New ligand systems incorporating two and three 4,4′-bipyridine units. Characterization of bi- and trimetallic rhodium and iridium complexes

Reto Dorta, Romano Dorta, Linda J W Shimon, David Milstein

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Abstract

The synthesis of new ligand systems based on the bipyridine unit for bi- and trimetallic complexes, including a rare example of a chiral bimetallic complex, is presented. Ligands BBPX (bis-bipyridine-xylene, 3) and TBPBX (trisbipyridine-bis-xylene, 4) were prepared in one step by reacting α,α′-dibromo-o-xylene (2) with 2 equiv of the monolithiated derivative of 4,4′-dimethyl-2,2′-bipyridine. Dilithium (S)-binaphtholate (5) reacted with 2 equiv of 4-bromomethyl-4′-methyl-2, 2′-bipyridine (6), affording ligand (S)-BBPBINAP (bis-bipyridine- binaphtholate, 7). These ligands reacted cleanly with 1, 1.5, and 1 equiv of the rhodium dimer [Rh2Cl2(HD)2] (HD = 1,5-hexadiene), respectively. Chloride abstraction led to the isolation of the cationic complexes BBPX[Rh(HD)BF4]2 (8), TBPBX[Rh(HD)BF4]3 (10), and (S)-BBPBINAP[Rh(HD)BF 4]2 (12). When BBPX (3), TBPBX (4), and (S)-BBPBINAP (7) were added to 2, 3, and 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene), respectively, clean formation of BBPX[Rh(NBD)BF4]2 (9), TBPBX[Rh(NBD)BF4]3 (11), and (S)-BBPBINAP[Rh(NBD)BF 4]2 (13) was observed. The neutral iridium complex (S)-BBPBINAP[IrCl(COD)]2 (14) was obtained by reaction of (S)-BBPBINAP (7) with 1 equiv of [Ir2Cl2(COD)2] (COD = cyclooctadiene). The complexes were fully characterized including X-ray structural studies of 8, 9, and 13, and preliminary studies on their catalytic activity were performed.

Original languageEnglish
Pages (from-to)7180-7186
Number of pages7
JournalInorganic Chemistry
Volume43
Issue number22
DOIs
Publication statusPublished - Nov 1 2004

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Iridium
Rhodium
xylene
iridium
rhodium
Ligands
ligands
crack opening displacement
Dimers
Chlorides
Catalyst activity
Derivatives
lead chlorides
X rays
hexadiene
3-xylene
4-xylene
catalytic activity
isolation
dimers

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

New ligand systems incorporating two and three 4,4′-bipyridine units. Characterization of bi- and trimetallic rhodium and iridium complexes. / Dorta, Reto; Dorta, Romano; Shimon, Linda J W; Milstein, David.

In: Inorganic Chemistry, Vol. 43, No. 22, 01.11.2004, p. 7180-7186.

Research output: Contribution to journalArticle

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abstract = "The synthesis of new ligand systems based on the bipyridine unit for bi- and trimetallic complexes, including a rare example of a chiral bimetallic complex, is presented. Ligands BBPX (bis-bipyridine-xylene, 3) and TBPBX (trisbipyridine-bis-xylene, 4) were prepared in one step by reacting α,α′-dibromo-o-xylene (2) with 2 equiv of the monolithiated derivative of 4,4′-dimethyl-2,2′-bipyridine. Dilithium (S)-binaphtholate (5) reacted with 2 equiv of 4-bromomethyl-4′-methyl-2, 2′-bipyridine (6), affording ligand (S)-BBPBINAP (bis-bipyridine- binaphtholate, 7). These ligands reacted cleanly with 1, 1.5, and 1 equiv of the rhodium dimer [Rh2Cl2(HD)2] (HD = 1,5-hexadiene), respectively. Chloride abstraction led to the isolation of the cationic complexes BBPX[Rh(HD)BF4]2 (8), TBPBX[Rh(HD)BF4]3 (10), and (S)-BBPBINAP[Rh(HD)BF 4]2 (12). When BBPX (3), TBPBX (4), and (S)-BBPBINAP (7) were added to 2, 3, and 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene), respectively, clean formation of BBPX[Rh(NBD)BF4]2 (9), TBPBX[Rh(NBD)BF4]3 (11), and (S)-BBPBINAP[Rh(NBD)BF 4]2 (13) was observed. The neutral iridium complex (S)-BBPBINAP[IrCl(COD)]2 (14) was obtained by reaction of (S)-BBPBINAP (7) with 1 equiv of [Ir2Cl2(COD)2] (COD = cyclooctadiene). The complexes were fully characterized including X-ray structural studies of 8, 9, and 13, and preliminary studies on their catalytic activity were performed.",
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T1 - New ligand systems incorporating two and three 4,4′-bipyridine units. Characterization of bi- and trimetallic rhodium and iridium complexes

AU - Dorta, Reto

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AU - Milstein, David

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N2 - The synthesis of new ligand systems based on the bipyridine unit for bi- and trimetallic complexes, including a rare example of a chiral bimetallic complex, is presented. Ligands BBPX (bis-bipyridine-xylene, 3) and TBPBX (trisbipyridine-bis-xylene, 4) were prepared in one step by reacting α,α′-dibromo-o-xylene (2) with 2 equiv of the monolithiated derivative of 4,4′-dimethyl-2,2′-bipyridine. Dilithium (S)-binaphtholate (5) reacted with 2 equiv of 4-bromomethyl-4′-methyl-2, 2′-bipyridine (6), affording ligand (S)-BBPBINAP (bis-bipyridine- binaphtholate, 7). These ligands reacted cleanly with 1, 1.5, and 1 equiv of the rhodium dimer [Rh2Cl2(HD)2] (HD = 1,5-hexadiene), respectively. Chloride abstraction led to the isolation of the cationic complexes BBPX[Rh(HD)BF4]2 (8), TBPBX[Rh(HD)BF4]3 (10), and (S)-BBPBINAP[Rh(HD)BF 4]2 (12). When BBPX (3), TBPBX (4), and (S)-BBPBINAP (7) were added to 2, 3, and 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene), respectively, clean formation of BBPX[Rh(NBD)BF4]2 (9), TBPBX[Rh(NBD)BF4]3 (11), and (S)-BBPBINAP[Rh(NBD)BF 4]2 (13) was observed. The neutral iridium complex (S)-BBPBINAP[IrCl(COD)]2 (14) was obtained by reaction of (S)-BBPBINAP (7) with 1 equiv of [Ir2Cl2(COD)2] (COD = cyclooctadiene). The complexes were fully characterized including X-ray structural studies of 8, 9, and 13, and preliminary studies on their catalytic activity were performed.

AB - The synthesis of new ligand systems based on the bipyridine unit for bi- and trimetallic complexes, including a rare example of a chiral bimetallic complex, is presented. Ligands BBPX (bis-bipyridine-xylene, 3) and TBPBX (trisbipyridine-bis-xylene, 4) were prepared in one step by reacting α,α′-dibromo-o-xylene (2) with 2 equiv of the monolithiated derivative of 4,4′-dimethyl-2,2′-bipyridine. Dilithium (S)-binaphtholate (5) reacted with 2 equiv of 4-bromomethyl-4′-methyl-2, 2′-bipyridine (6), affording ligand (S)-BBPBINAP (bis-bipyridine- binaphtholate, 7). These ligands reacted cleanly with 1, 1.5, and 1 equiv of the rhodium dimer [Rh2Cl2(HD)2] (HD = 1,5-hexadiene), respectively. Chloride abstraction led to the isolation of the cationic complexes BBPX[Rh(HD)BF4]2 (8), TBPBX[Rh(HD)BF4]3 (10), and (S)-BBPBINAP[Rh(HD)BF 4]2 (12). When BBPX (3), TBPBX (4), and (S)-BBPBINAP (7) were added to 2, 3, and 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene), respectively, clean formation of BBPX[Rh(NBD)BF4]2 (9), TBPBX[Rh(NBD)BF4]3 (11), and (S)-BBPBINAP[Rh(NBD)BF 4]2 (13) was observed. The neutral iridium complex (S)-BBPBINAP[IrCl(COD)]2 (14) was obtained by reaction of (S)-BBPBINAP (7) with 1 equiv of [Ir2Cl2(COD)2] (COD = cyclooctadiene). The complexes were fully characterized including X-ray structural studies of 8, 9, and 13, and preliminary studies on their catalytic activity were performed.

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