Thiol end-capped titanium–copper complexes: Synthesis, solid state structure and electrochemical behavior
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摘要
Die Darstellung zahlreicher donorfunktionalisierter Acetylide mit Ti(IV) und/oder Metallen der Gruppe II des Periodensystems der Elemente wird beschrieben. Bringt man [Ti]Cl2 (pan style='font-weight: bold'>1pan>) {[Ti]=(ηp>5p>-C5H4SiMe3)2Ti} mit zwei Äquivalenten LiCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>1p> [pan style='font-weight: bold'>2apan>: Rp>1p>=CMe=CH2; pan style='font-weight: bold'>2bpan>: Rp>1p>=C6H4Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N-4; pan style='font-weight: bold'>2cpan>: Rp>1p>=CH2NMe2; pan style='font-weight: bold'>2dpan>: R=C5H4N-4] zur Reaktion, so erhält man die Bis(alkinyl)-Titanocene [Ti](Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>1p>)2 [pan style='font-weight: bold'>3apan>: Rp>1p>=CMe=CH2; pan style='font-weight: bold'>3bpan>: Rp>1p>=C6H4Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N-4; pan style='font-weight: bold'>3cpan>: Rp>1p>=CH2NMe2] in guter Ausbeute. Während die Umsetzung von pan style='font-weight: bold'>1pan> mit zwei Äquivalenten pan style='font-weight: bold'>2dpan> ein untrennbares Produktgemisch ergibt, erhält man bei der 1:1 Reaktion von [Ti](Cl)(CH2SiMe3) (pan style='font-weight: bold'>4pan>) mit pan style='font-weight: bold'>2dpan> den Komplex [Ti](CH2SiMe3)(Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CC6H4N-4) (pan style='font-weight: bold'>5pan>) in sehr guter Ausbeute. Monomere, donorfunktionalisierte Kupfer(I)-Acetylide der allgemeinen Art {[Ti](Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>1p>)2}CuCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>3p> [Rp>1p>=p>pan style='font-style: italic'>tpan>p>Bu, pan style='font-weight: bold'>7apan>: Rp>3p>=Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CCH2CH3; pan style='font-weight: bold'>7bpan>: Rp>3p>=CMe=CH2; pan style='font-weight: bold'>7cpan>: Rp>3p>=C6H4Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N-4; Rp>1p>=SiMe3, pan style='font-weight: bold'>7dpan>: Rp>3p>=CMe=CH2; pan style='font-weight: bold'>7epan>: Rp>3p>=C6H4Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N-4] sind über folgende Reaktionswege zugänglich: (i) Umsetzung von {[Ti](Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">Cp>pan style='font-style: italic'>tpan>p>Bu)2}CuSC6H4CH2NMe2-2 (pan style='font-weight: bold'>6pan>) mit pan style='font-weight: bold'>2apan>–pan style='font-weight: bold'>2cpan> und (ii) Umsetzung von {[Ti](Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>1p>)2}CuCH3 (pan style='font-weight: bold'>8apan>: Rp>1p>=SiMe3; pan style='font-weight: bold'>8bpan>: Rp>1p>=p>pan style='font-style: italic'>tpan>p>Bu) mit HCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>3p> [pan style='font-weight: bold'>9apan>: Rp>3p>=Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CCH2CH3; pan style='font-weight: bold'>9bpan>: Rp>3p>=CMe=CH2; pan style='font-weight: bold'>9cpan>: Rp>3p>=C6H4Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N-4] im Verhältnis von 1:1. Das Reaktionsverhalten dieser Komplexe gegenüber ausgewählten Übergangsmetallver-bindungen wird vorgestellt. Die Bis(alkinyl)-Titanocene pan style='font-weight: bold'>3apan>–pan style='font-weight: bold'>3cpan> ergeben bei ihrer Reaktion mit MLn {pan style='font-weight: bold'>10apan>: MLpan style='font-style: italic'>npan>=CuCl; pan style='font-weight: bold'>10bpan>: MLpan style='font-style: italic'>npan>=CuI; pan style='font-weight: bold'>10cpan>: MLpan style='font-style: italic'>npan>=[Cu(CH3Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N)4][PF6]; pan style='font-weight: bold'>10dpan>: MLpan style='font-style: italic'>npan>=AgBF4; pan style='font-weight: bold'>10epan>: MLpan style='font-style: italic'>npan>=Ni(CO)4} die heterobimetallischen Pinzetten-moleküle {[Ti](Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CRp>1p>)2}ML [Rp>1p>=CMe=CH2; pan style='font-weight: bold'>11apan>: ML=CuCl; Rp>1p>=C6H4Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">N-4; pan style='font-weight: bold'>11bpan>: ML=CuCl; pan style='font-weight: bold'>11cpan>: ML=CuI; pan style='font-weight: bold'>11dpan>: ML=Ni(CO); Rp>1p>=CH2NMe2, pan style='font-weight: bold'>11epan>: ML=CuPF6; pan style='font-weight: bold'>11fpan>: ML=AgBF4]. In den Komplexen pan style='font-weight: bold'>11apan>–pan style='font-weight: bold'>11fpan> sind ein frühes [Ti(IV)] und ein spätes Übergangsmetallzentrum [z.B. Ni(0)] über die entsprechenden Rp>1p>Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">C Liganden der metallorganischen π-Pinzette miteinander verbrückt. Für die Verbindungen pan style='font-weight: bold'>11epan> und pan style='font-weight: bold'>11fpan> wird in Lösung ein dynamisches Verhalten beobachtet. Die Festkörperstrukturen von pan style='font-weight: bold'>3cpan> und pan style='font-weight: bold'>7apan> zeigen die für diese Verbindungstypen typischen strukturellen Merkmale: (i) Eine tetraedrische Umgebung um das Ti(IV)-Zentrum von pan style='font-weight: bold'>3cpan> und pan style='font-weight: bold'>7apan>, (ii) eine Verlängerung der Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">C Dreifachbindung durch die ηp>2p>-Koordination an das Übegangsmetallkomplex-Fragment CuCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">CC2H5, (iii) eine pan style='font-style: italic'>transpan>-Abwinkelung der Ti---Cp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">C---p>pan style='font-style: italic'>tpan>p>Bu-Einheit sowie (iv) eine Verkleinerung des Winkels CCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">C---Ti---CCp://www.sciencedirect.com/scidirimg/entities/tbnd6" alt="6-point triple bond; length half of m-dash" title="6-point triple bond; length half of m-dash">C für pan style='font-weight: bold'>7apan>.

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<p>Thiol end-capped titanium–copper complexes: Synthesis, solid state structure and electrochemical behavior

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