Settineri Nicholas S, Arnold John
Department of Chemistry , University of California , Berkeley , California 94720 , USA . Email:
Chemical Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , USA.
Chem Sci. 2018 Feb 16;9(10):2831-2841. doi: 10.1039/c7sc05328b. eCollection 2018 Mar 14.
The reactivity of the thorium monoalkyl complex Th(CHSiMe)(BIMA) [, BIMA = MeC(NPr)] with various small molecules is described. While steric congestion prohibits the insertion of ,'-diisopropylcarbodiimide into the Th-C bond in , the first thorium tetrakis(amidinate) complex, Th(BIMA) (), is synthesized an alternative salt metathesis route. Insertion of -tolyl azide leads to the triazenido complex Th(-tolyl)NNN(CHSiMe)-κN (), which then undergoes thermal decomposition to the amido species Th(-tolyl)N(SiMe) (). The reaction of with 2,6-dimethylphenylisocyanide results in the thorium iminoacyl complex Thη-(C[double bond, length as m-dash]N)-2,6-Me-CH(CHSiMe) (), while the reaction with isoelectronic CO leads to the products ThOC([double bond, length as m-dash]CH)SiMe () and ThOC(NPr)C(CHSiMe)(C(Me)N(Pr))O-κO,O' (), the latter being the result of CO coupling and insertion into an amidinate ligand. Protonolysis is achieved with several substrates, producing amido (), aryloxide (), phosphido (), acetylide (), and cationic () complexes. Ligand exchange with 9-borabicyclo[3.3.1]nonane (9-BBN) results in formation of the thorium borohydride complex (BIMA)Th(μ-H)[B(CH)] (). Complex also reacts under photolytic conditions to eliminate SiMe and produce Th(BIMA)(BIMA*) [, BIMA* = (Pr)NC(CH)N(Pr)], featuring a rare example of a dianionic amidinate ligand. Complexes , , , , , and were characterized by H and C{H} NMR spectroscopy, FTIR, EA, melting point and X-ray crystallography. All other complexes were identified by one or more of these spectroscopic techniques.
描述了单烷基钍配合物Th(CHSiMe)(BIMA) [BIMA = MeC(NPr)]与各种小分子的反应活性。虽然空间位阻阻止了,'-二异丙基碳二亚胺插入到中的Th-C键中，但通过另一种盐复分解途径合成了第一个四(脒基)钍配合物Th(BIMA) ()。-甲苯叠氮的插入导致三氮烯基配合物Th(-甲苯基)NNN(CHSiMe)-κN ()，然后该配合物热分解为酰胺基物种Th(-甲苯基)N(SiMe) ()。与2,6-二甲基苯基异氰酸酯的反应生成钍亚氨基酰基配合物Thη-(C[双键，长度为m破折号]N)-2,6-Me-CH(CHSiMe) ()，而与等电子体CO的反应生成产物ThOC([双键，长度为m破折号]CH)SiMe ()和ThOC(NPr)C(CHSiMe)(C(Me)N(Pr))O-κO,O' ()，后者是CO偶联并插入到一个脒基配体中的结果。用几种底物实现了质子解，生成了酰胺基()、芳氧基()、磷基()、乙炔基()和阳离子()配合物。与9-硼双环[3.3.1]壬烷(9-BBN)的配体交换导致形成硼氢化钍配合物(BIMA)Th(μ-H)[B(CH)] ()。配合物 也在光解条件下反应以消除SiMe并生成Th(BIMA)(BIMA*) [BIMA* = (Pr)NC(CH)N(Pr)]，其具有双阴离子脒基配体的罕见例子。配合物 、 、 、 、 、 和 通过H和C{H} NMR光谱、FTIR、EA、熔点和X射线晶体学进行了表征。所有其他配合物通过这些光谱技术中的一种或多种进行了鉴定。
