The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds

ME Smith; RL Cordiner; D Albesa-Jove; DS Yufit; F Hartl; JAK Howard; PJ Low

doi:10.1139/V05-238

The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds

ME Smith, RL Cordiner, D Albesa-Jove, DS Yufit, F Hartl, JAK Howard, PJ Low

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

12 Citations (Scopus)

Abstract

The cyanoacetylide complex Fe(CCCN)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(CCSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)(2)], [Ru(PPh3)(2)Cp](+), and [Ru(dppe)Cp*](+) affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-CCCN-MLn](n+), spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-CCCN-MLn]((n+1)+).

Original language	English
Pages (from-to)	154-163
Number of pages	10
Journal	Canadian Journal of Chemistry
Volume	84
Issue number	2
DOIs	https://doi.org/10.1139/V05-238
Publication status	Published - Feb 2006
Externally published	Yes

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@article{c1161d68e17841eca7af166ee4c9e4cd,

title = "The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds",

abstract = "The cyanoacetylide complex Fe(CCCN)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(CCSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)(2)], [Ru(PPh3)(2)Cp](+), and [Ru(dppe)Cp*](+) affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-CCCN-MLn](n+), spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-CCCN-MLn]((n+1)+).",

keywords = "cyanide, cyanoacetylide, crystal structure, NONLINEAR-OPTICAL PROPERTIES, RAY CRYSTAL-STRUCTURES, MIXED-VALENCE COMPLEX, ALKYNYL COMPLEXES, NUCLEOPHILIC PROPERTIES, COORDINATION CHEMISTRY, VINYLIDENE COMPLEXES, ELECTRONIC-STRUCTURE, MOLECULAR WIRES, IRON",

author = "ME Smith and RL Cordiner and D Albesa-Jove and DS Yufit and F Hartl and JAK Howard and PJ Low",

year = "2006",

month = feb,

doi = "10.1139/V05-238",

language = "English",

volume = "84",

pages = "154--163",

journal = "Canadian Journal of Chemistry",

issn = "0008-4042",

publisher = "CANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESS",

number = "2",

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TY - JOUR

T1 - The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds

AU - Smith, ME

AU - Cordiner, RL

AU - Albesa-Jove, D

AU - Yufit, DS

AU - Hartl, F

AU - Howard, JAK

AU - Low, PJ

PY - 2006/2

Y1 - 2006/2

N2 - The cyanoacetylide complex Fe(CCCN)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(CCSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)(2)], [Ru(PPh3)(2)Cp](+), and [Ru(dppe)Cp*](+) affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-CCCN-MLn](n+), spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-CCCN-MLn]((n+1)+).

AB - The cyanoacetylide complex Fe(CCCN)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(CCSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)(2)], [Ru(PPh3)(2)Cp](+), and [Ru(dppe)Cp*](+) affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-CCCN-MLn](n+), spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-CCCN-MLn]((n+1)+).

KW - cyanide

KW - cyanoacetylide

KW - crystal structure

KW - NONLINEAR-OPTICAL PROPERTIES

KW - RAY CRYSTAL-STRUCTURES

KW - MIXED-VALENCE COMPLEX

KW - ALKYNYL COMPLEXES

KW - NUCLEOPHILIC PROPERTIES

KW - COORDINATION CHEMISTRY

KW - VINYLIDENE COMPLEXES

KW - ELECTRONIC-STRUCTURE

KW - MOLECULAR WIRES

KW - IRON

U2 - 10.1139/V05-238

DO - 10.1139/V05-238

M3 - Article

SN - 0008-4042

VL - 84

SP - 154

EP - 163

JO - Canadian Journal of Chemistry

JF - Canadian Journal of Chemistry

IS - 2

ER -

The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds

Abstract

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