The reaction of scandium trifluoride with cyclopentadienyl salts and the crystal and molecular structure of the trimer of fluorodicyclopentadienylscandium

Syntheses and Structures of Bis(aryloxo)fluoroytterbium(III) Complexes, [Yb(OAr)2F(THF)]2 (OAr = OC6H2-2,6-tBu2-4-R; R = H, Me, tBu), and Bis(cyclopentadienyl)fluoroytterbium(III) Complexes, [YbCp2F]3, [Yb(MeCp)2F]4, [YbCp2F(OPPh3)]2, and [Yb(MeCp)2F(THF)]2

“…[21] Because of such reactions, the mass spectra are an uncertain guide as to solid state structures. In general the fragmentation patterns of the Cp complexes were similar to those of [YbCp 2 F(THF)] 2 [21] and [ScCp 2 F] 3 , [15] whilst those of the MeCp complexes showed features (loss of MeCp • , Me • , and, for the THF complex, H • ) similar to those of [Ln(MeCp) 3 ]. [34] However there was no evidence of the electron impact-induced ring expansions shown by [Ln(MeCp) 3 ].…”

“…Unsolvated bis(cyclopentadienyl)fluoroytterbium(III) crystallizes as a trimer with eight-coordinate ytterbium ions, and is the first unsolvated unsubstituted cyclopentadienyllanthanoid fluoride to be structurally characterized, though similar trimers have been observed for [ScCp 2 F] 3 , [15] [Sm(C 5 H 4 -tBu) 2 F] 3 , [20] and [Sm(C 5 Me 5 ) 2 -Cl] 3 . [42] Selected bond lengths and angles are given in (9) Yb (1) Table 4 and the structure is shown in Figure 3.…”

“…(For the methylcyclopentadienyl complexes, this ion was close to the instrument limit, hence the possibility of formation of tetranuclear ions cannot be ruled out.) An analogous ion was the highest observed in the spectra of [YbCp 2 F(THF)] 2 , [21] [ScCp 2 F] 3 , [15] and [Sm(tBuCp) 2 F] 3 . [20] Formation of trinuclear ions for the dimeric complexes [YbCp 2 F(OPPh 3 )] 2 and [Yb(MeCp) 2 F(THF)] 2 evidently involves thermally induced dissociation of the neutral ligand and further association, as observed for [YbCp 2 F(THF)] 2 .…”

“…[5] Complexes of this type are extremely rare, [6][7][8][9][10][11][12][13][14] there being no reported aryloxofluorolanthanoid complexes [9][10][11][12] and few examples of cyclopentadienylfluorolanthanoids. [3,[6][7][8][12][13][14][15][16][17][18][19][20][21] We now report the syntheses and structures of the first aryloxofluorolanthanoid complexes, [Yb(OAr) 2 F(THF)] 2 (OAr ϭ OC 6 H 2 -2,6-tBu 2 -4-R; R ϭ H, Me, tBu), and some [YbCp 2 F(OPPh 3 )] 2 . X-ray structure determinations revealed [Yb(OAr) 2 F(THF)] 2 (R = H or tBu) to be centrosymmetric fluoride-bridged dimers with five-coordination for ytterbium.…”

Von Ringen und Clustern: „Selbstorganisation” in der Organolanthanoidchemie

“…[1] Die thermische Abspaltung von L oder der ¹sterische Abbauª des Heteroliganden X können nun auch die Selbstorganisation zu Ringsystemen bewirken. Die Bildung einer Ringstruktur mit mehr als zwei Seltenerdmetallen und ohne Zentralatom wurde 1985 erstmals von Bottomley et al für [{Cp 2 Sc(m-F)} 3 ] 1 beschrieben [8] und später für Cp/Ln 2 noch mehrmals beobachtet (z. B.…”