On the reactivity of acetylenes coordinated to cobalt. 9. Effects of substitution and coordination on the 13C-NMR chemical shifts of the sp carbons of (μ2-R1C2R2)Co 2(CO)6 complexes. Molecular structure of (μ2-PhC2SiPh3)Co2(CO)6

Berit Happ, Tamás Bartik, Claudia Zucchi, Maria Cecilia Rossi, Franco Ghelfi, Gyula Pályi, Gyula Váradi, Gábor Szalontai, I. Horváth, Angiola Chiesi-Villa, Carlo Guastini

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

Thirty-four (μ2-R1C2R2)Co 2(CO)6 complexes (14 new) were prepared and characterized by their IRv(CO) and 1H- and 13C-NMR spectra. The 13C-NMR chemical shifts of the coordinated sp carbon atoms were correlated with those of the corresponding free acetylenes. This indicated that the interaction between the R1 and R2 groups and the C2Co2(CO)6 moiety is very sensitive not only to the donor/acceptor character of R1 and R2 but also to the orbital symmetry of the atoms attached directly to the C(sp) atoms. The changes of the δ(13C) values of the C(sp) atoms upon coordination were also analyzed in these terms. It is concluded that although the dinuclear μ2-coordination of the acetylene results in a high degree of excitation the stability of the C2Co2(CO)6 moiety diminished the reactivity of the organic ligand. Differences in the reactivity of the (μ2-R1C2R2)Co 2(CO)6 complexes in carbonylation are also discussed. The crystal and molecular structure of (PhC2SiPh3)Co2(CO)6 was determined by single crystal X-ray diffraction. This compound crystallizes in the orthorhombic Pbca space group with a = 28.790(2) Å, b = 11.577(1) Å, c = 17.833(2) Å, Z = 8. The structure was determined with R = 0.039, Rw = 0.036.

Original languageEnglish
Pages (from-to)809-819
Number of pages11
JournalOrganometallics
Volume14
Issue number2
Publication statusPublished - 1995

Fingerprint

Alkynes
Chemical shift
Cobalt
acetylene
Molecular structure
chemical equilibrium
Substitution reactions
molecular structure
cobalt
Carbon
reactivity
Nuclear magnetic resonance
substitutes
Atoms
nuclear magnetic resonance
carbon
atoms
Carbonylation
Acetylene
Crystal structure

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

On the reactivity of acetylenes coordinated to cobalt. 9. Effects of substitution and coordination on the 13C-NMR chemical shifts of the sp carbons of (μ2-R1C2R2)Co 2(CO)6 complexes. Molecular structure of (μ2-PhC2SiPh3)Co2(CO)6. / Happ, Berit; Bartik, Tamás; Zucchi, Claudia; Rossi, Maria Cecilia; Ghelfi, Franco; Pályi, Gyula; Váradi, Gyula; Szalontai, Gábor; Horváth, I.; Chiesi-Villa, Angiola; Guastini, Carlo.

In: Organometallics, Vol. 14, No. 2, 1995, p. 809-819.

Research output: Contribution to journalArticle

Happ, Berit ; Bartik, Tamás ; Zucchi, Claudia ; Rossi, Maria Cecilia ; Ghelfi, Franco ; Pályi, Gyula ; Váradi, Gyula ; Szalontai, Gábor ; Horváth, I. ; Chiesi-Villa, Angiola ; Guastini, Carlo. / On the reactivity of acetylenes coordinated to cobalt. 9. Effects of substitution and coordination on the 13C-NMR chemical shifts of the sp carbons of (μ2-R1C2R2)Co 2(CO)6 complexes. Molecular structure of (μ2-PhC2SiPh3)Co2(CO)6. In: Organometallics. 1995 ; Vol. 14, No. 2. pp. 809-819.
@article{b195cb21abed4fad9fa59d00e0186de1,
title = "On the reactivity of acetylenes coordinated to cobalt. 9. Effects of substitution and coordination on the 13C-NMR chemical shifts of the sp carbons of (μ2-R1C2R2)Co 2(CO)6 complexes. Molecular structure of (μ2-PhC2SiPh3)Co2(CO)6",
abstract = "Thirty-four (μ2-R1C2R2)Co 2(CO)6 complexes (14 new) were prepared and characterized by their IRv(CO) and 1H- and 13C-NMR spectra. The 13C-NMR chemical shifts of the coordinated sp carbon atoms were correlated with those of the corresponding free acetylenes. This indicated that the interaction between the R1 and R2 groups and the C2Co2(CO)6 moiety is very sensitive not only to the donor/acceptor character of R1 and R2 but also to the orbital symmetry of the atoms attached directly to the C(sp) atoms. The changes of the δ(13C) values of the C(sp) atoms upon coordination were also analyzed in these terms. It is concluded that although the dinuclear μ2-coordination of the acetylene results in a high degree of excitation the stability of the C2Co2(CO)6 moiety diminished the reactivity of the organic ligand. Differences in the reactivity of the (μ2-R1C2R2)Co 2(CO)6 complexes in carbonylation are also discussed. The crystal and molecular structure of (PhC2SiPh3)Co2(CO)6 was determined by single crystal X-ray diffraction. This compound crystallizes in the orthorhombic Pbca space group with a = 28.790(2) {\AA}, b = 11.577(1) {\AA}, c = 17.833(2) {\AA}, Z = 8. The structure was determined with R = 0.039, Rw = 0.036.",
author = "Berit Happ and Tam{\'a}s Bartik and Claudia Zucchi and Rossi, {Maria Cecilia} and Franco Ghelfi and Gyula P{\'a}lyi and Gyula V{\'a}radi and G{\'a}bor Szalontai and I. Horv{\'a}th and Angiola Chiesi-Villa and Carlo Guastini",
year = "1995",
language = "English",
volume = "14",
pages = "809--819",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - On the reactivity of acetylenes coordinated to cobalt. 9. Effects of substitution and coordination on the 13C-NMR chemical shifts of the sp carbons of (μ2-R1C2R2)Co 2(CO)6 complexes. Molecular structure of (μ2-PhC2SiPh3)Co2(CO)6

AU - Happ, Berit

AU - Bartik, Tamás

AU - Zucchi, Claudia

AU - Rossi, Maria Cecilia

AU - Ghelfi, Franco

AU - Pályi, Gyula

AU - Váradi, Gyula

AU - Szalontai, Gábor

AU - Horváth, I.

AU - Chiesi-Villa, Angiola

AU - Guastini, Carlo

PY - 1995

Y1 - 1995

N2 - Thirty-four (μ2-R1C2R2)Co 2(CO)6 complexes (14 new) were prepared and characterized by their IRv(CO) and 1H- and 13C-NMR spectra. The 13C-NMR chemical shifts of the coordinated sp carbon atoms were correlated with those of the corresponding free acetylenes. This indicated that the interaction between the R1 and R2 groups and the C2Co2(CO)6 moiety is very sensitive not only to the donor/acceptor character of R1 and R2 but also to the orbital symmetry of the atoms attached directly to the C(sp) atoms. The changes of the δ(13C) values of the C(sp) atoms upon coordination were also analyzed in these terms. It is concluded that although the dinuclear μ2-coordination of the acetylene results in a high degree of excitation the stability of the C2Co2(CO)6 moiety diminished the reactivity of the organic ligand. Differences in the reactivity of the (μ2-R1C2R2)Co 2(CO)6 complexes in carbonylation are also discussed. The crystal and molecular structure of (PhC2SiPh3)Co2(CO)6 was determined by single crystal X-ray diffraction. This compound crystallizes in the orthorhombic Pbca space group with a = 28.790(2) Å, b = 11.577(1) Å, c = 17.833(2) Å, Z = 8. The structure was determined with R = 0.039, Rw = 0.036.

AB - Thirty-four (μ2-R1C2R2)Co 2(CO)6 complexes (14 new) were prepared and characterized by their IRv(CO) and 1H- and 13C-NMR spectra. The 13C-NMR chemical shifts of the coordinated sp carbon atoms were correlated with those of the corresponding free acetylenes. This indicated that the interaction between the R1 and R2 groups and the C2Co2(CO)6 moiety is very sensitive not only to the donor/acceptor character of R1 and R2 but also to the orbital symmetry of the atoms attached directly to the C(sp) atoms. The changes of the δ(13C) values of the C(sp) atoms upon coordination were also analyzed in these terms. It is concluded that although the dinuclear μ2-coordination of the acetylene results in a high degree of excitation the stability of the C2Co2(CO)6 moiety diminished the reactivity of the organic ligand. Differences in the reactivity of the (μ2-R1C2R2)Co 2(CO)6 complexes in carbonylation are also discussed. The crystal and molecular structure of (PhC2SiPh3)Co2(CO)6 was determined by single crystal X-ray diffraction. This compound crystallizes in the orthorhombic Pbca space group with a = 28.790(2) Å, b = 11.577(1) Å, c = 17.833(2) Å, Z = 8. The structure was determined with R = 0.039, Rw = 0.036.

UR - http://www.scopus.com/inward/record.url?scp=0001510607&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001510607&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001510607

VL - 14

SP - 809

EP - 819

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 2

ER -