Synthesis, Structure, and Reactivity of Organolanthanide Carboranyl Compounds and Lanthanacarboranes Derived from a Versatile Ligand, Me₂C(C₅H₅)(C₂B₁₀H₁₁)

Abstract

The compound Me 2 C(C 5 H 5 )(C 2 B 10 H 11 ) (I) could be conveniently converted into the monoanion [Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )] -(I-1) and the dianion [Me 2 C(C 5 H 4 )(C 2 B 10 H 10 )] 2-(I-2) by treatment with excess NaH and 2 equiv of n-BuLi, respectively. The monoanion I-1 could be further converted into the trianion [Me 2 C(C 5 H 4 )(nido-C 2 B 10 H 11 )] 3-(I-3) by reaction with 2 equiv of Na metal in THF and into the pentaanion [Me 2 C(C 5 H 4 )(arachno-C 2 B 10 H 11 )] 5in the presence of LnCl 3 and excess Na metal in THF. Reactions of LnCl 3 with the monoanion I-1 in molar ratios of 1:1, 1:2, and 1:3 generated the mono-, bis-, and tris-ligated organolanthanide compounds 4), and [η 5 -Me 2 C(C 5 H 4 )-(C 2 B 10 H 11 )] 3 Sm‚0.5C 7 H 8 (5), respectively. Reaction of LnCl 3 with 1 or 2 equiv of the dianion I-2 gave the same compound, [{η 5 :σ-Me 2 C(C 5 H 4 )(C 2 B 10 H 10 )} 2 Ln][Li(DME) 3 ] (Ln ) Sm (6), Yb ( 7)). 6 could also be prepared by treatment of 2 with 1 equiv of the dianion I-2. Reaction of YbI 2 with 1 equiv of I-2, followed by treatment with 1 equiv of I-1, also gave compound 7. However, YbI 2 reacted with 2 equiv of I-1 to afford the organoytterbium(II) compound [η 5 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )] 2 Yb(THF) 2 (8). Interaction of SmI 2 with 2 equiv of I-1 yielded two compounds, the redox product [η 5 :η 6 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )]Sm(THF) 2 ( 9) and the tris-ligated compound 5. The compound [η 5 :η 6 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )]Er(THF) 2 ( 10), an analogue of 9, was prepared by treatment of 1 with 2 equiv of Na metal or by reaction of ErCl 3 with 1 equiv of I-3. Treatment of 10 with excess Na metal gave the first organolanthanide compound containing a η 7 -carboranyl ligand, [{[η 5 :η 7 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )]Er} 2 {Na 4 (THF) 9 }] n (11). Its Dy analogue, [{[η 5 :η 7 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )]Dy} 2 {Na 4 (THF) 9 }] n (12), could also be prepared by a "one-pot" reaction of DyCl 3 , I-1, and excess Na metal. Treatment of 11 with 2 equiv of ErCl 3 in THF gave the novel tetranuclear cluster [{η 5 :η 7 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )}Er 2 (µ-Cl)-(THF) 3 ] 2 (13), in which the Er 3+ ions replace all Na + ions in 11. All of these compounds were fully characterized by various spectroscopic data and elemental analyses. The solid-state structures of compounds 4-11 and 13 have been confirmed by single-crystal X-ray analyses.

Icosahedral boron clusters: a perfect tool for the enhancement of polymer features

“…27), is obtained by reaction of Me 2 Si(C 9 H 7 )(C 2 B 10 H 11 ) with excess of NaH in THF followed by addition of DyCl 3 in excess of Na. 54 These results indicate that the substituents indenyl or cyclopentadienyl, on carborane cage carbons may affect the overall molecular structures of the 13-vertex closo-metallacarborane complexes, but have little influence on the interactions between the central metal ion and the nido-or arachno-carborane ligand. X-ray analyses reveal a similar structure between these polymers and the polymer (85).…”

“…22). 54 The polymeric nature of (85) confirmed by X-ray diffraction indicates that each asymmetrical unit contains two [Z 5 :Z 7 -Me 2 C(C 5 H 4 )-(C 2 B 10 H 11 )Er] 2À structural motifs that are connected by three Na atoms through several B-HÁ Á ÁNa three-center-two-electron bonds (3c-2e). 3 ] n (83) (Fig.…”

“…The same polymer containing Dy, [{Me 2 Si(C 9 H 6 )(C 2 B 10 H 11 )]Dy} 2 {Na 4 (THF) 8 }] n (87) (Fig. 54 The average Ln-C(C 5 ring), Ln-C(cage) and Ln-B(cage) distances in (86) and (87) are longer than the corresponding values found in its cyclopentadienyl analogue of [{[Z 5 :Z 7 -Me 2 C(C 5 H 4 )(C 2 B 10 H 11 )]Er} 2 {Na 4 (THF) 9 }] n (85). 53 The two infinite polymeric chains are isostructural and isomorphous.…”

Mono(cyclopentadienyl) Complexes of the Rare-Earth Metals

“…36,37 The crystallographically characterized analogous samarium complex [Sm(η 5 :η 6 -C 5 H 4 CMe 2 C 2 B 10 H 11 )(THF) 2 ] was obtained in THF from SmI 2 and the mono(sodium) salt of the ligand. 36 …”

Exploring Ag⋯H–B interactions in coordination polymers: silver–alkanedinitrile networks with cobalt carbaborane anions

“…Although they are considered to be weakly coordinating anions, carbaborane compounds may be involved in agostic interactions with diverse metal centres. [30][31][32][33][34][35][36][37][38][39][40] In a recent study we reported a series of coordination complexes (either discrete, 1D or 3D polymers) of Ag(I) and smaller alkane dinitriles…”