Facile synthesis of bifunctional ligands using LiCH2PPh 2=NPh obtained from [PhNH-PPh3+][Br -]

Thi Phuong Anh Cao; Elina Payet; Audrey Auffrant; Xavier F. Le Goff; Pascal Le Floch

doi:10.1021/om100695b

Facile synthesis of bifunctional ligands using LiCH₂PPh ₂=NPh obtained from [PhNH-PPh₃⁺][Br ^-]

Thi Phuong Anh Cao
, Elina Payet
, Audrey Auffrant
, Xavier F. Le Goff
, Pascal Le Floch

CNRS

Research output: Contribution to journal › Article › peer-review

Abstract

The LiCH₂PPh₂=NPh derivative 2 was cleanly prepared from the aminophosphonium salt [PhNH-PPh₃⁺][Br ^-] (1) and MeLi. After formation of the iminophosphorane PPh ₃=NPh, nucleophilic displacement of one phenyl ring of the P atom by a methyl group occurred. This sequence was demonstrated to highly depend on the experimental conditions and on the substituent pattern at the nitrogen atom. Then, 2 was reacted with various electrophiles, among which phosphine chlorides, silyl chloride, stannyl chloride, and cyanophosphole, leading to bifunctional ligands. Depending on the electrophiles, the products were isolated either as the aminophosphonium salts or the iminophosphorane derivatives. All of these products were characterized by multinuclear NMR spectrocopy and in two cases by X-ray analysis. In particular, reaction of 2 with S₈ gave rise to the thiolate derivative (LiSCH₂PPh₂=NPh) (9), which was subsequently coordinated to Pd(II) and Ru(II) metal centers to give respectively [(PhNPPh₂CH₂S)Pd(PPh₃)Cl] and [(PhNPPh ₂CH₂S)Ru(p-cymene)Cl].

Original language	English
Pages (from-to)	3991-3996
Number of pages	6
Journal	Organometallics
Volume	29
Issue number	17
DOIs	https://doi.org/10.1021/om100695b
Publication status	Published - 13 Sept 2010
Externally published	Yes

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@article{fc855fa08cba408b8df0d4f394f76afb,

title = "Facile synthesis of bifunctional ligands using LiCH2PPh 2=NPh obtained from [PhNH-PPh3+][Br -]",

abstract = "The LiCH2PPh2=NPh derivative 2 was cleanly prepared from the aminophosphonium salt [PhNH-PPh3+][Br -] (1) and MeLi. After formation of the iminophosphorane PPh 3=NPh, nucleophilic displacement of one phenyl ring of the P atom by a methyl group occurred. This sequence was demonstrated to highly depend on the experimental conditions and on the substituent pattern at the nitrogen atom. Then, 2 was reacted with various electrophiles, among which phosphine chlorides, silyl chloride, stannyl chloride, and cyanophosphole, leading to bifunctional ligands. Depending on the electrophiles, the products were isolated either as the aminophosphonium salts or the iminophosphorane derivatives. All of these products were characterized by multinuclear NMR spectrocopy and in two cases by X-ray analysis. In particular, reaction of 2 with S8 gave rise to the thiolate derivative (LiSCH2PPh2=NPh) (9), which was subsequently coordinated to Pd(II) and Ru(II) metal centers to give respectively [(PhNPPh2CH2S)Pd(PPh3)Cl] and [(PhNPPh 2CH2S)Ru(p-cymene)Cl].",

author = "Cao, \{Thi Phuong Anh\} and Elina Payet and Audrey Auffrant and \{Le Goff\}, \{Xavier F.\} and \{Le Floch\}, Pascal",

year = "2010",

month = sep,

day = "13",

doi = "10.1021/om100695b",

language = "English",

volume = "29",

pages = "3991--3996",

journal = "Organometallics",

issn = "0276-7333",

number = "17",

}

TY - JOUR

T1 - Facile synthesis of bifunctional ligands using LiCH2PPh 2=NPh obtained from [PhNH-PPh3+][Br -]

AU - Cao, Thi Phuong Anh

AU - Payet, Elina

AU - Auffrant, Audrey

AU - Le Goff, Xavier F.

AU - Le Floch, Pascal

PY - 2010/9/13

Y1 - 2010/9/13

N2 - The LiCH2PPh2=NPh derivative 2 was cleanly prepared from the aminophosphonium salt [PhNH-PPh3+][Br -] (1) and MeLi. After formation of the iminophosphorane PPh 3=NPh, nucleophilic displacement of one phenyl ring of the P atom by a methyl group occurred. This sequence was demonstrated to highly depend on the experimental conditions and on the substituent pattern at the nitrogen atom. Then, 2 was reacted with various electrophiles, among which phosphine chlorides, silyl chloride, stannyl chloride, and cyanophosphole, leading to bifunctional ligands. Depending on the electrophiles, the products were isolated either as the aminophosphonium salts or the iminophosphorane derivatives. All of these products were characterized by multinuclear NMR spectrocopy and in two cases by X-ray analysis. In particular, reaction of 2 with S8 gave rise to the thiolate derivative (LiSCH2PPh2=NPh) (9), which was subsequently coordinated to Pd(II) and Ru(II) metal centers to give respectively [(PhNPPh2CH2S)Pd(PPh3)Cl] and [(PhNPPh 2CH2S)Ru(p-cymene)Cl].

AB - The LiCH2PPh2=NPh derivative 2 was cleanly prepared from the aminophosphonium salt [PhNH-PPh3+][Br -] (1) and MeLi. After formation of the iminophosphorane PPh 3=NPh, nucleophilic displacement of one phenyl ring of the P atom by a methyl group occurred. This sequence was demonstrated to highly depend on the experimental conditions and on the substituent pattern at the nitrogen atom. Then, 2 was reacted with various electrophiles, among which phosphine chlorides, silyl chloride, stannyl chloride, and cyanophosphole, leading to bifunctional ligands. Depending on the electrophiles, the products were isolated either as the aminophosphonium salts or the iminophosphorane derivatives. All of these products were characterized by multinuclear NMR spectrocopy and in two cases by X-ray analysis. In particular, reaction of 2 with S8 gave rise to the thiolate derivative (LiSCH2PPh2=NPh) (9), which was subsequently coordinated to Pd(II) and Ru(II) metal centers to give respectively [(PhNPPh2CH2S)Pd(PPh3)Cl] and [(PhNPPh 2CH2S)Ru(p-cymene)Cl].

U2 - 10.1021/om100695b

DO - 10.1021/om100695b

M3 - Article

AN - SCOPUS:77956399438

SN - 0276-7333

VL - 29

SP - 3991

EP - 3996

JO - Organometallics

JF - Organometallics

IS - 17

ER -

Facile synthesis of bifunctional ligands using LiCH2PPh 2=NPh obtained from [PhNH-PPh3+][Br -]

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Facile synthesis of bifunctional ligands using LiCH₂PPh ₂=NPh obtained from [PhNH-PPh₃⁺][Br ^-]