Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Complexes [{Ru(CO)Cl(P<jats:italic>i</jats:italic>Pr<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>(μ‐2,5‐(CHCH)<jats:sub>2</jats:sub>‐<jats:sup><jats:italic>c</jats:italic></jats:sup>C<jats:sub>4</jats:sub>H<jats:sub>2</jats:sub>E] (E=NR; R=C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>‐4‐NMe<jats:sub>2</jats:sub> (<jats:bold>10 a</jats:bold>), C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>‐4‐OMe (<jats:bold>10 b</jats:bold>), C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>‐4‐Me (<jats:bold>10 c</jats:bold>), C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub> (<jats:bold>10 d</jats:bold>), C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>‐4‐CO<jats:sub>2</jats:sub>Et (<jats:bold>10 e</jats:bold>), C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>‐4‐NO<jats:sub>2</jats:sub> (<jats:bold>10 f</jats:bold>), C<jats:sub>6</jats:sub>H<jats:sub>3</jats:sub>‐3,5‐(CF<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub> (<jats:bold>10 g</jats:bold>), CH<jats:sub>3</jats:sub> (<jats:bold>11</jats:bold>); E=O (<jats:bold>12</jats:bold>), S (<jats:bold>13</jats:bold>)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro)electrochemical studies show a moderate influence of the nature of the heteroatom and the electron‐donating or ‐withdrawing substituents R in <jats:bold>10 a</jats:bold>–<jats:bold>g</jats:bold> on the electrochemical and spectroscopic properties. The CVs display two consecutive one‐electron redox events with Δ<jats:italic>E</jats:italic>°′=350–495 mV. A linear relationship between Δ<jats:italic>E</jats:italic>°′ and the <jats:italic>σ</jats:italic><jats:sub>p</jats:sub> Hammett constant for <jats:bold>10 a–f</jats:bold> was found. IR, UV/Vis/NIR and EPR studies for <jats:bold>10</jats:bold><jats:sup>+</jats:sup>–<jats:bold>13</jats:bold><jats:sup>+</jats:sup> confirm full charge delocalization over the {Ru}CHCH‐heterocycle‐CHCH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT‐optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.</jats:p>