Trans-Chelating Chiral Peralkyldiphosphine Ligands (R,R) -(S,S)-2,2″-Bis[1-(dialkylphosphino)ethyl]-1,1″-biferrocenes (AlkyITRAPs) and Their Transition Metal Complexes

Ryoichi Kuwano, Masaya Sawamura, Satoshi Okuda, Tomohito Asai, Yoshihiko Ito, Martine Redon, Alain Krieff

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

New chiral peralkyldiphosphines (S,S)-2,2″-bis[(R)-1-(dialkylphosphino)ethyl]-1,1″-biferrocenes ((R,R)-(S,S)-al-kylTRAPs) were synthesized from (R)-N,N-dimethyl-1-ferrocenylethylamine in four steps in 38-68% overall yields (MeTRAP: 38%, EtTRAP: 68%, PrTRAP: 53%, BuTRAP: 56%, i-BuTRAP: 51%, i-PrTRAP: 42%). The reactions of alkylTRAP (Et-, Bu-, i-Bu, and i-PrTRAP) with 1 molar amount Of PdBr2 gave tran-[PdBr2(alkylTRAP)] in good yields. The X-ray crystal structures of these palladium complexes revealed that alkylTRAPs coordinated to a palladium atom in a trans-chelating manner regardless of the P-alkyl substituents. The structures of palladium complexes of Et-, Bu-, and i-PrTRAP had nearly C2-symmetry, but that of i-BuTRAP was deviated from C2-symmetry significantly. AlkylTRAPs also reacted with [PtCl2(MeCN2] and [RhCl(CO2]2, giving the corresponding trans-chelate platinum and rhodium complexes. The crystal structure of tran [RhCl(CO)(BuTRAP)] revealed that the conformation of the BuTRAP ligand in the complex was almost the same as that in the palladium complex trans-[PdBr2(BuTRAP)].

Original languageEnglish
Pages (from-to)2807-2822
Number of pages16
JournalBulletin of the Chemical Society of Japan
Volume70
Issue number11
DOIs
Publication statusPublished - Jan 1 1997
Externally publishedYes

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Coordination Complexes
Palladium
Chelation
Transition metals
Ligands
Crystal structure
Rhodium
Carbon Monoxide
Platinum
Conformations
X rays
Atoms

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Trans-Chelating Chiral Peralkyldiphosphine Ligands (R,R) -(S,S)-2,2″-Bis[1-(dialkylphosphino)ethyl]-1,1″-biferrocenes (AlkyITRAPs) and Their Transition Metal Complexes. / Kuwano, Ryoichi; Sawamura, Masaya; Okuda, Satoshi; Asai, Tomohito; Ito, Yoshihiko; Redon, Martine; Krieff, Alain.

In: Bulletin of the Chemical Society of Japan, Vol. 70, No. 11, 01.01.1997, p. 2807-2822.

Research output: Contribution to journalArticle

Kuwano, Ryoichi ; Sawamura, Masaya ; Okuda, Satoshi ; Asai, Tomohito ; Ito, Yoshihiko ; Redon, Martine ; Krieff, Alain. / Trans-Chelating Chiral Peralkyldiphosphine Ligands (R,R) -(S,S)-2,2″-Bis[1-(dialkylphosphino)ethyl]-1,1″-biferrocenes (AlkyITRAPs) and Their Transition Metal Complexes. In: Bulletin of the Chemical Society of Japan. 1997 ; Vol. 70, No. 11. pp. 2807-2822.
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abstract = "New chiral peralkyldiphosphines (S,S)-2,2″-bis[(R)-1-(dialkylphosphino)ethyl]-1,1″-biferrocenes ((R,R)-(S,S)-al-kylTRAPs) were synthesized from (R)-N,N-dimethyl-1-ferrocenylethylamine in four steps in 38-68{\%} overall yields (MeTRAP: 38{\%}, EtTRAP: 68{\%}, PrTRAP: 53{\%}, BuTRAP: 56{\%}, i-BuTRAP: 51{\%}, i-PrTRAP: 42{\%}). The reactions of alkylTRAP (Et-, Bu-, i-Bu, and i-PrTRAP) with 1 molar amount Of PdBr2 gave tran-[PdBr2(alkylTRAP)] in good yields. The X-ray crystal structures of these palladium complexes revealed that alkylTRAPs coordinated to a palladium atom in a trans-chelating manner regardless of the P-alkyl substituents. The structures of palladium complexes of Et-, Bu-, and i-PrTRAP had nearly C2-symmetry, but that of i-BuTRAP was deviated from C2-symmetry significantly. AlkylTRAPs also reacted with [PtCl2(MeCN2] and [RhCl(CO2]2, giving the corresponding trans-chelate platinum and rhodium complexes. The crystal structure of tran [RhCl(CO)(BuTRAP)] revealed that the conformation of the BuTRAP ligand in the complex was almost the same as that in the palladium complex trans-[PdBr2(BuTRAP)].",
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T1 - Trans-Chelating Chiral Peralkyldiphosphine Ligands (R,R) -(S,S)-2,2″-Bis[1-(dialkylphosphino)ethyl]-1,1″-biferrocenes (AlkyITRAPs) and Their Transition Metal Complexes

AU - Kuwano, Ryoichi

AU - Sawamura, Masaya

AU - Okuda, Satoshi

AU - Asai, Tomohito

AU - Ito, Yoshihiko

AU - Redon, Martine

AU - Krieff, Alain

PY - 1997/1/1

Y1 - 1997/1/1

N2 - New chiral peralkyldiphosphines (S,S)-2,2″-bis[(R)-1-(dialkylphosphino)ethyl]-1,1″-biferrocenes ((R,R)-(S,S)-al-kylTRAPs) were synthesized from (R)-N,N-dimethyl-1-ferrocenylethylamine in four steps in 38-68% overall yields (MeTRAP: 38%, EtTRAP: 68%, PrTRAP: 53%, BuTRAP: 56%, i-BuTRAP: 51%, i-PrTRAP: 42%). The reactions of alkylTRAP (Et-, Bu-, i-Bu, and i-PrTRAP) with 1 molar amount Of PdBr2 gave tran-[PdBr2(alkylTRAP)] in good yields. The X-ray crystal structures of these palladium complexes revealed that alkylTRAPs coordinated to a palladium atom in a trans-chelating manner regardless of the P-alkyl substituents. The structures of palladium complexes of Et-, Bu-, and i-PrTRAP had nearly C2-symmetry, but that of i-BuTRAP was deviated from C2-symmetry significantly. AlkylTRAPs also reacted with [PtCl2(MeCN2] and [RhCl(CO2]2, giving the corresponding trans-chelate platinum and rhodium complexes. The crystal structure of tran [RhCl(CO)(BuTRAP)] revealed that the conformation of the BuTRAP ligand in the complex was almost the same as that in the palladium complex trans-[PdBr2(BuTRAP)].

AB - New chiral peralkyldiphosphines (S,S)-2,2″-bis[(R)-1-(dialkylphosphino)ethyl]-1,1″-biferrocenes ((R,R)-(S,S)-al-kylTRAPs) were synthesized from (R)-N,N-dimethyl-1-ferrocenylethylamine in four steps in 38-68% overall yields (MeTRAP: 38%, EtTRAP: 68%, PrTRAP: 53%, BuTRAP: 56%, i-BuTRAP: 51%, i-PrTRAP: 42%). The reactions of alkylTRAP (Et-, Bu-, i-Bu, and i-PrTRAP) with 1 molar amount Of PdBr2 gave tran-[PdBr2(alkylTRAP)] in good yields. The X-ray crystal structures of these palladium complexes revealed that alkylTRAPs coordinated to a palladium atom in a trans-chelating manner regardless of the P-alkyl substituents. The structures of palladium complexes of Et-, Bu-, and i-PrTRAP had nearly C2-symmetry, but that of i-BuTRAP was deviated from C2-symmetry significantly. AlkylTRAPs also reacted with [PtCl2(MeCN2] and [RhCl(CO2]2, giving the corresponding trans-chelate platinum and rhodium complexes. The crystal structure of tran [RhCl(CO)(BuTRAP)] revealed that the conformation of the BuTRAP ligand in the complex was almost the same as that in the palladium complex trans-[PdBr2(BuTRAP)].

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