Bonding mode of a bifunctional P∼SI-H ligand in the ruthenium complex "Ru(PPh2CH2OSiMe2H)3"

Virginia Montiel-Palma; Olivier Piechaciyk; Alexandre Picot; Audrey Auffrant; Laure Vendier; Pascal Le Floch; Sylviane Sabo-Etienne

doi:10.1021/ic801327a

Bonding mode of a bifunctional P∼SI-H ligand in the ruthenium complex "Ru(PPh₂CH₂OSiMe₂H)₃"

Virginia Montiel-Palma
, Olivier Piechaciyk
, Alexandre Picot
, Audrey Auffrant
, Laure Vendier
, Pascal Le Floch
, Sylviane Sabo-Etienne

Centro de Investigaciones Quimicas
CNRS
CNRS UPR 8241

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

Abstract

The phosphinosilane compound PPh₂CH₂OSiMe ₂H is potentially a bifunctional P∼Si-H ligand. By treatment with the Ru^II precursor RuH₂(H₂) ₂(PCy₃)₂, the complex Ru(PPh₂CH ₂OSiMe₂H)₃ (2), resulting from the coordination of three ligands and the displacement of two PCy₃ and two dihydrogen ligands, was formed. The different bonding modes for each of the three bifunctional P∼Si-H ligands are discussed on the basis of multinuclear NMR, X-ray diffraction, and density functional theory studies. One ligand acts as a monodentate phosphine ligand with a pendant Si-H group, whereas the two others act as bidentate ligands with different Si-H bond activations. Indeed, an intermediate structure between two arrested forms 2a and 2b can be proposed: a dihydrido(disilyl)-ruthenium(IV) species (form 2a) resulting from two Si-H oxidative additions or a hydrido(silyl)ruthenium(II) species (form 2b) presenting an agostic Si-H bond and only one oxidative addition.

Original language	English
Pages (from-to)	8601-8603
Number of pages	3
Journal	Inorganic Chemistry
Volume	47
Issue number	19
DOIs	https://doi.org/10.1021/ic801327a
Publication status	Published - 6 Oct 2008
Externally published	Yes

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@article{ca7fd54f118542179a35b2eae69aa2ee,

title = "Bonding mode of a bifunctional P∼SI-H ligand in the ruthenium complex {"}Ru(PPh2CH2OSiMe2H)3{"}",

abstract = "The phosphinosilane compound PPh2CH2OSiMe 2H is potentially a bifunctional P∼Si-H ligand. By treatment with the RuII precursor RuH2(H2) 2(PCy3)2, the complex Ru(PPh2CH 2OSiMe2H)3 (2), resulting from the coordination of three ligands and the displacement of two PCy3 and two dihydrogen ligands, was formed. The different bonding modes for each of the three bifunctional P∼Si-H ligands are discussed on the basis of multinuclear NMR, X-ray diffraction, and density functional theory studies. One ligand acts as a monodentate phosphine ligand with a pendant Si-H group, whereas the two others act as bidentate ligands with different Si-H bond activations. Indeed, an intermediate structure between two arrested forms 2a and 2b can be proposed: a dihydrido(disilyl)-ruthenium(IV) species (form 2a) resulting from two Si-H oxidative additions or a hydrido(silyl)ruthenium(II) species (form 2b) presenting an agostic Si-H bond and only one oxidative addition.",

author = "Virginia Montiel-Palma and Olivier Piechaciyk and Alexandre Picot and Audrey Auffrant and Laure Vendier and \{Le Floch\}, Pascal and Sylviane Sabo-Etienne",

year = "2008",

month = oct,

day = "6",

doi = "10.1021/ic801327a",

language = "English",

volume = "47",

pages = "8601--8603",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "19",

}

TY - JOUR

T1 - Bonding mode of a bifunctional P∼SI-H ligand in the ruthenium complex "Ru(PPh2CH2OSiMe2H)3"

AU - Montiel-Palma, Virginia

AU - Piechaciyk, Olivier

AU - Picot, Alexandre

AU - Auffrant, Audrey

AU - Vendier, Laure

AU - Le Floch, Pascal

AU - Sabo-Etienne, Sylviane

PY - 2008/10/6

Y1 - 2008/10/6

N2 - The phosphinosilane compound PPh2CH2OSiMe 2H is potentially a bifunctional P∼Si-H ligand. By treatment with the RuII precursor RuH2(H2) 2(PCy3)2, the complex Ru(PPh2CH 2OSiMe2H)3 (2), resulting from the coordination of three ligands and the displacement of two PCy3 and two dihydrogen ligands, was formed. The different bonding modes for each of the three bifunctional P∼Si-H ligands are discussed on the basis of multinuclear NMR, X-ray diffraction, and density functional theory studies. One ligand acts as a monodentate phosphine ligand with a pendant Si-H group, whereas the two others act as bidentate ligands with different Si-H bond activations. Indeed, an intermediate structure between two arrested forms 2a and 2b can be proposed: a dihydrido(disilyl)-ruthenium(IV) species (form 2a) resulting from two Si-H oxidative additions or a hydrido(silyl)ruthenium(II) species (form 2b) presenting an agostic Si-H bond and only one oxidative addition.

AB - The phosphinosilane compound PPh2CH2OSiMe 2H is potentially a bifunctional P∼Si-H ligand. By treatment with the RuII precursor RuH2(H2) 2(PCy3)2, the complex Ru(PPh2CH 2OSiMe2H)3 (2), resulting from the coordination of three ligands and the displacement of two PCy3 and two dihydrogen ligands, was formed. The different bonding modes for each of the three bifunctional P∼Si-H ligands are discussed on the basis of multinuclear NMR, X-ray diffraction, and density functional theory studies. One ligand acts as a monodentate phosphine ligand with a pendant Si-H group, whereas the two others act as bidentate ligands with different Si-H bond activations. Indeed, an intermediate structure between two arrested forms 2a and 2b can be proposed: a dihydrido(disilyl)-ruthenium(IV) species (form 2a) resulting from two Si-H oxidative additions or a hydrido(silyl)ruthenium(II) species (form 2b) presenting an agostic Si-H bond and only one oxidative addition.

U2 - 10.1021/ic801327a

DO - 10.1021/ic801327a

M3 - Article

AN - SCOPUS:54149110542

SN - 0020-1669

VL - 47

SP - 8601

EP - 8603

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 19

ER -

Bonding mode of a bifunctional P∼SI-H ligand in the ruthenium complex "Ru(PPh2CH2OSiMe2H)3"

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Bonding mode of a bifunctional P∼SI-H ligand in the ruthenium complex "Ru(PPh₂CH₂OSiMe₂H)₃"