Rare-earth-metal methyl, amide, and imide complexes supported by a superbulky scorpionate ligand.
Rare-earth-metal methyl, amide, and imide complexes supported by a superbulky scorpionate ligand.
复制标题
由超大蝎形配体支持的稀土金属甲基、酰胺和酰亚胺配合物
作者：
Schädle;Maichle-Mössmer;Schädle;Anwander
单体[(TptBu,Me)LuMe2] （TptBu,Me=tris（3‐Me‐5‐tBu‐吡唑基）硼酸盐）与伯脂肪胺H2NR （R=tBu, Ad=adamantyl）反应生成了镥甲基伯胺配合物[(TptBu,Me)LuMe(NHR)]，通过XRD分析确定了其固体结构。混合甲基/四甲基铝酸盐化合物[(TptBu,Me)LnMe({μ2‐Me}AlMe3)] （Ln=Y, Ho）根据甲烷消除作用与H2NR选择性高收率反应，得到杂双金属配合物[(TptBu,Me)Ln({μ2‐Me}AlMe2)(μ2‐NR)] （Ln=Y, Ho）。X射线结构分析表明，单体烷基铝负载的亚胺配合物具有等结构，具有桥接甲基和亚胺配体。通过不同温度下1h和13c核磁共振波谱研究和1h - 89y HSQC核磁共振波谱，对溶液中的流动行为有了更深入的了解。用H2NtBu处理[(TptBu,Me)LnMe(AlMe4)]得到二甲基化合物[(TptBu,Me)LnMe2]作为中型金属钇和钬的次要副产物，对较小的镥收率很高。通过在N，N,N′，N′‐四亚甲基乙二胺（tmeda）中[(TptBu,Me)LnMe2] （Ln=Y, Ho, Lu）的铝酸盐解理，获得了制备规模的配合物[(TptBu,Me)LnMe2] （Ln=Y, Ho, Lu）。用XRD分析了[(TptBu,Me)HoMe(AlMe4)]和[(TptBu,Me)HoMe2]的固态结构。
The reaction of monomeric [(TptBu,Me)LuMe2] (TptBu,Me=tris(3‐Me‐5‐tBu‐pyrazolyl)borate) with primary aliphatic amines H2NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(TptBu,Me)LuMe(NHR)], the solid‐state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(TptBu,Me)LnMe({μ2‐Me}AlMe3)] (Ln=Y, Ho) reacted selectively and in high yield with H2NR, according to methane elimination, to afford heterobimetallic complexes: [(TptBu,Me)Ln({μ2‐Me}AlMe2)(μ2‐NR)] (Ln=Y, Ho). X‐ray structure analyses revealed that the monomeric alkylaluminum‐supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by1H and13C NMR spectroscopic studies at variable temperatures and1H–89Y HSQC NMR spectroscopy. Treatment of [(TptBu,Me)LnMe(AlMe4)] with H2NtBu gave dimethyl compounds [(TptBu,Me)LnMe2] as minor side products for the mid‐sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative‐scale amounts of complexes [(TptBu,Me)LnMe2] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(TptBu,Me)LnMe(AlMe4)] withN,N,N′,N′‐tetramethylethylenediamine (tmeda). The solid‐state structures of [(TptBu,Me)HoMe(AlMe4)] and [(TptBu,Me)HoMe2] were analyzed by XRD.
登录
查看更多内容
锂和铊的苯基三(3-叔丁基吡唑基)硼酸配合物，[PhTpBut]M (M = Li, Tl)：单体三(吡唑基)硼酸铊配合物的新颖结构及其立体化学非刚性的研究 1H 和
DOI：
--
发表时间：
1999
期刊：
影响因子：
--
作者：
J. Kisko;T. Hascall;C. Kimblin;G. Parkin
通讯作者：
G. Parkin
邻位金属化镥芳基配合物中金属环开环的动力学和机理研究
DOI：
--
发表时间：
2011
期刊：
影响因子：
--
作者：
Kevin R. D. Johnson;Paul G. Hayes
通讯作者：
Paul G. Hayes
影响因子：
2.8
作者：
BUSCH, MA;HARLOW, R;WATSON, PL
通讯作者：
WATSON, PL
“亚稳态”Lu(GaMe4)3 的反应类似于掩蔽 [LuMe3]：非溶剂化镧系元素二甲基配合物的合成
影响因子：
2.8
作者：
Melanie Zimmermann;Rannveig Litlabø;K. Törnroos;R. Anwander
通讯作者：
R. Anwander
DOI：
--
发表时间：
1996
期刊：
影响因子：
--
作者：
D. Atwood;Drew Rutherford
通讯作者：
Drew Rutherford