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 language | English |
|---|---|
| Pages (from-to) | 332-340 |
| Number of pages | 9 |
| Journal | Organometallics |
| Volume | 14 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 1995 Jan 1 |
Fingerprint
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
Cite this
}
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 journal › Article
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
PY - 1995/1/1
Y1 - 1995/1/1
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.
UR - http://www.scopus.com/inward/record.url?scp=0029184612&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0029184612&partnerID=8YFLogxK
U2 - 10.1021/om00001a048
DO - 10.1021/om00001a048
M3 - Article
VL - 14
SP - 332
EP - 340
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 1
ER -