Dissecting out the effect of Ru-OAr bonding in a five-coordinate complex of ruthenium (II)

Sebastien Monfette; João A. Duarte Silva; Serge I. Gorelsky; Scott J. Dalgarno; Eduardo N. Dos Santos; Maria H. Araujo; Deryn E. Fogg

doi:10.1139/V08-147

Dissecting out the effect of Ru-OAr bonding in a five-coordinate complex of ruthenium (II)

Sebastien Monfette, João A. Duarte Silva, Serge I. Gorelsky, Scott J. Dalgarno, Eduardo N. Dos Santos, Maria H. Araujo, Deryn E. Fogg

School of Engineering & Physical Sciences

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

6 Citations (Scopus)

Abstract

Blue Ru(o-cat)(PPh₃)₃ (5; o-cat = ortho-catecholate), obtained in 94% yield by reaction of RuCl₂(PPh₃) ₃ (4) with dithallium catecholate, was characterized by NMR, MALDI-MS, IR, and single crystal X-ray analysis, and by a combined electronic spectroscopy and time-dependent density functional theory (TD-DFT) study. The frontier orbitals in 5 participate in a low-energy charge transfer excitation involving donation from the Ru-catecholate p bond (largely localized on catecholate) to a low-lying s^z.ast; orbital on Ru-PPh _3(apical). The energy of this transition increases on binding a pyridine ligand in the sixth site. © 2008 NRC Canada.

Original language	English
Pages (from-to)	361-367
Number of pages	7
Journal	Canadian Journal of Chemistry
Volume	87
Issue number	1 SPEC. ISS.
DOIs	https://doi.org/10.1139/V08-147
Publication status	Published - Jan 2009

Keywords

Catecholate
Electronic spectroscopy
Phosphine
Ruthenium aryloxide
Time-dependent DFT

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10.1139/V08-147

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@article{302c580b6d6b4093b4fd31e68db95275,

title = "Dissecting out the effect of Ru-OAr bonding in a five-coordinate complex of ruthenium (II)",

abstract = "Blue Ru(o-cat)(PPh3)3 (5; o-cat = ortho-catecholate), obtained in 94% yield by reaction of RuCl2(PPh3) 3 (4) with dithallium catecholate, was characterized by NMR, MALDI-MS, IR, and single crystal X-ray analysis, and by a combined electronic spectroscopy and time-dependent density functional theory (TD-DFT) study. The frontier orbitals in 5 participate in a low-energy charge transfer excitation involving donation from the Ru-catecholate p bond (largely localized on catecholate) to a low-lying sz.ast; orbital on Ru-PPh 3(apical). The energy of this transition increases on binding a pyridine ligand in the sixth site. {\textcopyright} 2008 NRC Canada.",

keywords = "Catecholate, Electronic spectroscopy, Phosphine, Ruthenium aryloxide, Time-dependent DFT",

author = "Sebastien Monfette and {Duarte Silva}, {Jo{\~a}o A.} and Gorelsky, {Serge I.} and Dalgarno, {Scott J.} and {Dos Santos}, {Eduardo N.} and Araujo, {Maria H.} and Fogg, {Deryn E.}",

year = "2009",

month = jan,

doi = "10.1139/V08-147",

language = "English",

volume = "87",

pages = "361--367",

journal = "Canadian Journal of Chemistry",

issn = "0008-4042",

publisher = "National Research Council of Canada",

number = "1 SPEC. ISS.",

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TY - JOUR

T1 - Dissecting out the effect of Ru-OAr bonding in a five-coordinate complex of ruthenium (II)

AU - Monfette, Sebastien

AU - Duarte Silva, João A.

AU - Gorelsky, Serge I.

AU - Dalgarno, Scott J.

AU - Dos Santos, Eduardo N.

AU - Araujo, Maria H.

AU - Fogg, Deryn E.

PY - 2009/1

Y1 - 2009/1

N2 - Blue Ru(o-cat)(PPh3)3 (5; o-cat = ortho-catecholate), obtained in 94% yield by reaction of RuCl2(PPh3) 3 (4) with dithallium catecholate, was characterized by NMR, MALDI-MS, IR, and single crystal X-ray analysis, and by a combined electronic spectroscopy and time-dependent density functional theory (TD-DFT) study. The frontier orbitals in 5 participate in a low-energy charge transfer excitation involving donation from the Ru-catecholate p bond (largely localized on catecholate) to a low-lying sz.ast; orbital on Ru-PPh 3(apical). The energy of this transition increases on binding a pyridine ligand in the sixth site. © 2008 NRC Canada.

AB - Blue Ru(o-cat)(PPh3)3 (5; o-cat = ortho-catecholate), obtained in 94% yield by reaction of RuCl2(PPh3) 3 (4) with dithallium catecholate, was characterized by NMR, MALDI-MS, IR, and single crystal X-ray analysis, and by a combined electronic spectroscopy and time-dependent density functional theory (TD-DFT) study. The frontier orbitals in 5 participate in a low-energy charge transfer excitation involving donation from the Ru-catecholate p bond (largely localized on catecholate) to a low-lying sz.ast; orbital on Ru-PPh 3(apical). The energy of this transition increases on binding a pyridine ligand in the sixth site. © 2008 NRC Canada.

KW - Catecholate

KW - Electronic spectroscopy

KW - Phosphine

KW - Ruthenium aryloxide

KW - Time-dependent DFT

UR - http://www.scopus.com/inward/record.url?scp=67650911654&partnerID=8YFLogxK

U2 - 10.1139/V08-147

DO - 10.1139/V08-147

M3 - Article

SN - 0008-4042

VL - 87

SP - 361

EP - 367

JO - Canadian Journal of Chemistry

JF - Canadian Journal of Chemistry

IS - 1 SPEC. ISS.

ER -

Dissecting out the effect of Ru-OAr bonding in a five-coordinate complex of ruthenium (II)

Abstract

Keywords

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