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首页> 外文期刊>Chemistry: A European journal >Small Molecule Activation by POC_(sp3)OP-Nickel Complexes
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Small Molecule Activation by POC_(sp3)OP-Nickel Complexes

机译：POC_（sp3）OP-镍配合物激活小分子

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摘要

This contribution describes the reactivities of CO_2, CO, O_2, and ArNC with the pincer-type complexes [(k~P,k~C,k~(P’)-POC_(sp3)OP)NiX] (POC_(sp3)OP=(R_2POCH_2)_2CH; R=iPr; X=OSiMe_3, NArH; Ar=2,6-iPr_2C_6H_3). Reaction of the amido derivative with CO_2 and CO leads to a simple insertion into the Ni-N bond to give stable carbamate and carbamoyl derivatives, respectively, the pincer ligand backbone remaining intact in both cases. In contrast, the analogous reactions with the siloxide derivative produced kinetically labile insertion products that either revert to the starting material (in the case of CO_2) or react further to give the mixed-valent, dinickel species [(POC_(sp3)OP)Ni~(II){m,k~O,k~P,k~(P’)-OCOCH(CH_2CH_2OPR_2)_2}Ni~0(CO)_2]. The zero-valent center in the latter compound is ligated by a new ligand arising from transformation of the POC_(sp3)OP ligand backbone. The carbonylation and carboxylation of the siloxido derivative also produced minor quantities of a side-product identified as the trinickel species, [{(h~3-allyl)-Ni(μ~O,k~P-R2PO)_2}_2Ni], arising from total dismantling of the POC_(sp3)OP ligand. Similar reactivities were observed with isonitrile, ArNC: reaction with the siloxido derivative resulted in a complex sequence of steps involving initial insertion, a 1,3-hydrogen shift, and an Arbuzov rearrangement to give [Ni(CNAr)_4] and a methacrylamide based on fragments of the POC_(sp3)OP ligand. Oxygenation of the amido and siloxido derivatives led to the phosphinate derivative, [(POC_(sp3)OP)Ni(OP(O)R_2)], arising from oxidative transformation of the original ligand frame; the reaction with the Ni-NHAr derivative also gave ArHNP(O)R_2 through a complex N-P bond-forming reaction.
机译：该贡献描述了CO_2，CO，O_2和ArNC与钳型配合物[（k〜P，k〜C，k〜（P'）-POC_（sp3）OP）NiX]（POC_（sp3）的反应性OP =（R_2POCH_2）_2CH; R = iPr; X = OSiMe_3，NArH; Ar = 2,6-iPr_2C_6H_3）。酰胺基衍生物与CO_2和CO的反应导致分别简单插入Ni-N键中，分别得到稳定的氨基甲酸酯和氨基甲酰基衍生物，在两种情况下，钳位配体主链均保持完整。相反，与氧化硅衍生物的类似反应产生了动力学不稳定的插入产物，该产物要么转变为起始原料（在CO_2的情况下），要么进一步反应生成混合价的二镍物质[（POC_（sp3）OP）Ni 〜（II）{m，k〜O，k〜P，k〜（P'）-OCOCH（CH_2CH_2OPR_2）_2} Ni〜0（CO）_2]。后一种化合物中的零价中心被POC_（sp3）OP配体主链转化产生的新配体连接。硅烷氧化物衍生物的羰基化和羧化也产生了少量的副产物，即三{[（h〜3-烯丙基）-Ni（μ〜O，k〜P-R2PO）_2} _2Ni]。完全由POC_（sp3）OP配体的分解引起的。用异腈ArNC观察到相似的反应性：与甲硅烷基衍生物的反应导致一系列复杂的步骤，包括初始插入，1,3-氢位移和Arbuzov重排，得到[Ni（CNAr）_4]和甲基丙烯酰胺基在POC_（sp3）OP配体的片段上。酰胺基和甲硅烷氧基衍生物的氧化导致次膦酸酯衍生物[（POC_（sp3）OP）Ni（OP（O）R_2）]，这是由于原始配体骨架的氧化转化引起的;与Ni-NHAr衍生物的反应也通过复杂的N-P键形成反应得到ArHNP（O）R_2。

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