Heterometallic early–late π-tweezer complexes: their synthesis, electrochemical behaviour and the solid-state structures of (η5-C5H4SiMe3)2Ti(CCPh)2 and [(η5-C5H4SiMe3)2Ti(CCPh)2]Pd(PPh3)

Titanocene-based group-11 metal ions; solid-state structure of {[(η5-C5H4SiMe3)2Ti(CCPh)2]2Ag}NO3

“…In this context, however, the interatomic bond distances of the alkynyl units C (1) Table 2) are almost not affected, when compared to [Ti](C"CPh) 2 (1b) [1,21]. This differs from systems reported so far in organometallic p-tweezer chemistry, where elongations between 0.1 and 0.2 Å are typical [1].…”

“…This can be assigned to the Ti(IV)/Ti(III) reduction. In comparison to 1b [Ti(IV)/Ti(III): E 0 = À1.76 V (DE = 150 mV)] [21] this reduction is significantly shifted to a more negative value. Similar data were found for {[Ti](l-r,p-C"CPh) 2 }Ni(CO), where the Ti(VI)/Ti(III) redox couple appears at E 0 = À2.45 V (DE = 150 mV) [21].…”

“…In comparison to 1b [Ti(IV)/Ti(III): E 0 = À1.76 V (DE = 150 mV)] [21] this reduction is significantly shifted to a more negative value. Similar data were found for {[Ti](l-r,p-C"CPh) 2 }Ni(CO), where the Ti(VI)/Ti(III) redox couple appears at E 0 = À2.45 V (DE = 150 mV) [21]. Thus, the nature of the chemical species, which is formed after the Cu(I)/Cu(0) reduction process in 3c can hardly be determined by means of cyclic voltammetric investigations.…”

“…1). The two tweezer entities [Ti](C"CPh) 2 Through the side-on coordination of the C"C triple bonds to a tetra-coordinated silver(I) ion the bite angles C a -Ti-C 0 a in 3e show, as typical for tweezer-type molecules [1], a reduction from 96.1(2)°in 1b [1,20,21] to 94.2(1)°and 93.7(1)°in 3e [1,21].…”

4‐Thiolatobenzoato‐Bridged Rhodium/Zirconium Complexes: 32‐Membered Metallamacrocycles and Their Linear Dinuclear Counterparts

“…These can be achieved either by direct contact of the metal centres within the compounds [6] or with the help of bridging ligands which allow electronic interactions through π-conjugated bridges. [7] To elucidate the influence of the second metal centre, it is useful to compare the properties of the heterometallic complexes with those of their mononuclear precursors. Therefore, the preferred synthesis of ELHBs starts with the preparation of a monometallic complex, which is then employed as a so-called metalloligand to coordinate the second metal centre.…”