Synthesis and Structures of Trans-Chelating Chiral Diphosphine Ligands Bearing Aromatic P-Substituents, (S,S)-(R,R)- and (R,R)- (S,S)-2,2″-Bis [ 1-(diarylphosphino)ethyl] -1,1″-biferrocenes (ArylTRAPs), and Their Transition Metal Complexes

Masaya Sawamura, Hitoshi Hamashima, Masanobu Sugawara, Ryoichi Kuwano, Yoshihiko Ito

Research output: Contribution to journalArticle

121 Citations (Scopus)

Abstract

The trans-chelating chiral phosphine ligand (S,S)-(R,R)-2,2'-bis[l-(diphenylphosphino)-ethyl]-1,1'-biferrocene (1a, abbreviated to PhTRAP) was synthesized from (S)-1-(N,N- dimethylamino)ethylferrocene (2) in four steps in 51% overall yield. (R,R)-(S,S)-PhTRAP and other arylTRAP derivatives (1b, AnisTRAP; 1c, Cl-PhTRAP, 1d, FurTRAP; le, Tol-PhTRAP) were synthesized in a similar manner. Through-space 31P-31P spin couplings were observed indirectly in the and 13C{1H} NMR spectra of -1a-e and directly in the 31P{1H} NMR spectrum of asymmetrical TRAP 1e, indicating that the two phosphorus atoms of the ligands are in close proximity. Results of NOE experiments showed that PhTRAP is a fairly rigid molecule and in a conformation favorable for trans-chelation. As square planar transition metal complexes bearing arylTRAPs as trans-chelating ligands, trans-[PdX2{(S,S)-(R,R)-PhTRAP}] (7, X = Br; 8, X = I; 9, X = Cl), trans-[PtCl2{(R,R(-(S,S)-PhTRAP}] (10), trans-[PtCl2{(S,S)-(R,R)-1e}] (11), trans-[IrCl(CO){(S,S)-(R,R)-PhTRAP}] (12), trans-[RhCl-(CO){(S,S)-(R,R)-PhTRAP}] (13), and trans-[RhCl(CO){(S,S)-(R,R)-FurTRAP}] (14) were prepared and fully characterized. X-ray crystal structures were determined for the palladium complex 7 and the rhodium complex 14.

Original languageEnglish
Pages (from-to)4549-4558
Number of pages10
JournalOrganometallics
Volume14
Issue number10
DOIs
Publication statusPublished - Jan 1 1995
Externally publishedYes

Fingerprint

Bearings (structural)
Coordination Complexes
Carbon Monoxide
Chelation
Transition metals
phosphine
transition metals
Ligands
ligands
synthesis
Nuclear magnetic resonance
Rhodium
nuclear magnetic resonance
chelation
Palladium
rhodium
phosphines
Phosphorus
Conformations
phosphorus

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{f13671614c6545bc8aa89de899eacb77,
title = "Synthesis and Structures of Trans-Chelating Chiral Diphosphine Ligands Bearing Aromatic P-Substituents, (S,S)-(R,R)- and (R,R)- (S,S)-2,2″-Bis [ 1-(diarylphosphino)ethyl] -1,1″-biferrocenes (ArylTRAPs), and Their Transition Metal Complexes",
abstract = "The trans-chelating chiral phosphine ligand (S,S)-(R,R)-2,2'-bis[l-(diphenylphosphino)-ethyl]-1,1'-biferrocene (1a, abbreviated to PhTRAP) was synthesized from (S)-1-(N,N- dimethylamino)ethylferrocene (2) in four steps in 51{\%} overall yield. (R,R)-(S,S)-PhTRAP and other arylTRAP derivatives (1b, AnisTRAP; 1c, Cl-PhTRAP, 1d, FurTRAP; le, Tol-PhTRAP) were synthesized in a similar manner. Through-space 31P-31P spin couplings were observed indirectly in the and 13C{1H} NMR spectra of -1a-e and directly in the 31P{1H} NMR spectrum of asymmetrical TRAP 1e, indicating that the two phosphorus atoms of the ligands are in close proximity. Results of NOE experiments showed that PhTRAP is a fairly rigid molecule and in a conformation favorable for trans-chelation. As square planar transition metal complexes bearing arylTRAPs as trans-chelating ligands, trans-[PdX2{(S,S)-(R,R)-PhTRAP}] (7, X = Br; 8, X = I; 9, X = Cl), trans-[PtCl2{(R,R(-(S,S)-PhTRAP}] (10), trans-[PtCl2{(S,S)-(R,R)-1e}] (11), trans-[IrCl(CO){(S,S)-(R,R)-PhTRAP}] (12), trans-[RhCl-(CO){(S,S)-(R,R)-PhTRAP}] (13), and trans-[RhCl(CO){(S,S)-(R,R)-FurTRAP}] (14) were prepared and fully characterized. X-ray crystal structures were determined for the palladium complex 7 and the rhodium complex 14.",
author = "Masaya Sawamura and Hitoshi Hamashima and Masanobu Sugawara and Ryoichi Kuwano and Yoshihiko Ito",
year = "1995",
month = "1",
day = "1",
doi = "10.1021/om00010a020",
language = "English",
volume = "14",
pages = "4549--4558",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Synthesis and Structures of Trans-Chelating Chiral Diphosphine Ligands Bearing Aromatic P-Substituents, (S,S)-(R,R)- and (R,R)- (S,S)-2,2″-Bis [ 1-(diarylphosphino)ethyl] -1,1″-biferrocenes (ArylTRAPs), and Their Transition Metal Complexes

AU - Sawamura, Masaya

AU - Hamashima, Hitoshi

AU - Sugawara, Masanobu

AU - Kuwano, Ryoichi

AU - Ito, Yoshihiko

PY - 1995/1/1

Y1 - 1995/1/1

N2 - The trans-chelating chiral phosphine ligand (S,S)-(R,R)-2,2'-bis[l-(diphenylphosphino)-ethyl]-1,1'-biferrocene (1a, abbreviated to PhTRAP) was synthesized from (S)-1-(N,N- dimethylamino)ethylferrocene (2) in four steps in 51% overall yield. (R,R)-(S,S)-PhTRAP and other arylTRAP derivatives (1b, AnisTRAP; 1c, Cl-PhTRAP, 1d, FurTRAP; le, Tol-PhTRAP) were synthesized in a similar manner. Through-space 31P-31P spin couplings were observed indirectly in the and 13C{1H} NMR spectra of -1a-e and directly in the 31P{1H} NMR spectrum of asymmetrical TRAP 1e, indicating that the two phosphorus atoms of the ligands are in close proximity. Results of NOE experiments showed that PhTRAP is a fairly rigid molecule and in a conformation favorable for trans-chelation. As square planar transition metal complexes bearing arylTRAPs as trans-chelating ligands, trans-[PdX2{(S,S)-(R,R)-PhTRAP}] (7, X = Br; 8, X = I; 9, X = Cl), trans-[PtCl2{(R,R(-(S,S)-PhTRAP}] (10), trans-[PtCl2{(S,S)-(R,R)-1e}] (11), trans-[IrCl(CO){(S,S)-(R,R)-PhTRAP}] (12), trans-[RhCl-(CO){(S,S)-(R,R)-PhTRAP}] (13), and trans-[RhCl(CO){(S,S)-(R,R)-FurTRAP}] (14) were prepared and fully characterized. X-ray crystal structures were determined for the palladium complex 7 and the rhodium complex 14.

AB - The trans-chelating chiral phosphine ligand (S,S)-(R,R)-2,2'-bis[l-(diphenylphosphino)-ethyl]-1,1'-biferrocene (1a, abbreviated to PhTRAP) was synthesized from (S)-1-(N,N- dimethylamino)ethylferrocene (2) in four steps in 51% overall yield. (R,R)-(S,S)-PhTRAP and other arylTRAP derivatives (1b, AnisTRAP; 1c, Cl-PhTRAP, 1d, FurTRAP; le, Tol-PhTRAP) were synthesized in a similar manner. Through-space 31P-31P spin couplings were observed indirectly in the and 13C{1H} NMR spectra of -1a-e and directly in the 31P{1H} NMR spectrum of asymmetrical TRAP 1e, indicating that the two phosphorus atoms of the ligands are in close proximity. Results of NOE experiments showed that PhTRAP is a fairly rigid molecule and in a conformation favorable for trans-chelation. As square planar transition metal complexes bearing arylTRAPs as trans-chelating ligands, trans-[PdX2{(S,S)-(R,R)-PhTRAP}] (7, X = Br; 8, X = I; 9, X = Cl), trans-[PtCl2{(R,R(-(S,S)-PhTRAP}] (10), trans-[PtCl2{(S,S)-(R,R)-1e}] (11), trans-[IrCl(CO){(S,S)-(R,R)-PhTRAP}] (12), trans-[RhCl-(CO){(S,S)-(R,R)-PhTRAP}] (13), and trans-[RhCl(CO){(S,S)-(R,R)-FurTRAP}] (14) were prepared and fully characterized. X-ray crystal structures were determined for the palladium complex 7 and the rhodium complex 14.

UR - http://www.scopus.com/inward/record.url?scp=0000920053&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000920053&partnerID=8YFLogxK

U2 - 10.1021/om00010a020

DO - 10.1021/om00010a020

M3 - Article

AN - SCOPUS:0000920053

VL - 14

SP - 4549

EP - 4558

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -