Diphenylbutadiene-bridged gadolinium complex [GdCl2(THF) 3]2(μ-Ph2C4H4) · 3THF: The synthesis and crystal structure

Yb(II) Triple-Decker Complex with the μ-Bridging Naphthalene Dianion [CpBn5Yb(DME)]2(μ-η4:η4-C10H8). Oxidative Substitution of [C10H8]2– by 1,4-Diphenylbuta-1,3-diene and P4 and Protonolysis of the Yb–C10H8 Bond by PhPH2

“…An analogous bonding situation within a DPB ligand was formerly documented for a La complex . The mean Yb–Cp center distance in 4 (2.41(2) Å) falls into the interval typical for Yb­(II) sandwich [(Me 3 Si) 2 C 5 H 3 ] 2 Yb­(THF) (2.39 Å) and half-sandwich [(C 5 Me 5 )­YbI­(THF) 2 ] 2 (2.41 Å) complexes. The Yb–Cp center and Yb–O (2.447(3) and 2.463(3) Å) bond distances are both indicative of the divalent state of ytterbium (for a comparison of Yb–Cp center and Yb–O bond lengths in Yb­(II) complexes see refs and ).…”

“…In contrast with the related DPB complex of Gd incorporating a distorted diphenylbutadiene ligand, in 4 the DPB ligand adopts a planar structure. Thus, the C–C bond lengths within the butadiene fragment of 4 are noticeably different: the bond C(47)–C(45) (1.265(8) Å) is the shortest, while C(45)–C(46) is the longest (1.44(2) Å).…”

“…Within the rhombic Yb(1)− P(1)−Yb(1A)−P(1A) fragment the Yb−P bonds have similar lengths (2.9174(9) and 2.956(2) Å) and are close to those reported for six-coordinate Yb(II) phosphido complexes: 2) Å) bond distances are consistent with the divalent state of ytterbium. 30,31,16 To the best of our knowledge, Ln(II) phosphinidene complexes still remain unknown. 40b−d In an attempt to synthesize Yb(II) phosphinidene complexes, the reaction of equimolar amounts of 1 and PhPH 2 was carried out in toluene at 20 °C (Scheme 5).…”

Trivalent lanthanide–alkene complexes: Crystallographic and NMR evidence for coordination of tethered alkenes in the solid state and solution

“…The bridging ethylene derivative (C 5 Me 5 ) 2 Yb(m-C 2 H 4 )Pt(PPh 3 ) 2 was reported several years ago but since backbonding from Pt clearly dominates the structural parameters, this complex is not comparable to those reported here [21]. There are also two reports of lanthanide 1,4-diphenylbutadiene complexes but in both cases, the diene ligand is clearly reduced and cannot be compared with the neutral alkene complexes discussed here [43,44]. The only trivalent lanthanideealkene complex that has been structurally characterized is the [(C 5 Me 4 SiMe 2 CH 2 CH¼CH 2 ) 2 Sm] þ cation of Id (Chart 1) [22].…”

Novel synthesis of lanthanoid complexes starting from metallic lanthanoid sources

“…30 Closely related is the neutral gadolinium complex [(THF) 3 Cl 2 Gd(µη 4 : η 4 -s-cis-PhCHCHCHCHPh)GdCl 2 (THF) 3 ] 8, prepared by reduction of GdCl 3 by a potassium salt of 1,4-diphenyl-1,3butadiene in THF, and the anionic lutetium complex {[K(THF) 2 ][Lu(s-cis-PhCHCHCHCHPh) 2 (THF) 2 ]} n 9. 31,32 The X-ray analysis of a highly air-sensitive crystal of com- 35 On the basis of the structural similarities of 7 and 10 with their lithium analogs, it is reasonably assumed that the 'lanthanoid()' moiety acts as alkali metal-like, just like the 'lanthanoid()' species acts as alkaline earth metal-like.…”