

DOI

http://dx.doi.org/10.1007/s10870-005-2964-3

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1036770935


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/2008/0306", 
        "inDefinedTermSet": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/", 
        "name": "Physical Chemistry (incl. Structural)", 
        "type": "DefinedTerm"
      }, 
      {
        "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"
      }
    ], 
    "author": [
      {
        "affiliation": {
          "alternateName": "Texas Christian University", 
          "id": "https://www.grid.ac/institutes/grid.264766.7", 
          "name": [
            "Department of Chemistry, Texas Christian University, 76129, Fort Worth, Texas"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Watson", 
        "givenName": "William H.", 
        "id": "sg:person.01251243510.43", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01251243510.43"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "University of North Texas", 
          "id": "https://www.grid.ac/institutes/grid.266869.5", 
          "name": [
            "Department of Chemistry, University of North Texas, 76203, Denton, Texas"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Liu", 
        "givenName": "Jie", 
        "id": "sg:person.07627161513.96", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.07627161513.96"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "University of North Texas", 
          "id": "https://www.grid.ac/institutes/grid.266869.5", 
          "name": [
            "Department of Chemistry, University of North Texas, 76203, Denton, Texas"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Richmond", 
        "givenName": "Michael G.", 
        "id": "sg:person.014740162521.20", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.014740162521.20"
        ], 
        "type": "Person"
      }
    ], 
    "citation": [
      {
        "id": "sg:pub.10.1023/a:1026159424303", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1005657207", 
          "https://doi.org/10.1023/a:1026159424303"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1016/s0022-328x(00)00082-6", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1009643338"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/c39820001217", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1031500971"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/dt98900000s1", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1039084879"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1023/a:1016616208442", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1043883622", 
          "https://doi.org/10.1023/a:1016616208442"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1016/s0022-328x(99)00608-7", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1050747679"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ic991279r", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055590326"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ic991279r", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055590326"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/om00083a033", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1056266641"
        ], 
        "type": "CreativeWork"
      }
    ], 
    "datePublished": "2005-03", 
    "datePublishedReg": "2005-03-01", 
    "description": "The reaction of the terminal alkyne methyl propiolate with the heterometallic dimers CoRu(CO)7(\u03bc-PPh2) (1) and CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](\u03bc-PPh2) (2) has been investigated at 65\u2218C in toluene. In the reaction of 1, chromatographic purification afforded a minor band, from which the two species RuCo(CO)4(\u03bc-CO)[\u03bc-PPh2C(O)CHC(CO2Me)] and RuCo(CO)4(\u03bc-CO)[\u03bc-PPh2CHC(CO2Me)] were observed by 1H NMR spectroscopy, and one major band, whose 1H NMR spectrum revealed the presence of multiple species. The identity of one of the compounds in the major component has been established as that of CoRu(CO)4(\u03bc-CO)[\u03bc-PPh2C(O)CH(CCO2Me)C(O)CHC(CO2Me)] (3) by X-ray diffraction analysis. The solid-state structure of 3 confirms the double insertion of CO and head-to-head coupling of the methyl propiolate that accompanies the formation of this product. Compound 3 crystallizes in the triclinic space group P-1, a = 8.4035(4), b = 9.6721(5), c = 17.678(1) \u00c5, \u03b1 = 94.135(2), \u03b2 = 103.318(2), \u03b3 = 101.336(2)\u2218, V = 1360.5(1) \u00c53, Z = 2, Dcalc = 1.732 Mg/m3; R = 0.0300, Rw = 0.0760 for 8630 reflections with I > 2\u03c3(I). The ruthenium-bound diphosphine ligand in 2 exerts a controlling influence on the reaction with added alkyne insomuch as only the mono-insertion product CoRu(CO)3(\u03bc-CO)[(Z)-Ph2PCH=CHPPh2][\u03bc-PPh2C(O)C(CO2Me)CH] (4) is formed as a single regioisomer. The molecular structure of 4 was established by X-ray diffraction analysis and 4 was found to crystallize in the monoclinic space group P21/c, a = 19.483(7), b = 11.905(4), c = 20.131(7) \u00c5, \u03b2 = 110.455(6)\u2218, V = 4375(3) \u00c53, Z = 4, Dcalc = 1.466 Mg/m3; R = 0.0961, Rw = 0.1683 for 6262 reflections with I > 2\u03c3(I). The reactivity of methyl propiolate with 1 and 2 is compared with the known reactivity that has been reported for other alkynes.", 
    "genre": "research_article", 
    "id": "sg:pub.10.1007/s10870-005-2964-3", 
    "inLanguage": [
      "en"
    ], 
    "isAccessibleForFree": false, 
    "isPartOf": [
      {
        "id": "sg:journal.1093566", 
        "issn": [
          "1074-1542", 
          "1572-8854"
        ], 
        "name": "Journal of Chemical Crystallography", 
        "type": "Periodical"
      }, 
      {
        "issueNumber": "3", 
        "type": "PublicationIssue"
      }, 
      {
        "type": "PublicationVolume", 
        "volumeNumber": "35"
      }
    ], 
    "name": "Alkyne insertion and coupling reactions of methyl propiolate with the heterometallic dimers CoRu(CO)7(\u03bc-PPh2) and CoRu(CO)5[(Z)-Ph2PCH = CHPPh2](\u03bc-PPh2): X-ray diffraction structures of CoRu(CO)4(\u03bc-CO)[\u03bc-PPh2C(O)CH(CCO2Me)C(O)CHC (CO2Me)] and CoRu(CO)3(\u03bc-CO)[(Z)-Ph2PCH = CHPPh2][\u03bc-PPh2C(O)C(CO2Me)CH]", 
    "pagination": "249-258", 
    "productId": [
      {
        "name": "doi", 
        "type": "PropertyValue", 
        "value": [
          "10.1007/s10870-005-2964-3"
        ]
      }, 
      {
        "name": "readcube_id", 
        "type": "PropertyValue", 
        "value": [
          "af29d04a7bb15b8162405f5fb2ec04f72cd7562853809e03764a02fff2b076b1"
        ]
      }, 
      {
        "name": "dimensions_id", 
        "type": "PropertyValue", 
        "value": [
          "pub.1036770935"
        ]
      }
    ], 
    "sameAs": [
      "https://doi.org/10.1007/s10870-005-2964-3", 
      "https://app.dimensions.ai/details/publication/pub.1036770935"
    ], 
    "sdDataset": "articles", 
    "sdDatePublished": "2019-04-15T09:17", 
    "sdLicense": "https://scigraph.springernature.com/explorer/license/", 
    "sdPublisher": {
      "name": "Springer Nature - SN SciGraph project", 
      "type": "Organization"
    }, 
    "sdSource": "s3://com-uberresearch-data-dimensions-target-20181106-alternative/cleanup/v134/2549eaecd7973599484d7c17b260dba0a4ecb94b/merge/v9/a6c9fde33151104705d4d7ff012ea9563521a3ce/jats-lookup/v90/0000000376_0000000376/records_56173_00000001.jsonl", 
    "type": "ScholarlyArticle", 
    "url": "http://link.springer.com/10.1007/s10870-005-2964-3"
  }
]
 

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/s10870-005-2964-3'

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/s10870-005-2964-3'

Turtle is a human-readable linked data format.

curl -H 'Accept: text/turtle' 'https://scigraph.springernature.com/pub.10.1007/s10870-005-2964-3'

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

curl -H 'Accept: application/rdf+xml' 'https://scigraph.springernature.com/pub.10.1007/s10870-005-2964-3'


 

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

104 TRIPLES      21 PREDICATES      35 URIs      19 LITERALS      7 BLANK NODES

Subject Predicate Object
1 sg:pub.10.1007/s10870-005-2964-3 schema:about anzsrc-for:03
2 anzsrc-for:0306
3 schema:author N361e6a645d874399b0cb85d23c9abf87
4 schema:citation sg:pub.10.1023/a:1016616208442
5 sg:pub.10.1023/a:1026159424303
6 https://doi.org/10.1016/s0022-328x(00)00082-6
7 https://doi.org/10.1016/s0022-328x(99)00608-7
8 https://doi.org/10.1021/ic991279r
9 https://doi.org/10.1021/om00083a033
10 https://doi.org/10.1039/c39820001217
11 https://doi.org/10.1039/dt98900000s1
12 schema:datePublished 2005-03
13 schema:datePublishedReg 2005-03-01
14 schema:description The reaction of the terminal alkyne methyl propiolate with the heterometallic dimers CoRu(CO)7(μ-PPh2) (1) and CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) (2) has been investigated at 65∘C in toluene. In the reaction of 1, chromatographic purification afforded a minor band, from which the two species RuCo(CO)4(μ-CO)[μ-PPh2C(O)CHC(CO2Me)] and RuCo(CO)4(μ-CO)[μ-PPh2CHC(CO2Me)] were observed by 1H NMR spectroscopy, and one major band, whose 1H NMR spectrum revealed the presence of multiple species. The identity of one of the compounds in the major component has been established as that of CoRu(CO)4(μ-CO)[μ-PPh2C(O)CH(CCO2Me)C(O)CHC(CO2Me)] (3) by X-ray diffraction analysis. The solid-state structure of 3 confirms the double insertion of CO and head-to-head coupling of the methyl propiolate that accompanies the formation of this product. Compound 3 crystallizes in the triclinic space group P-1, a = 8.4035(4), b = 9.6721(5), c = 17.678(1) Å, α = 94.135(2), β = 103.318(2), γ = 101.336(2)∘, V = 1360.5(1) Å3, Z = 2, Dcalc = 1.732 Mg/m3; R = 0.0300, Rw = 0.0760 for 8630 reflections with I > 2σ(I). The ruthenium-bound diphosphine ligand in 2 exerts a controlling influence on the reaction with added alkyne insomuch as only the mono-insertion product CoRu(CO)3(μ-CO)[(Z)-Ph2PCH=CHPPh2][μ-PPh2C(O)C(CO2Me)CH] (4) is formed as a single regioisomer. The molecular structure of 4 was established by X-ray diffraction analysis and 4 was found to crystallize in the monoclinic space group P21/c, a = 19.483(7), b = 11.905(4), c = 20.131(7) Å, β = 110.455(6)∘, V = 4375(3) Å3, Z = 4, Dcalc = 1.466 Mg/m3; R = 0.0961, Rw = 0.1683 for 6262 reflections with I > 2σ(I). The reactivity of methyl propiolate with 1 and 2 is compared with the known reactivity that has been reported for other alkynes.
15 schema:genre research_article
16 schema:inLanguage en
17 schema:isAccessibleForFree false
18 schema:isPartOf N7050f7cb3070438784d5617647e1f4ff
19 Naa63bc0ec5f64d5ab7da2c238054364c
20 sg:journal.1093566
21 schema:name Alkyne insertion and coupling reactions of methyl propiolate with the heterometallic dimers CoRu(CO)7(μ-PPh2) and CoRu(CO)5[(Z)-Ph2PCH = CHPPh2](μ-PPh2): X-ray diffraction structures of CoRu(CO)4(μ-CO)[μ-PPh2C(O)CH(CCO2Me)C(O)CHC (CO2Me)] and CoRu(CO)3(μ-CO)[(Z)-Ph2PCH = CHPPh2][μ-PPh2C(O)C(CO2Me)CH]
22 schema:pagination 249-258
23 schema:productId N037e1ca19db24a66a8d7ac6f229126e4
24 N28b1a724f62142e4844650c275346fb9
25 N3affea21087941969eac55e7e543486a
26 schema:sameAs https://app.dimensions.ai/details/publication/pub.1036770935
27 https://doi.org/10.1007/s10870-005-2964-3
28 schema:sdDatePublished 2019-04-15T09:17
29 schema:sdLicense https://scigraph.springernature.com/explorer/license/
30 schema:sdPublisher Ncd7ff5ee702f42c797267a1e922a7e9e
31 schema:url http://link.springer.com/10.1007/s10870-005-2964-3
32 sgo:license sg:explorer/license/
33 sgo:sdDataset articles
34 rdf:type schema:ScholarlyArticle
35 N037e1ca19db24a66a8d7ac6f229126e4 schema:name doi
36 schema:value 10.1007/s10870-005-2964-3
37 rdf:type schema:PropertyValue
38 N28b1a724f62142e4844650c275346fb9 schema:name readcube_id
39 schema:value af29d04a7bb15b8162405f5fb2ec04f72cd7562853809e03764a02fff2b076b1
40 rdf:type schema:PropertyValue
41 N361e6a645d874399b0cb85d23c9abf87 rdf:first sg:person.01251243510.43
42 rdf:rest N516470053c1a48d291c619b89a96eb4e
43 N3affea21087941969eac55e7e543486a schema:name dimensions_id
44 schema:value pub.1036770935
45 rdf:type schema:PropertyValue
46 N516470053c1a48d291c619b89a96eb4e rdf:first sg:person.07627161513.96
47 rdf:rest Neeadf590838c44b58da3adbdbd752e0d
48 N7050f7cb3070438784d5617647e1f4ff schema:volumeNumber 35
49 rdf:type schema:PublicationVolume
50 Naa63bc0ec5f64d5ab7da2c238054364c schema:issueNumber 3
51 rdf:type schema:PublicationIssue
52 Ncd7ff5ee702f42c797267a1e922a7e9e schema:name Springer Nature - SN SciGraph project
53 rdf:type schema:Organization
54 Neeadf590838c44b58da3adbdbd752e0d rdf:first sg:person.014740162521.20
55 rdf:rest rdf:nil
56 anzsrc-for:03 schema:inDefinedTermSet anzsrc-for:
57 schema:name Chemical Sciences
58 rdf:type schema:DefinedTerm
59 anzsrc-for:0306 schema:inDefinedTermSet anzsrc-for:
60 schema:name Physical Chemistry (incl. Structural)
61 rdf:type schema:DefinedTerm
62 sg:journal.1093566 schema:issn 1074-1542
63 1572-8854
64 schema:name Journal of Chemical Crystallography
65 rdf:type schema:Periodical
66 sg:person.01251243510.43 schema:affiliation https://www.grid.ac/institutes/grid.264766.7
67 schema:familyName Watson
68 schema:givenName William H.
69 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01251243510.43
70 rdf:type schema:Person
71 sg:person.014740162521.20 schema:affiliation https://www.grid.ac/institutes/grid.266869.5
72 schema:familyName Richmond
73 schema:givenName Michael G.
74 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.014740162521.20
75 rdf:type schema:Person
76 sg:person.07627161513.96 schema:affiliation https://www.grid.ac/institutes/grid.266869.5
77 schema:familyName Liu
78 schema:givenName Jie
79 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.07627161513.96
80 rdf:type schema:Person
81 sg:pub.10.1023/a:1016616208442 schema:sameAs https://app.dimensions.ai/details/publication/pub.1043883622
82 https://doi.org/10.1023/a:1016616208442
83 rdf:type schema:CreativeWork
84 sg:pub.10.1023/a:1026159424303 schema:sameAs https://app.dimensions.ai/details/publication/pub.1005657207
85 https://doi.org/10.1023/a:1026159424303
86 rdf:type schema:CreativeWork
87 https://doi.org/10.1016/s0022-328x(00)00082-6 schema:sameAs https://app.dimensions.ai/details/publication/pub.1009643338
88 rdf:type schema:CreativeWork
89 https://doi.org/10.1016/s0022-328x(99)00608-7 schema:sameAs https://app.dimensions.ai/details/publication/pub.1050747679
90 rdf:type schema:CreativeWork
91 https://doi.org/10.1021/ic991279r schema:sameAs https://app.dimensions.ai/details/publication/pub.1055590326
92 rdf:type schema:CreativeWork
93 https://doi.org/10.1021/om00083a033 schema:sameAs https://app.dimensions.ai/details/publication/pub.1056266641
94 rdf:type schema:CreativeWork
95 https://doi.org/10.1039/c39820001217 schema:sameAs https://app.dimensions.ai/details/publication/pub.1031500971
96 rdf:type schema:CreativeWork
97 https://doi.org/10.1039/dt98900000s1 schema:sameAs https://app.dimensions.ai/details/publication/pub.1039084879
98 rdf:type schema:CreativeWork
99 https://www.grid.ac/institutes/grid.264766.7 schema:alternateName Texas Christian University
100 schema:name Department of Chemistry, Texas Christian University, 76129, Fort Worth, Texas
101 rdf:type schema:Organization
102 https://www.grid.ac/institutes/grid.266869.5 schema:alternateName University of North Texas
103 schema:name Department of Chemistry, University of North Texas, 76203, Denton, Texas
104 rdf:type schema:Organization
 




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


...