1,2,4-三叔丁基环戊二烯基配体对钍联吡啶茂金属[η-1,2,4-(MeC)CH]Th(bipy)反应活性的影响

Influence of 1,2,4-Tri--butylcyclopentadienyl Ligand on the Reactivity of the Thorium Bipyridyl Metallocene [η-1,2,4-(MeC)CH]Th(bipy)].

作者信息

Wang Dongwei, Heng Yi, Li Tongyu, Ding Wanjian, Hou Guohua, Zi Guofu, Walter Marc D

机构信息

Department of Chemistry, Beijing Normal University, Beijing 100875, China.

Technische Universität Braunschweig, Institut für Anorganische und Analytische Chemie, Hagenring 30, Braunschweig 38106, Germany.

出版信息

Inorg Chem. 2024 Oct 14;63(41):19188-19212. doi: 10.1021/acs.inorgchem.4c02782. Epub 2024 Oct 3.

The thorium bipyridyl metallocene (Cp)Th(bipy) (; Cp = η-1,2,4-(MeC)CH) shows a rich reactivity toward a series of small molecules. For example, complex may act as a synthon for the (Cp)Th(II) fragment as illustrated by its reactivity toward to CuI, hydrazine derivative (PhNH), Ph ( = S, Se), elemental sulfur (S) and selenium (Se), organic azides, CS, and isothiocyanates. Moreover, in the presence of polar multiple bonds, such as those in ketones PhCO and (CH)CO, aldehydes -MePhCHO and -ClPhCHO, seleno-ketone (-MeOPh)CSe, nitriles PhCN, PhCHCN, CHCN, and -(NC)Ph, and benzoyl cyanide PhCOCN, C-C coupling occurs to furnish (Cp)Th[(bipy)(PhCO)] (), (Cp)Th[(bipy)((CH)CO)] (), (Cp)Th[(bipy)(-MePhCHO)] (), (Cp)Th[(bipy)(-ClPhCHO)] (), (Cp)Th[(bipy){(-MeOPh)CSe}] (), (Cp)Th[(bipy)(PhCN)] (), (Cp)Th[(bipy)(PhCHCN)] (), (Cp)Th[(bipy)(CHCN)] (), [(Cp)Th]{μ-(bipy)-Ph(CN)} (), and (Cp)Th{(bipy)[PhC(CN)O]} (), respectively. Nevertheless, ketazine (PhCH═N) or benzyl nitrile PhCHCN forms the dimeric complexes [(Cp)Th][μ-NC(Ph)(bipy)] () and (Cp)Th[(bipy){C(═CHPh)NH}] (), respectively. In contrast, C-N bond cleavage and C-C coupling processes occur upon addition of isonitriles MeCNC and CHNC to to yield the thorium isocyanido amido complexes (Cp)Th4-(MeC)bipy () and (Cp)Th4-(CH)bipy (), respectively. Furthermore, a single-electron transfer (SET) process ensues when 1 equiv of CuI is added to to yield the Th(VI) bipyridyl iodide complex (Cp)Th(I)(bipy) ().

钍联吡啶茂金属（Cp）Th（bipy）（；Cp = η-1,2,4-（MeC）CH）对一系列小分子表现出丰富的反应活性。例如，配合物可作为（Cp）Th（II）片段的合成子，这可由其对CuI、肼衍生物（PhNH）、Ph （ = S，Se）、元素硫（S）和硒（Se）、有机叠氮化物、CS和异硫氰酸酯的反应活性说明。此外，在极性多重键存在的情况下，如在酮PhCO和（CH）CO、醛 -MePhCHO和 -ClPhCHO、硒酮（-MeOPh）CSe、腈PhCN、PhCHCN、CHCN和 -（NC）Ph以及苯甲酰腈PhCOCN中，会发生C-C偶联反应，分别生成（Cp）Th[（bipy）（PhCO）]（）、（Cp）Th[（bipy）（（CH）CO）]（）、（Cp）Th[（bipy）（-MePhCHO）]（）、（Cp）Th[（bipy）（-ClPhCHO）]（）、（Cp）Th[（bipy）{（-MeOPh）CSe}]（）、（Cp）Th[（bipy）（PhCN）]（）、（Cp）Th[（bipy）（PhCHCN）]（）、（Cp）Th[（bipy）（CHCN）]（）、[（Cp）Th]{μ-（bipy）[-Ph（CN）]（bipy）}（）和（Cp）Th{（bipy）[PhC（CN）O]}（）。然而，酮连氮（PhCH═N）或苄腈PhCHCN分别形成二聚配合物[（Cp）Th][μ-NC（Ph）（bipy）]（）和（Cp）Th[（bipy）{C（═CHPh）NH}]（）。相反，将异腈MeCNC和CHNC加入到中时会发生C-N键断裂和C-C偶联过程，分别生成钍异氰基酰胺配合物（Cp）Th[4-（MeC）bipy]（NC）（）和（Cp）Th[4-（CH）bipy]（NC）（）。此外，当向中加入1当量的CuI时会发生单电子转移（SET）过程，生成Th（VI）联吡啶碘化物配合物（Cp）Th（I）（bipy）（）。