Lutetium complexes with tetraphenylethylene dianion. Synthesis and structure

Lutetium complexes with the 1,3-diphenylcyclopentadienyl ligand. Syntheses and molecular structures of the complexes {(Ph2C5H3)Lu(C2Ph4)(THF)} and {(Ph2C5H3)LuCl2(THF)3}

“…The interaction between the tetraphenylethylene dianion and the lutetium cation can be best described as the bis allyl η 6 coordination of the tetraphenylethylene dianion analo gous to that found in the [Na(diglyme) 2 ][Lu(Ph 4 C 2 ) 2 ] and (C 5 H 5 )Lu(Ph 4 C 2 )(THF) 2 complexes. 4 In complex 1, the Lu-C 1 , Lu-C 2 , and Lu-C 3 distances (Table 3) are similar to those found 4 in the [Na(diglyme) 2 ][Lu(Ph 4 C 2 ) 2 ](THF) 0.5 (3) and {CpLu(Ph 4 C 2 )(DME)}(DME) (4) complexes. The gen eral atomic numbering of the carbon atoms in the com plexes with the tetraphenylethylene ligand is given below.…”

“…A strong shift of the absorption band of the coordinated tetraphenylethylene dianion (λ max = 390 nm) to shorter wavelengths com pared to the sodium and potassium adducts of tetraphenyl ethylene (λ max = 485 nm) 6 is evidence for the strong co ordination of the tetraphenylethylene dianion to the Lu 3+ cation. 4 The shift of the absorption band in the spectrum of complex 1 (∆λ max = 95 nm) is the maximum of all the shifts observed in the spectra of lanthanide com plexes with the tetraphenylethylene dianion, whereas the smallest shift (75 nm) is observed for the complex with the unsubstituted Cp ligand, (C 5 H 5 )Lu(Ph 4 C 2 )(THF) 2 . Apparently, the introduction of Ph substituents decreases the electron density on the atoms of the Cp ring, which, in turn, reduces the electron density on the lutetium cat ion and results in a strengthening of the Lu-(C 2 Ph 4 ) bond and, consequently, in a larger shift of the absorption band of the tetraphenylethylene dianion.…”

“…The solvents were purified and stored according to procedures described earlier. 4 The LuCl 3 (THF) 3 complex was isolated by extraction of anhydrous lutetium tri chloride, which was prepared from the hexahydrate, 17 with hot THF. Tetraphenylethylene (Acros, 98%) was purified by re crystallization from toluene and dried in vacuo.…”

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

“…Related yttrium and lutetium complexes of the readily available tetraphenylethylene dianion have been reported with similar structural features (Chart 23) (Roitershtein et al, 1998;Roitershtein et al, 2004). In both molecular structures of M 2 -stilbene (M = Y, La), the central C-C bond was flipped and disordered over two symmetrical positions (Huang et al, 2014).…”

Group 3 metal stilbene complexes: synthesis, reactivity, and electronic structure studies

“…25 Related yttrium and lutetium complexes of the readily available tetraphenylethylene dianion have been reported with similar structural features. 26,27 Addition of 1.25 equiv KC8 to a pre-mixed THF solution of (NN TBS )YI(THF)2 and 0.5 equiv (E)-stilbene at -78 °C resulted in an immediate color change to dark green (Scheme 1). After stirring at 0 °C for 1 h, the color gradually changed to red.…”