Synthesis of ROMP Monomers Containing Metal–Metal Bonds

Methods for the synthesis of cyclic monomers that have both metal–metal bonds and carbon–carbon double bonds are reported. Ring opening metathesis polymerization (ROMP) of these monomers would yield polymers that are photochemically degradable. The first method investigated involved substitution of Cp2Fe2(CO)4 by the bidentate phosphine ligand DPPEN (Ph2P \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${-}$$\end{document}CH=CH–PPh2). Cp2Fe2(CO)2( \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\upmu$$\end{document}-DPPEN) was synthesized and the X-ray crystal structure is reported but the molecule could not be polymerized by a ROMP method using Grubbs’s catalyst. The inability of this monomer to polymerize (or copolymerize with cyclooctatetraene) was attributed to the bulky phenyl rings being in close proximity to the C=C in the DPPEN ligand, which prevents coordination of the monomer to the catalyst. To decrease the steric interactions, the DPPBN ligand was synthesized (DPPBN=Ph \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}CH \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}CH=CH \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${-}$$\end{document}CH \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}PPh2). However, the reaction of DPPBN with Cp2Fe2(CO)4 yielded the product Cp2Fe2(CO)2( \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\upmu$$\end{document}-1,2,4-triphos), where the 1,2,4-triphos ligand is a tridentate ligand formed by the formal additional of Ph2PH to DPPBN (1,2,4-triphos=Ph \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}CH \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}CH(PPh2) \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${-}$$\end{document}CH \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}CH \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_{2}{-}$$\end{document}PPh2). An X-ray structure of the Cp2Fe2(CO)2( \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\upmu$$\end{document}-1,2,4-triphos) complex revealed that the 1,2,4-triphos ligand chelates exclusively through the two phosphorus atoms that are bridged by two carbon atoms. It is suggested that this structural feature may simply reflect the increased stability of the 6-membered ring over the 7- and 8-membered rings. The reactions of the Cp2Mo2(CO)6 and Cp2Mo2(CO)4 dimers with DPPBN were investigated next. Reactions of Cp2Mo2(CO)6 and Cp2Mo2(CO)4 with the DPPEN and DPPBN ligands resulted in the disproportionation of the dimers. The X-ray crystal structure of [CpMo(CO)2(DPPEN)][CpMo(CO)3] was determined and is reported. The CpMo(CO)(DPPEN)Cl complex was formed when these same reactions were carried out in the presence of CH2Cl2. The X-ray crystal structure of this molecule is also reported.