Rhenium carbonyl complexes with monodentate-coordinated diphosphines: Activation of terminal phosphino groups towards amine-oxide oxidation

Wei Fan; Rui Zhang; Weng Kee Leong; Chit Kay Chu; Yaw Kai Yan

doi:10.1016/j.jorganchem.2005.05.010

Rhenium carbonyl complexes with monodentate-coordinated diphosphines: Activation of terminal phosphino groups towards amine-oxide oxidation

Wei Fan, Rui Zhang, Weng Kee Leong, Chit Kay Chu, Yaw Kai Yan^*

^*Corresponding author for this work

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

12 Citations (Scopus)

Abstract

Terminal phosphino groups of [Re₂(CO)₉(η ¹-P-P)] (P-P = diphosphines) are activated towards oxidation by Me₃NO. The respective reactions of Me₃NO with [Re ₂(CO)₉{η¹-P(o-anisyl)₂(CH ₂)₃PPh₂}], [Re₂(CO) ₉{η¹-PPh₂(CH₂) ₃P(o-anisyl)₂}] and [Re₂(CO) ₉(η¹-trans-PPh₂CH=CHPPh₂)] were studied to investigate the mechanism of this oxidation. The results are consistent with an intramolecular pathway involving a cyclic intermediate, without exchange of the coordinated and terminal phosphino groups. A mechanism which involves an interaction of the terminal phosphino group with a carbonyl ligand is proposed. In sharp contrast to eq-[Re₂(CO) ₉(η¹-P-P)] (P-P = Ph₂P(CH₂) _nPPh₂, n = 1-6), eq-[Re₂(CO) ₉(η¹-trans-PPh₂CHCHPPh₂)] appears to be indefinitely stable towards equatorial → axial isomerization at room temperature, thus, allowing its crystal structure to be determined.

Original language	English
Pages (from-to)	3765-3773
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	16
DOIs	https://doi.org/10.1016/j.jorganchem.2005.05.010
Publication status	Published - Aug 15 2005
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Amine-oxide
Carbonyl
Equatorial isomer
Monodentate diphosphines
Phosphine-oxide complexes
Rhenium

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10.1016/j.jorganchem.2005.05.010

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@article{a88e658e7ee7462cabca0e1154cded5f,

title = "Rhenium carbonyl complexes with monodentate-coordinated diphosphines: Activation of terminal phosphino groups towards amine-oxide oxidation",

abstract = "Terminal phosphino groups of [Re2(CO)9(η 1-P-P)] (P-P = diphosphines) are activated towards oxidation by Me3NO. The respective reactions of Me3NO with [Re 2(CO)9{η1-P(o-anisyl)2(CH 2)3PPh2}], [Re2(CO) 9{η1-PPh2(CH2) 3P(o-anisyl)2}] and [Re2(CO) 9(η1-trans-PPh2CH=CHPPh2)] were studied to investigate the mechanism of this oxidation. The results are consistent with an intramolecular pathway involving a cyclic intermediate, without exchange of the coordinated and terminal phosphino groups. A mechanism which involves an interaction of the terminal phosphino group with a carbonyl ligand is proposed. In sharp contrast to eq-[Re2(CO) 9(η1-P-P)] (P-P = Ph2P(CH2) nPPh2, n = 1-6), eq-[Re2(CO) 9(η1-trans-PPh2CHCHPPh2)] appears to be indefinitely stable towards equatorial → axial isomerization at room temperature, thus, allowing its crystal structure to be determined.",

keywords = "Amine-oxide, Carbonyl, Equatorial isomer, Monodentate diphosphines, Phosphine-oxide complexes, Rhenium",

author = "Wei Fan and Rui Zhang and Leong, {Weng Kee} and Chu, {Chit Kay} and Yan, {Yaw Kai}",

year = "2005",

month = aug,

day = "15",

doi = "10.1016/j.jorganchem.2005.05.010",

language = "English",

volume = "690",

pages = "3765--3773",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "16",

}

TY - JOUR

T1 - Rhenium carbonyl complexes with monodentate-coordinated diphosphines

T2 - Activation of terminal phosphino groups towards amine-oxide oxidation

AU - Fan, Wei

AU - Zhang, Rui

AU - Leong, Weng Kee

AU - Chu, Chit Kay

AU - Yan, Yaw Kai

PY - 2005/8/15

Y1 - 2005/8/15

N2 - Terminal phosphino groups of [Re2(CO)9(η 1-P-P)] (P-P = diphosphines) are activated towards oxidation by Me3NO. The respective reactions of Me3NO with [Re 2(CO)9{η1-P(o-anisyl)2(CH 2)3PPh2}], [Re2(CO) 9{η1-PPh2(CH2) 3P(o-anisyl)2}] and [Re2(CO) 9(η1-trans-PPh2CH=CHPPh2)] were studied to investigate the mechanism of this oxidation. The results are consistent with an intramolecular pathway involving a cyclic intermediate, without exchange of the coordinated and terminal phosphino groups. A mechanism which involves an interaction of the terminal phosphino group with a carbonyl ligand is proposed. In sharp contrast to eq-[Re2(CO) 9(η1-P-P)] (P-P = Ph2P(CH2) nPPh2, n = 1-6), eq-[Re2(CO) 9(η1-trans-PPh2CHCHPPh2)] appears to be indefinitely stable towards equatorial → axial isomerization at room temperature, thus, allowing its crystal structure to be determined.

AB - Terminal phosphino groups of [Re2(CO)9(η 1-P-P)] (P-P = diphosphines) are activated towards oxidation by Me3NO. The respective reactions of Me3NO with [Re 2(CO)9{η1-P(o-anisyl)2(CH 2)3PPh2}], [Re2(CO) 9{η1-PPh2(CH2) 3P(o-anisyl)2}] and [Re2(CO) 9(η1-trans-PPh2CH=CHPPh2)] were studied to investigate the mechanism of this oxidation. The results are consistent with an intramolecular pathway involving a cyclic intermediate, without exchange of the coordinated and terminal phosphino groups. A mechanism which involves an interaction of the terminal phosphino group with a carbonyl ligand is proposed. In sharp contrast to eq-[Re2(CO) 9(η1-P-P)] (P-P = Ph2P(CH2) nPPh2, n = 1-6), eq-[Re2(CO) 9(η1-trans-PPh2CHCHPPh2)] appears to be indefinitely stable towards equatorial → axial isomerization at room temperature, thus, allowing its crystal structure to be determined.

KW - Amine-oxide

KW - Carbonyl

KW - Equatorial isomer

KW - Monodentate diphosphines

KW - Phosphine-oxide complexes

KW - Rhenium

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U2 - 10.1016/j.jorganchem.2005.05.010

DO - 10.1016/j.jorganchem.2005.05.010

M3 - Article

AN - SCOPUS:23844538152

SN - 0022-328X

VL - 690

SP - 3765

EP - 3773

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 16

ER -

Rhenium carbonyl complexes with monodentate-coordinated diphosphines: Activation of terminal phosphino groups towards amine-oxide oxidation

Abstract

ASJC Scopus Subject Areas

Keywords

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