Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes

Muhammad S. Khan; Ashok K. Kakkar; Scott L. Ingham; Paul R. Raithby; Jack Lewis; Brock Spencer; Felix Wittmann; Richard H. Friend

doi:10.1016/0022-328X(94)80211-4

Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes

Muhammad S. Khan, Ashok K. Kakkar, Scott L. Ingham, Paul R. Raithby, Jack Lewis, Brock Spencer, Felix Wittmann, Richard H. Friend

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

Abstract

Syntheses of the mono-, bis- and poly-nuclear Ru-σ-acetylide complexes, trans-[Ru(CO)₂(PⁿBu₃)₂(CC C₆H₅)₂], trans-[ClRu(CO)₂(PⁿBu₃)₂CCpC₆H₄C₆H₄ pCCRu(CO)₂(PⁿBu₃)₂Cl] and trans-[Ru(CO)₂(PⁿBu₃)₂CC RCC]_n(R = p-C₆H₄, p(CH₃)₂C₆H₂) are reported. A study of the electronic structure of model metal-acetylide complexes of Group 8, M(L)₂,(L′)₂(RH)₂, ClRu(L or L′)₄RRu(L or L′)₄ Cl, [M(PH₃)₄(RH)]₂R and [M(L)(L)₂(R)]_n, (M Fe, Ru; L L′ PH₃, PMe₃; L CO, L′ PH₃; R CC, CCC₆H₄CC, CH CHpC₆H₄CHCH) has been carried out using the Fenske-Hall molecular orbital model. These results and a comparison of the IR (v_CC stretching frequencies) and optical absorption (π-π{black star} energy band gap) spectra of these complexes provide evidence for the role of (i) auxiliary ligands, (ii) metal, and (iii) the bridging alkyne units in determining the extent of π-electron conjugation in the backbone of these rigid rod organometallic complexes.

Original language	English
Pages (from-to)	247-255
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	472
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(94)80211-4
Publication status	Published - 14 Jun 1994

Funding

We thank the SERC (M.S. Khan, S.L. Ingham), Kobe Steel Europe Ltd. (M.S. Khan) and the NSERC of Canada (A.K. Kakkar) for financial support. We also thank Dr. I. Hinton at Ciba-Geigy Plastics for determinationo f molecularw eights.

Funders	Funder number
Kobe Steel Europe Ltd.
Université Laval
Connecticut State Emergency Response Commission

Keywords

Acetylene
Electronic structure
Molecular orbital calculations
Phosphine
Polymer
Ruthenium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/0022-328X(94)80211-4

Cite this

@article{ffdbf9b729c344b5984dda462ae333db,

title = "Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes",

abstract = "Syntheses of the mono-, bis- and poly-nuclear Ru-σ-acetylide complexes, trans-[Ru(CO)2(PnBu3)2(CC C6H5)2], trans-[ClRu(CO)2(PnBu3)2CCpC6H4C6H4 pCCRu(CO)2(PnBu3)2Cl] and trans-[Ru(CO)2(PnBu3)2CC RCC]n(R = p-C6H4, p(CH3)2C6H2) are reported. A study of the electronic structure of model metal-acetylide complexes of Group 8, M(L)2,(L′)2(RH)2, ClRu(L or L′)4RRu(L or L′)4 Cl, [M(PH3)4(RH)]2R and [M(L)(L)2(R)]n, (M Fe, Ru; L L′ PH3, PMe3; L CO, L′ PH3; R CC, CCC6H4CC, CH CHpC6H4CHCH) has been carried out using the Fenske-Hall molecular orbital model. These results and a comparison of the IR (vCC stretching frequencies) and optical absorption (π-π{black star} energy band gap) spectra of these complexes provide evidence for the role of (i) auxiliary ligands, (ii) metal, and (iii) the bridging alkyne units in determining the extent of π-electron conjugation in the backbone of these rigid rod organometallic complexes.",

keywords = "Acetylene, Electronic structure, Molecular orbital calculations, Phosphine, Polymer, Ruthenium",

author = "Khan, {Muhammad S.} and Kakkar, {Ashok K.} and Ingham, {Scott L.} and Raithby, {Paul R.} and Jack Lewis and Brock Spencer and Felix Wittmann and Friend, {Richard H.}",

year = "1994",

month = jun,

day = "14",

doi = "10.1016/0022-328X(94)80211-4",

language = "English",

volume = "472",

pages = "247--255",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

T1 - Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes

AU - Khan, Muhammad S.

AU - Kakkar, Ashok K.

AU - Ingham, Scott L.

AU - Raithby, Paul R.

AU - Lewis, Jack

AU - Spencer, Brock

AU - Wittmann, Felix

AU - Friend, Richard H.

PY - 1994/6/14

Y1 - 1994/6/14

N2 - Syntheses of the mono-, bis- and poly-nuclear Ru-σ-acetylide complexes, trans-[Ru(CO)2(PnBu3)2(CC C6H5)2], trans-[ClRu(CO)2(PnBu3)2CCpC6H4C6H4 pCCRu(CO)2(PnBu3)2Cl] and trans-[Ru(CO)2(PnBu3)2CC RCC]n(R = p-C6H4, p(CH3)2C6H2) are reported. A study of the electronic structure of model metal-acetylide complexes of Group 8, M(L)2,(L′)2(RH)2, ClRu(L or L′)4RRu(L or L′)4 Cl, [M(PH3)4(RH)]2R and [M(L)(L)2(R)]n, (M Fe, Ru; L L′ PH3, PMe3; L CO, L′ PH3; R CC, CCC6H4CC, CH CHpC6H4CHCH) has been carried out using the Fenske-Hall molecular orbital model. These results and a comparison of the IR (vCC stretching frequencies) and optical absorption (π-π{black star} energy band gap) spectra of these complexes provide evidence for the role of (i) auxiliary ligands, (ii) metal, and (iii) the bridging alkyne units in determining the extent of π-electron conjugation in the backbone of these rigid rod organometallic complexes.

AB - Syntheses of the mono-, bis- and poly-nuclear Ru-σ-acetylide complexes, trans-[Ru(CO)2(PnBu3)2(CC C6H5)2], trans-[ClRu(CO)2(PnBu3)2CCpC6H4C6H4 pCCRu(CO)2(PnBu3)2Cl] and trans-[Ru(CO)2(PnBu3)2CC RCC]n(R = p-C6H4, p(CH3)2C6H2) are reported. A study of the electronic structure of model metal-acetylide complexes of Group 8, M(L)2,(L′)2(RH)2, ClRu(L or L′)4RRu(L or L′)4 Cl, [M(PH3)4(RH)]2R and [M(L)(L)2(R)]n, (M Fe, Ru; L L′ PH3, PMe3; L CO, L′ PH3; R CC, CCC6H4CC, CH CHpC6H4CHCH) has been carried out using the Fenske-Hall molecular orbital model. These results and a comparison of the IR (vCC stretching frequencies) and optical absorption (π-π{black star} energy band gap) spectra of these complexes provide evidence for the role of (i) auxiliary ligands, (ii) metal, and (iii) the bridging alkyne units in determining the extent of π-electron conjugation in the backbone of these rigid rod organometallic complexes.

KW - Acetylene

KW - Electronic structure

KW - Molecular orbital calculations

KW - Phosphine

KW - Polymer

KW - Ruthenium

UR - http://www.scopus.com/inward/record.url?scp=0000730784&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(94)80211-4

DO - 10.1016/0022-328X(94)80211-4

M3 - Article

AN - SCOPUS:0000730784

SN - 0022-328X

VL - 472

SP - 247

EP - 255

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this