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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Tetrahydropentalenyl-phosphazene constrained geometry complexes of rare-earth metal alkyls
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Tetrahydropentalenyl-phosphazene constrained geometry complexes of rare-earth metal alkyls

机译：四氢戊烯基-磷腈约束的稀土金属烷基的几何配合物

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摘要

Reactions of Cp~(TM)HPPh_2 (1, diphenyl(4,4,6,6-tetramethyl-1,4,5,6-tetrahydropentalen-2-yl)phosphane) with the organic azides AdN_3 and DipN_3 (Ad = 1-adamantyl; Dip = 2,6-di-iso-propylphenyl) led to the formation of two novel CpPN ligands: P-amino-cyclopentadienylidene-phosphorane (Cp~(TM)PPh_2NHAd; L_(Ad)H) and P-cyclopentadienyl-iminophosphorane (Cp~(TM)HPPh_2NDip; LDipH). Both were characterized by NMR spectroscopy and X-ray structure analysis. For both compounds only one isomer was observed. Neither possesses any detectable prototropic or elementotropic isomers. Reactions of these ligands with [Lu(CH_2SiMe_3)_3(thf)_2] or with rare-earth metal halides and three equivalents of LiCH_2SiMe_3 produced the desired bis(alkyl) Cp~(TM)PN complexes: [{Cp~(TM)PN}M(CH_2SiMe_3)_2] (M = Sc (1_(Ad), 1_(Dip)), Lu (2_(Ad), 2_(Dip)), Y (3_(Ad), 3_(Dip)), Sm (4_(Ad)), Nd (5_(Ad)), Pr (6_(Ad)), Yb (7_(Ad))). These complexes were characterized by extensive NMR studies for the diamagnetic and the paramagnetic complexes with full signal assignment. An almost mirror inverted order of the paramagnetic shifts has been observed for ytterbium complex 7_(Ad) compared to 4_(Ad), 5_(Ad) and 6_(Ad). For the assignment of the NMR signals [{η~1: η~5-C_5Me_4PMe_2NAd}Yb(CH_2SiMe_3)_2] 7 was synthesized, characterized and the ~1H NMR signals were compared to 7_(Ad) and to other paramagnetic lanthanide complexes with the same ligand. 1_(Ad), 2_(Ad), 2_(Dip), 3_(Ad) and 3_(Dip) were characterized by X-ray structure analysis revealing a sterically congested constrained geometry structure.
机译：Cp〜TMHPPh_2（1，二苯基（4,4,6,6-四甲基-1,4,5,6-四氢戊二烯-2-基）膦）与有机叠氮化物AdN_3和DipN_3（Ad = 1 -金刚烷基; Dip = 2,6-二异丙基苯基）导致形成两个新的CpPN配体：P-氨基-环戊二烯亚基-膦烷（Cp〜TMPPh_2NHAd; L_（Ad）H）和P-环戊二烯基-亚氨基膦烷（CpTMHPPh_2NDip; LDipH）。两者均通过NMR光谱和X射线结构分析表征。对于这两种化合物，仅观察到一种异构体。两者都不具有任何可检测到的质子或元亲异构体。这些配体与[Lu（CH_2SiMe_3）_3（thf）_2]或与稀土金属卤化物和三当量的LiCH_2SiMe_3的反应产生所需的双（烷基）Cp〜TMPN配合物：[{Cp〜（TM） PN} M（CH_2SiMe_3）_2]（M = Sc（1_（Ad），1_（Dip）），Lu（2_（Ad），2_（Dip）），Y（3_（Ad），3_（Dip））， Sm（4_（Ad）），Nd（5_（Ad）），Pr（6_（Ad）），Yb（7_（Ad）））。这些配合物的特征是，对具有完整信号分配的反磁性和顺磁性配合物进行了广泛的NMR研究。与4_（Ad），5_（Ad）和6_（Ad）相比，complex配合物7_（Ad）几乎观察到顺磁位移的镜像倒置顺序。为了分配NMR信号[{η〜1：η〜5-C_5Me_4PMe_2NAd} Yb（CH_2SiMe_3）_2]进行了合成，表征，并将〜1H NMR信号与7_（Ad）和其他顺磁性镧系元素络合物进行了比较，相同的配体。通过X射线结构分析表征了1_（Ad），2_（Ad），2_（Dip），3_（Ad）和3_（Dip），揭示了空间拥塞的受约束几何结构。

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