title: Rare-earth metal hydrides supported by silicon-bridged boratabenzene fluorenyl ligands: synthesis, structure and reactivity.
abstract: The reactions of rare-earth metal benzyl complexes supported by silicon-bridged boratabenzene fluorenyl ligands with PhSiH3in toluene gave the corresponding dinuclear hydrides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-H)(THF)]2(3-Ln; Ln = La, Nd, Gd), wherein the rare-earth metal ions are linked by both silicon-bridged boratabenzene fluorenyl ligands and hydrido ligands. The reactivity of these hydrides toward unsaturated substrates was studied. Among these, alkynides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-CCPh)]2(4-Ln; Ln = La, Nd) were obtained via the σ-bond metathesis reaction, when 3-Ln (Ln = La, Nd) was treated with phenylacetylene. While reacting with 3-hexyne, the mono-addition product [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln]2(μ-H)[μ-C(Et)[double bond, length as m-dash]C(H)Et] (5-Ln; Ln = La, Nd) was formed. Further investigations on the reactivity of 3-La displayed that benzonitrile and tert-butyl isonitrile readily inserted into the La-H bonds, affording an azomethine complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ-N[double bond, length as m-dash]C(H)Ph}]2(6-La) and an N-tert-butylformimidoyl complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ,η2-C(H)[double bond, length as m-dash]NtBu}]2(7-La), respectively. The reaction with N,N'-diisopropylcarbodiimide at room temperature or at 75 °C gave a dimeric complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La]2(μ-H)[μ-N(iPr)CHN(iPr)] (8-La) or a monomeric complex [Me2Si(C13H8)(C5H4BNEt2)]La[N(iPr)CHN(iPr)] (9-La), respectively.
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China. xiangli@sioc.ac.cn yaofchen@mail.sioc.ac.cn.
authors.forename: Chunhong
authors.initials: C
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China. xiangli@sioc.ac.cn yaofchen@mail.sioc.ac.cn.
authors.forename: Li
authors.initials: L
authors.lastname: Xiang
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China. xiangli@sioc.ac.cn yaofchen@mail.sioc.ac.cn.
authors.forename: Xuebing
authors.initials: X
authors.lastname: Leng
authors.affiliation: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China. xiangli@sioc.ac.cn yaofchen@mail.sioc.ac.cn.
authors.forename: Yaofeng
authors.identifier: http://orcid.org/0000-0003-4664-8980
authors.initials: Y
authors.lastname: Chen