Synthesis and Structure of the First Trinuclear, Half‐Sandwich Carboranegadolinium(<scp>III</scp>) Cluster

Rare-earth elements include scandium, yttrium and fifteen lanthanides. Since Wilkinson and Birmingham reported the fist example of rare-earth organometallic complex, the chemistry of rare-earth organometallic complexes has had a great advance during the past sixty years. A variety of Cp containing rare-earth metal complexes, including mono-Cp, bis-Cp, and tri-Cp complexes, have been synthesized. Variation of the size of substituent on Cp ring, introducing the nitrogen or oxygen containing pendant arm to Cp ring or using ansa bis-Cp ligands make the synthesis and stabilization of these three types of rare-earth metal Cp complexes available. The Cp related ligands, such as indenyl and fluorenyl, also have been applied for the rare-earth organometallic complexes. From 1990's, there was a tendency to explore the rare-earth organometallic complexes with ancillary ligands beyond Cp and its derivatives in order to search for more efficient rare-earth metal catalysts. Non-Cp ligands, such as biphenolates, β-diketiminates, amidinates, guanidinates, etc. have been introduced into the chemistry of rare-earth organometallic complexes, and a larger number of non-Cp rare-earth organometallic complexes have been synthesized and characterized. The application of non-cyclopentadienyl ligands not only resulted in the rare-earth organometallic complexes with new structural features, but also the catalysts with high activity and high selectivity for the polymer synthesis and organic synthesis. The rare-earth organometallic complexes catalyze homo-and co-polymerization of olefins as well as specific polymerization of dienes and polar monomers. The discovery of the catalytic system composed of the neutral rare-earth metal dialkyls/borate enables to synthesize some interesting polymers which are difficult to be prepared by using other catalytic system. The rare-earth organometallic complexes are also able to catalyze some important organic reactions, such as hydroamination, hydrophosphinylation, and hydroalkoxylation, etc. Different from the late-translation metal catalyzed organic reactions, most of the rare-earth metal catalyzed ones do not involve oxidative addition and reductive elimination steps. The review describes some important developments of the chemistry of rare-earth organometallic complexes in the past sixty years.

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Section: 基于其它配体的稀土金属有机配合物unclassified

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

Changtao¹,

Wang²,

Chen³

2014

Acta Chim. Sinica

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“…Gd, Tb, Dy, Ho, and Nd), instead of the expected full-sandwich lanthanacarboranes as shown in Scheme 3. 39 These clusters, shown in Fig. 2, are composed of three half-sandwich lanthanacarboranes and three lithiacarboranes arranged around an oxide ion and a methoxide ion, respectively.…”

Section: Lanthanacarboranes Involving C 2 B 4 Carboranesmentioning

confidence: 99%

“…2, are composed of three half-sandwich lanthanacarboranes and three lithiacarboranes arranged around an oxide ion and a methoxide ion, respectively. 39 These unexpected products were believed to arise from the initial formation of a half-sandwich lanthanacarborane, which reacts further with the THF solvent, or its decomposition product, to form the final trinuclear cluster. On the other hand, the reaction of the TMEDA-solvated dilithium salt of the [2,3- 40 In addition, several half-sandwich complexes have been reported.…”

Section: Lanthanacarboranes Involving C 2 B 4 Carboranesmentioning

confidence: 99%

Advances in the metallacarborane chemistry of f-block elements

et al. 2010

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The role of carborane clusters in organometallic chemistry is diverse. A number of carborane cage systems such as C(2)B(4), C(2)B(9) and C(2)B(10) clusters have been extensively used for the synthesis of numerous metallacarboranes of s, p, d and f-block elements. An introduction to the chemistry of metallacarboranes is provided with an emphasis on the recent advances on the metallacarboranes of f-block elements.

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“…1) shows that (1) is a novel dinuclear holmacarborane bent-sandwich complex in which the central (commo) Ho atom is 775. bonded to each of the 'carbons apart' C2B3 faces with Ho...centroid distances of 2.340 and 2.349/k. 358-2.399,4,;Oki, Zhang & Hosmane, 1992;Zhang, Oki, Wang, Maguire & Hosmane, 1995). 358-2.399,4,;Oki, Zhang & Hosmane, 1992;Zhang, Oki, Wang, Maguire & Hosmane, 1995).…”

Section: = C-sime 3 • = Hmentioning

confidence: 99%