Electronic and Structural Variations of a Nickel(0) N-Heterocyclic Phosphenium Complex in Comparison to Group 10 Analogues
Electronic and Structural Variations of a Nickel(0) N-Heterocyclic Phosphenium Complex in Comparison to Group 10 Analogues
复制标题
与第 10 族类似物相比，镍 (0) N-杂环磷配合物的电子和结构变化
DOI：
10.1021/acs.inorgchem.2c03302
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发表时间：
2022
影响因子：
4.6
通讯作者：
Thomas, Christine M.
中科院分区：
文献类型：
--
作者：
Oliemuller, Leah K.;Moore, Curtis E.;Thomas, Christine M.
研究了一个以N-杂环膦/膦（NHP±）为中心的双膦钳形配体与镍的成键作用和电子结构.在双电子膦供体配体PMe 3存在下，用钳形配体[PPP]Cl处理Ni（COD）2生成氯膦络合物（PPCIP）Ni（PMe 3）（2a）。阳离子镍配合物[（PPP）Ni（PMe 3）][BPh 4]（3a）可以通过随后用NaBPh 4从2a中提取卤素来制备。根据结构参数分析和计算研究，将3a归属为Ni 0/NHP+配合物，与先前报道的10族MII/NHP-（M = Pd，Pt）类似物相反。通过添加异丙醇以提供金属氢化物物质[（PPOiPrP）Ni（PMe 3）（H）][BPh 4]（4）来证明跨Ni-PNHP键的O-H键的活化。值得注意的是，通过用LiAlH 4处理2a在NHP单元中安装P-H键产生（PPHP）Ni（PMe 3）（6）。通过与Pd类似物（PPHP）Pd（PPh 3）（8）相比，P-H键裂解的反应性研究证明了P-H键的两亲性。
The bonding interactions and electronic structure of a diphosphine pincer ligand featuring an N-heterocyclic phosphenium/phosphido (NHP±) central moiety with nickel are explored. Treating Ni(COD)2with the pincer ligand [PPP]Cl in the presence of a two-electron phosphine donor ligand PMe3generates chlorophosphine complex (PPClP)Ni(PMe3) (2a). The cationic Ni complex [(PPP)Ni(PMe3)][BPh4] (3a) can be prepared by subsequent halide abstraction from2awith NaBPh4. The assignment of3aas a Ni0/NHP+complex, based on analysis of structural parameters and computational investigations, lies in contrast to its previously reported group 10 MII/NHP–(M = Pd, Pt) analogues. The activation of O–H bonds across the Ni–PNHPbond is demonstrated by the addition of isopropanol to afford the metal hydride species [(PPOiPrP)Ni(PMe3)(H)][BPh4] (4). Notably, the installation of a P–H bond in the NHP unit by treatment of2awith LiAlH4yields (PPHP)Ni(PMe3) (6). The ambiphilic nature of the P–H bond was demonstrated through reactivity studies of P–H bond cleavage in comparison to a Pd analogue (PPHP)Pd(PPh3) (8).