TY - JOUR
T1 - Synthesis and characterization of dinuclear metal σ-acetylides and mononuclear metal σ-allenylidenes
AU - Colbert, Michael C.B.
AU - Lewis, Jack
AU - Long, Nicholas J.
AU - Raithby, Paul R.
AU - Younus, Muhammad
AU - White, Andrew J.P.
AU - Williams, David J.
AU - Payne, Nicholas N.
AU - Yellowlees, Lesley
AU - Beljonne, David
AU - Chawdhury, Nazia
AU - Friend, Richard H.
PY - 1998/7/6
Y1 - 1998/7/6
N2 - A series of dinuclear metal σ-acetylides of the type trans-[Cl(P-P)2MC≡CRC≡CM(P-P)2Cl] (M = Fe, Ru, Os; P-P = 1,2-bis(diphenylphosphino)methane (dppm), 1,2-bis(diethylphosphino)ethane (depe), 1,2-bis(dimethylphosphino)ethane (dmpe); R = 1,4-benzenediyl, 1,3-benzenediyl, 2,5-xylenediyl, 2,5-pyridinediyl, 2,5-thiophenediyl) have been formed. Electrochemistry of these complexes shows that there is a metal-metal interaction which is dependent upon the metal and the π-conjugated bridging ligand. Coulometry and optical absorbance spectroscopic studies show the presence of mixed-valence oxidized species which possess a delocalized allenylidene structure and can be classified as Robin and Day "class II" mixed-valence species. Theoretical calculations have been carried out to optimize the geometric structure of the bridging acetylide ligand and indicate that the conjugated system undergoes a structural change upon oxidation to give a quinoid-like geometry. Two mononuclear metal-allenylidene complexes, [Cl(dppm)2M=C=C=CHPh][PF6] (10, M = Ru; 11, M = Os), have also been synthesized and an X-ray crystal structure determination on 10 undertaken. This shows a distorted-octahedral coordination about ruthenium and distinct double-bond character extending along the M-C-C-C chain, which is essentially linear. Structural and spectroscopic details on the metal allenylidenes have been compared to those of the mixed-valence oxidized dinuclear metal acetylides and show that the latter exist in a delocalized allenylidene form.
AB - A series of dinuclear metal σ-acetylides of the type trans-[Cl(P-P)2MC≡CRC≡CM(P-P)2Cl] (M = Fe, Ru, Os; P-P = 1,2-bis(diphenylphosphino)methane (dppm), 1,2-bis(diethylphosphino)ethane (depe), 1,2-bis(dimethylphosphino)ethane (dmpe); R = 1,4-benzenediyl, 1,3-benzenediyl, 2,5-xylenediyl, 2,5-pyridinediyl, 2,5-thiophenediyl) have been formed. Electrochemistry of these complexes shows that there is a metal-metal interaction which is dependent upon the metal and the π-conjugated bridging ligand. Coulometry and optical absorbance spectroscopic studies show the presence of mixed-valence oxidized species which possess a delocalized allenylidene structure and can be classified as Robin and Day "class II" mixed-valence species. Theoretical calculations have been carried out to optimize the geometric structure of the bridging acetylide ligand and indicate that the conjugated system undergoes a structural change upon oxidation to give a quinoid-like geometry. Two mononuclear metal-allenylidene complexes, [Cl(dppm)2M=C=C=CHPh][PF6] (10, M = Ru; 11, M = Os), have also been synthesized and an X-ray crystal structure determination on 10 undertaken. This shows a distorted-octahedral coordination about ruthenium and distinct double-bond character extending along the M-C-C-C chain, which is essentially linear. Structural and spectroscopic details on the metal allenylidenes have been compared to those of the mixed-valence oxidized dinuclear metal acetylides and show that the latter exist in a delocalized allenylidene form.
UR - http://www.scopus.com/inward/record.url?scp=0000829107&partnerID=8YFLogxK
U2 - 10.1021/om970130p
DO - 10.1021/om970130p
M3 - Article
AN - SCOPUS:0000829107
VL - 17
SP - 3034
EP - 3043
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 14
ER -