Synthesis, Reactions, and 77Se NMR Studies of η5-Selenophene Complexes of Chromium, Manganese, Ruthenium, and Iridium

Carter J. White, Robert J. Angelici, Moon-Gun Choi

Research output: Contribution to journalArticle

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Abstract

The series of η5-selenophene transition metal complexes (η5-Seln)Cr(CO)3 (1-3), [(η5-Seln)Mn(CO)3]SO3CF3(4–6), [(η5-Seln)RuCp*]SO3CF3(7–9), and [(η5-Seln)IrCp*](BF4)2 (10-12), where Seln = selenophene (Sel), 2-methylselenophene (2-MeSel), or 2,5-dimethylselenophene (2,5-Me2Sel), were synthesized and characterized by 1H, 13C, and 77Se NMR and IR spectroscopy. The molecular structure of (η5-2,5-Me2Sel)Cr(CO)3 (3) was determined. Reactions of [(η5-Sel)Mn(CO)3]SO3CF3(4) with nucleophiles (Nuc = H-, CN-) give the neutral addition products [(Sel-Nuc)Mn(CO)3] [Nuc = H-(4a), Nuc = CN-(4b)] in which three carbon atoms and the Se are bonded to the Mn. The reaction of [(η5-Sel)RuCp*]SO3CF3(7) with H-, however, results in cleavage of the C-Se bond to form a butadiene selenide complex ((η5-SeCH═CHCH═CH2)RuCp*) (7a). Still another type of product results from the reaction of [(η5-2,5-Me2Sel)IrCp*](BF4)2 (12) with 2 equiv of H-; in this case, the H- acts as a reducing agent to give the ring-opened complex (C, Se-2,5-Me2Sel)IrCp* (12a). All of these reactions are similar to those of the analogous η5-thiophene complexes. The 77Se NMR chemical shift values for the η5-Seln ligands in complexes 1–12 fall within a range of 225 ppm; they are influenced by the metal and its ligands, the charge on the complex, and the number of methyl groups in the selenophene.

Original languageEnglish
Pages (from-to)332-340
Number of pages9
JournalOrganometallics
Volume14
Issue number1
DOIs
Publication statusPublished - 1995 Jan 1

Fingerprint

Iridium
Ruthenium
Chromium
Carbon Monoxide
Manganese
iridium
ruthenium
manganese
chromium
Nuclear magnetic resonance
nuclear magnetic resonance
synthesis
ligands
selenides
nucleophiles
Ligands
products
butadiene
Thiophenes
thiophenes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

White, Carter J. ; Angelici, Robert J. ; Choi, Moon-Gun. / Synthesis, Reactions, and 77Se NMR Studies of η5-Selenophene Complexes of Chromium, Manganese, Ruthenium, and Iridium. In: Organometallics. 1995 ; Vol. 14, No. 1. pp. 332-340.
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title = "Synthesis, Reactions, and 77Se NMR Studies of η5-Selenophene Complexes of Chromium, Manganese, Ruthenium, and Iridium",
abstract = "The series of η5-selenophene transition metal complexes (η5-Seln)Cr(CO)3 (1-3), [(η5-Seln)Mn(CO)3]SO3CF3(4–6), [(η5-Seln)RuCp*]SO3CF3(7–9), and [(η5-Seln)IrCp*](BF4)2 (10-12), where Seln = selenophene (Sel), 2-methylselenophene (2-MeSel), or 2,5-dimethylselenophene (2,5-Me2Sel), were synthesized and characterized by 1H, 13C, and 77Se NMR and IR spectroscopy. The molecular structure of (η5-2,5-Me2Sel)Cr(CO)3 (3) was determined. Reactions of [(η5-Sel)Mn(CO)3]SO3CF3(4) with nucleophiles (Nuc = H-, CN-) give the neutral addition products [(Sel-Nuc)Mn(CO)3] [Nuc = H-(4a), Nuc = CN-(4b)] in which three carbon atoms and the Se are bonded to the Mn. The reaction of [(η5-Sel)RuCp*]SO3CF3(7) with H-, however, results in cleavage of the C-Se bond to form a butadiene selenide complex ((η5-SeCH═CHCH═CH2)RuCp*) (7a). Still another type of product results from the reaction of [(η5-2,5-Me2Sel)IrCp*](BF4)2 (12) with 2 equiv of H-; in this case, the H- acts as a reducing agent to give the ring-opened complex (C, Se-2,5-Me2Sel)IrCp* (12a). All of these reactions are similar to those of the analogous η5-thiophene complexes. The 77Se NMR chemical shift values for the η5-Seln ligands in complexes 1–12 fall within a range of 225 ppm; they are influenced by the metal and its ligands, the charge on the complex, and the number of methyl groups in the selenophene.",
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Synthesis, Reactions, and 77Se NMR Studies of η5-Selenophene Complexes of Chromium, Manganese, Ruthenium, and Iridium. / White, Carter J.; Angelici, Robert J.; Choi, Moon-Gun.

In: Organometallics, Vol. 14, No. 1, 01.01.1995, p. 332-340.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, Reactions, and 77Se NMR Studies of η5-Selenophene Complexes of Chromium, Manganese, Ruthenium, and Iridium

AU - White, Carter J.

AU - Angelici, Robert J.

AU - Choi, Moon-Gun

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N2 - The series of η5-selenophene transition metal complexes (η5-Seln)Cr(CO)3 (1-3), [(η5-Seln)Mn(CO)3]SO3CF3(4–6), [(η5-Seln)RuCp*]SO3CF3(7–9), and [(η5-Seln)IrCp*](BF4)2 (10-12), where Seln = selenophene (Sel), 2-methylselenophene (2-MeSel), or 2,5-dimethylselenophene (2,5-Me2Sel), were synthesized and characterized by 1H, 13C, and 77Se NMR and IR spectroscopy. The molecular structure of (η5-2,5-Me2Sel)Cr(CO)3 (3) was determined. Reactions of [(η5-Sel)Mn(CO)3]SO3CF3(4) with nucleophiles (Nuc = H-, CN-) give the neutral addition products [(Sel-Nuc)Mn(CO)3] [Nuc = H-(4a), Nuc = CN-(4b)] in which three carbon atoms and the Se are bonded to the Mn. The reaction of [(η5-Sel)RuCp*]SO3CF3(7) with H-, however, results in cleavage of the C-Se bond to form a butadiene selenide complex ((η5-SeCH═CHCH═CH2)RuCp*) (7a). Still another type of product results from the reaction of [(η5-2,5-Me2Sel)IrCp*](BF4)2 (12) with 2 equiv of H-; in this case, the H- acts as a reducing agent to give the ring-opened complex (C, Se-2,5-Me2Sel)IrCp* (12a). All of these reactions are similar to those of the analogous η5-thiophene complexes. The 77Se NMR chemical shift values for the η5-Seln ligands in complexes 1–12 fall within a range of 225 ppm; they are influenced by the metal and its ligands, the charge on the complex, and the number of methyl groups in the selenophene.

AB - The series of η5-selenophene transition metal complexes (η5-Seln)Cr(CO)3 (1-3), [(η5-Seln)Mn(CO)3]SO3CF3(4–6), [(η5-Seln)RuCp*]SO3CF3(7–9), and [(η5-Seln)IrCp*](BF4)2 (10-12), where Seln = selenophene (Sel), 2-methylselenophene (2-MeSel), or 2,5-dimethylselenophene (2,5-Me2Sel), were synthesized and characterized by 1H, 13C, and 77Se NMR and IR spectroscopy. The molecular structure of (η5-2,5-Me2Sel)Cr(CO)3 (3) was determined. Reactions of [(η5-Sel)Mn(CO)3]SO3CF3(4) with nucleophiles (Nuc = H-, CN-) give the neutral addition products [(Sel-Nuc)Mn(CO)3] [Nuc = H-(4a), Nuc = CN-(4b)] in which three carbon atoms and the Se are bonded to the Mn. The reaction of [(η5-Sel)RuCp*]SO3CF3(7) with H-, however, results in cleavage of the C-Se bond to form a butadiene selenide complex ((η5-SeCH═CHCH═CH2)RuCp*) (7a). Still another type of product results from the reaction of [(η5-2,5-Me2Sel)IrCp*](BF4)2 (12) with 2 equiv of H-; in this case, the H- acts as a reducing agent to give the ring-opened complex (C, Se-2,5-Me2Sel)IrCp* (12a). All of these reactions are similar to those of the analogous η5-thiophene complexes. The 77Se NMR chemical shift values for the η5-Seln ligands in complexes 1–12 fall within a range of 225 ppm; they are influenced by the metal and its ligands, the charge on the complex, and the number of methyl groups in the selenophene.

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