Electrochemistry of [{Ru3(CO)9(μ3-η2-CCtBu)}2Hg] and [Ru3(CO)9(μ3-η2-C CtBu)HgX] {X Re(CO)5 or MoCp(CO)3}

Domenico Osella; Luciano Milone; Sergei V. Kukharenko; Vladimir V. Strelets; Edward Rosenberg; Sharad Hajela

doi:10.1016/0022-328X(93)83020-V

Electrochemistry of [{Ru₃(CO)₉(μ₃-η²-CC^tBu)}₂Hg] and [Ru₃(CO)₉(μ₃-η²-C C^tBu)HgX] {X Re(CO)₅ or MoCp(CO)₃}

Domenico Osella, Luciano Milone, Sergei V. Kukharenko, Vladimir V. Strelets, Edward Rosenberg, Sharad Hajela

Risultato della ricerca: Contributo su rivista › Articolo in rivista › peer review

Abstract

The electrochemical reduction of [{Ru₃(CO)₉(μ₃-η²-CC^tBu)}₂Hg] and [Ru₃(CO)₉(μ₃-η²- CC^tBu)HgX] {X Re(CO)₅ or MoCP(CO)₃} has been investigated at both Pt and Hg electrodes in tetrahydrofuran (THF) at different temperatures by means of cyclic voltammetry and coulometry. All the compounds undergo chemically irreversible reduction followed by the formation of [Ru₃(CO)₉(μ₃-η²-CC^tBu)]^- anion, mercury, and organometallic radical X^· at essentially the same potential. Despite the isolobal relationship between the proton in [Ru₃(μ-H)(CO)₉(μ₃η² -CC^tBu)] and the HgX fragment, the reduction potentials of title compounds are significantly less negative (ca. 0.3 V) suggesting that the LUMO in these complexes is at lower energy than in the corresponding hydride, and has significant mercury character.

Lingua originale	Inglese
pagine (da-a)	153-156
Numero di pagine	4
Rivista	Journal of Organometallic Chemistry
Volume	451
Numero di pubblicazione	1-2
DOI	https://doi.org/10.1016/0022-328X(93)83020-V
Stato di pubblicazione	Pubblicato - 1 giu 1993
Pubblicato esternamente	Sì

Accesso al documento

10.1016/0022-328X(93)83020-V

Altri file e collegamenti

Link to publication in Scopus

Cita questo

@article{32d6507ace854012a6492b7916972dbe,

title = "Electrochemistry of [{Ru3(CO)9(μ3-η2-CCtBu)}2Hg] and [Ru3(CO)9(μ3-η2-C CtBu)HgX] {X Re(CO)5 or MoCp(CO)3}",

abstract = "The electrochemical reduction of [{Ru3(CO)9(μ3-η2-CCtBu)}2Hg] and [Ru3(CO)9(μ3-η2- CCtBu)HgX] {X Re(CO)5 or MoCP(CO)3} has been investigated at both Pt and Hg electrodes in tetrahydrofuran (THF) at different temperatures by means of cyclic voltammetry and coulometry. All the compounds undergo chemically irreversible reduction followed by the formation of [Ru3(CO)9(μ3-η2-CCtBu)]- anion, mercury, and organometallic radical X · at essentially the same potential. Despite the isolobal relationship between the proton in [Ru3(μ-H)(CO)9(μ3η2 -CCtBu)] and the HgX fragment, the reduction potentials of title compounds are significantly less negative (ca. 0.3 V) suggesting that the LUMO in these complexes is at lower energy than in the corresponding hydride, and has significant mercury character.",

author = "Domenico Osella and Luciano Milone and Kukharenko, {Sergei V.} and Strelets, {Vladimir V.} and Edward Rosenberg and Sharad Hajela",

note = "Funding Information: We thank CNR, MURST, NATO (870705a) nd NSF (CHE-9016495)fo r financial support,J ohnson Matthey Ltd. for a generousl oan of RuCl,, and P.A. Loveday (University Chemical Laboratory, Cambridge,U K) for high-pressures ynthesiso f Ru,(CO),,.",

year = "1993",

month = jun,

day = "1",

doi = "10.1016/0022-328X(93)83020-V",

language = "English",

volume = "451",

pages = "153--156",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

TY - JOUR

T1 - Electrochemistry of [{Ru3(CO)9(μ3-η2-CCtBu)}2Hg] and [Ru3(CO)9(μ3-η2-C CtBu)HgX] {X Re(CO)5 or MoCp(CO)3}

AU - Osella, Domenico

AU - Milone, Luciano

AU - Kukharenko, Sergei V.

AU - Strelets, Vladimir V.

AU - Rosenberg, Edward

AU - Hajela, Sharad

N1 - Funding Information: We thank CNR, MURST, NATO (870705a) nd NSF (CHE-9016495)fo r financial support,J ohnson Matthey Ltd. for a generousl oan of RuCl,, and P.A. Loveday (University Chemical Laboratory, Cambridge,U K) for high-pressures ynthesiso f Ru,(CO),,.

PY - 1993/6/1

Y1 - 1993/6/1

N2 - The electrochemical reduction of [{Ru3(CO)9(μ3-η2-CCtBu)}2Hg] and [Ru3(CO)9(μ3-η2- CCtBu)HgX] {X Re(CO)5 or MoCP(CO)3} has been investigated at both Pt and Hg electrodes in tetrahydrofuran (THF) at different temperatures by means of cyclic voltammetry and coulometry. All the compounds undergo chemically irreversible reduction followed by the formation of [Ru3(CO)9(μ3-η2-CCtBu)]- anion, mercury, and organometallic radical X · at essentially the same potential. Despite the isolobal relationship between the proton in [Ru3(μ-H)(CO)9(μ3η2 -CCtBu)] and the HgX fragment, the reduction potentials of title compounds are significantly less negative (ca. 0.3 V) suggesting that the LUMO in these complexes is at lower energy than in the corresponding hydride, and has significant mercury character.

AB - The electrochemical reduction of [{Ru3(CO)9(μ3-η2-CCtBu)}2Hg] and [Ru3(CO)9(μ3-η2- CCtBu)HgX] {X Re(CO)5 or MoCP(CO)3} has been investigated at both Pt and Hg electrodes in tetrahydrofuran (THF) at different temperatures by means of cyclic voltammetry and coulometry. All the compounds undergo chemically irreversible reduction followed by the formation of [Ru3(CO)9(μ3-η2-CCtBu)]- anion, mercury, and organometallic radical X · at essentially the same potential. Despite the isolobal relationship between the proton in [Ru3(μ-H)(CO)9(μ3η2 -CCtBu)] and the HgX fragment, the reduction potentials of title compounds are significantly less negative (ca. 0.3 V) suggesting that the LUMO in these complexes is at lower energy than in the corresponding hydride, and has significant mercury character.

UR - http://www.scopus.com/inward/record.url?scp=0011658776&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(93)83020-V

DO - 10.1016/0022-328X(93)83020-V

M3 - Article

SN - 0022-328X

VL - 451

SP - 153

EP - 156

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2