Reactivity of the diphosphinodithio ligated nickel(0) complex toward alkyl halides and resultant nickel( I) and nickel( II)- alkyl complexes

Zhang Ailing; Wang Congxiao; Lai Xiaoyu; Zhai Xiaofang; Pang Maofu; Tung Chen-Ho; Wang Wenguang

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Reactivity of the diphosphinodithio ligated nickel(0) complex toward alkyl halides and resultant nickel( I) and nickel( II)- alkyl complexes

机译：二磷二硫代硅皮镍（0）络合物对烷基卤化物和所得镍（I）和镍（II） - 烷基复合物的反应性

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Diphosphinodithio ligated complexes of nickel(0), nickel(i) and nickel(ii)-alkyl with a reactivity relevant to the C-C bond formation were described. Stoichiometric reactions of the nickel(0) complex, [(P2S2)Ni] ([1](0), P2S2 = (Ph2PC6H4CH2S)(2)(C2H4)), with alkyl halides (RX) such as C6H5CH2Br, C2H3CH2Br, C2H5I and (CH3)(2)CHI were investigated, from which the products were found to be highly dependent on the nature of RX used. Oxidative addition of C2H3CH2Br to [1](0) provides the stable Ni(ii)-alkyl complexes [1-allyl](+). The reaction of [1](0) with C6H5CH2Br proceeds through a radical pathway resulting in the formation of the nickel(i) complex [1](+) and an organic homo-coupled product 1,2-diphenylethane. Oxidative addition of C2H5I or (CH3)(2)CHI to [1](0) can be achieved but it competes with the halogen atom abstraction reaction as found for C6H5CH2Br. [1](0) was shown to be an active catalyst for the coupling reactions of primary halides and alkyl Grignard reagents.

机译：描述了二磷二硫代镍镍（0），镍（I）和镍（II） - 与与C-C键形成相关的反应性的镍（II）烷基的连接复合物。镍（0）复合物的化学计量反应，[（P2S2）Ni]（[1]（0），P2S2 =（PH2PC6H4CH 2 S）（2）（C 2 H 4）），烷基卤化物（Rx）如C6H5CH2BR，C 2 H 3 CH 2B，C2H5I （第3章）（2）被研究，发现产品从中依赖于所用Rx的性质。 C 2 H 3 CH 2R至[1]（0）的氧化加入提供稳定的Ni（II） - 烷基复合物[1-烯丙基]（+）。 [1]（0）与C6H5CH 2BR的反应通过基流途径，导致镍（I）复合物[1]（+）和有机均偶联产物1,2-二苯基乙烷的形成。可以实现C 2 H 1或（2）CHI至[1]（0）的氧化加入，但与C6H5CH2BR的卤素原子抽象反应竞争。 [1]（0）显示为初级卤化物和烷基格氏试剂的偶联反应的活性催化剂。

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《Dalton transactions: An international journal of inorganic chemistry》 |2018年第44期|共8页
作者
Zhang Ailing; Wang Congxiao; Lai Xiaoyu; Zhai Xiaofang; Pang Maofu; Tung Chen-Ho; Wang Wenguang;
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Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

Shandong Univ Key Lab Colloid &

Interface Chem Educ Minist Sch Chem &

Chem Engn Jinan 250100 Shandong Peoples R China;

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中图分类化学;无机化学;
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1. Reactivity of the diphosphinodithio ligated nickel(0) complex toward alkyl halides and resultant nickel( I) and nickel( II)- alkyl complexes [J] . Zhang Ailing, Wang Congxiao, Lai Xiaoyu, Dalton transactions: An international journal of inorganic chemistry . 2018,第44期

机译：二磷二硫代硅皮镍（0）络合物对烷基卤化物和所得镍（I）和镍（II） - 烷基复合物的反应性
2. Impact of Oxidation State on Reactivity and Selectivity Differences between Nickel(III) and Nickel(IV) Alkyl Complexes [J] . Roberts Courtney C., Camasso Nicole M., Bowes Eric G., Angewandte Chemie . 2019,第27期

机译：氧化态对镍（III）和镍（IV）烷基复合物的反应性和选择性差异的影响
3. PADLOCK MACROCYCLIC COMPLEXES - THE SYNTHESIS OF A RANGE OF NICKEL(II) COMPLEXES OF N-ALKYL AZACYCLAMS AND THE CRYSTAL STRUCTURE OF (3-ETHYL-1,3,5,8,12-PENTA-AZACYCLOTETRADECANE) NICKEL(II) PERCHLORATE [J] . Hay RW., Lightfoot P., Lampeka YD., Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1997,第16期

机译：挂锁式大环复合物-N-烷基氮杂双环镍（II）配合物的合成和（3-乙基-1,3,5,8,12-戊五氮杂环戊烷）（II）高氯酸盐的晶体结构
4. Reduction of alkyl halides by electrogenerated cobalt(I) salen and nickel(I) salen: reactions of alkyl radicals with no and O_2 [C] . Dennis G. Peters, Chang Ji, Benjamin J. Wozniak, International Manuel M. Baizer Symposium . 2002

机译：通过电子化钴（I）盐和镍（I）盐来减少烷基卤化物：烷基的反应没有NO和O_2
5. Reactions of alkyl halides with electrogenerated square-planar nickel(I)-containing complexes: Formation of aldehydes. [D] . Vanalabhpatana, Parichatr. 2005

机译：卤代烷与电生成的含方形平面镍（I）的配合物的反应：醛的形成。
6. Nickel–Alkyl Complexes with a Reactive PNC‐Pincer Ligand [O] . Linda S. Jongbloed, Nicolas Vogt, Aaron Sandleben, -1

机译：具有反应性PNC针状配体的镍烷基络合物
7. SELECTIVE FORMATION OF KETONE, DIKETONE AND ALDEHYDE BY THE CO INSERTION INTO NICKEL–ALKYL BONDS OF DIALKYLNICKEL COMPLEXES. A NOVEL NICKEL-CATALYZED SYNTHESES OF KETONES AND TERTIARY ALCOHOLS FROM GRIGNARD REAGENTS, ARYL HALIDES, AND CARBON MONOXIDE [O] . Takakazu Yamamoto, Teiji Kohara, Akio Yamamoto 1976

机译：CO插入二烷基尼克尔配合物的镍烷基键，选择性地形成酮，二酮和醛。一种新的镍催化的酮和来自格氏试剂，芳基和一氧化碳的叔醇的合成
8. Study of Fundamental Reaction Pathways for Transition Metal Alkyl Complexes. I. The Reaction of a Nickel Methyl Complex with Alkynes. II. The Mechanism of Aldehyde Formation in the Reaction of a Molybdenum Hydride with Molybdenum [R] . Huggins, J. M. 1980

机译：过渡金属烷基配合物的基本反应途径研究。 I.镍甲基配合物与炔烃的反应。 II。氢化钼与钼反应生成醛的机理

Reactivity of the diphosphinodithio ligated nickel(0) complex toward alkyl halides and resultant nickel( I) and nickel( II)- alkyl complexes

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