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.
N1 - Funding Information:
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.
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
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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 -