Exploring the reactivity of tungsten bis(imido) dimethyl complexes with methyl aluminium reagents: Implications for ethylene dimerization

Wright W.R.H.; Batsanov A.S.; Howard J.A.K.; Tooze R.P.; Hanton M.J.; Dyer P.W.

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Exploring the reactivity of tungsten bis(imido) dimethyl complexes with methyl aluminium reagents: Implications for ethylene dimerization

机译：用甲基铝试剂探索双（亚氨基）二甲基钨配合物的反应性：对乙烯二聚的意义

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The reaction of [WCl_2(NAr)_2(DME)] (1) with excess Me_3Al affords the dimethyl complex [WMe_2(N{Ar}AlMe _2{μ-Cl})(NAr)] (2), which on treatment with THF or MeAlCl _2 yields [WMe_2(NAr)_2(THF)] (3) and [WMe _2(N{Ar}AlMe(Cl){μ-Cl})(NAr)] (5), respectively. Complex 3 is unstable in solution dissociating to form [WMe_2(NAr)_2] (4) that may be isolated as an adduct with PMe_3, [WMe _2(NAr)_2(PMe_3)] (6). While complex 2 is inert towards ethylene, complex 3 reacts rapidly to afford a mixture of methane and but-1-ene (1:4). Neither complex 2 nor 3 react with propylene. Reaction of 3 with a C_2H_4/C_2D_4 (1:1) affords a mixture of isotopomers that is consistent with complete isotopic scrambling. The structures of complexes 1, 2, and 3 have been determined by X-ray diffraction.

机译：[WCl_2（NAr）_2（DME）]（1）与过量的Me_3Al反应得到二甲基络合物[WMe_2（N {Ar} AlMe _2 {μ-Cl}）（NAr）]（2），将其与THF或MeAlCl _2分别产生[WMe_2（NAr）_2（THF）]（3）和[WMe_2（N {Ar} AlMe（Cl）{μ-Cl}）（NAr）]（5）。络合物3在溶液中不稳定，解离形成[WMe_2（NAr）_2]（4），可以作为与PMe_3，[WMe _2（NAr）_2（PMe_3）]的加合物分离出来（6）。配合物2对乙烯呈惰性时，配合物3快速反应，生成甲烷和丁-1-烯（1：4）的混合物。配合物2和3都不与丙烯反应。 3与C_2H_4 / C_2D_4（1：1）的反应提供了同位素异构体的混合物，与完全同位素加扰一致。配合物1、2和3的结构已经通过X射线衍射确定。

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《Dalton transactions: An international journal of inorganic chemistry》 |2010年第30期|共8页
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Wright W.R.H.; Batsanov A.S.; Howard J.A.K.; Tooze R.P.; Hanton M.J.; Dyer P.W.;
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1. Exploring the reactivity of tungsten bis(imido) dimethyl complexes with methyl aluminium reagents: Implications for ethylene dimerization [J] . Wright W.R.H., Batsanov A.S., Howard J.A.K., Dalton transactions: An international journal of inorganic chemistry . 2010,第30期

机译：用甲基铝试剂探索双（亚氨基）二甲基钨配合物的反应性：对乙烯二聚的意义
2. Exploration of Homogeneous Ethylene Dimerization Mediated by Tungsten Mono(imido) Complexes [J] . Messinis Antonis M., Wright William R. H., Batsanov Andrei S., ACS catalysis . 2018,第12期

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4. Synthesis of (Imido)niobium(V) Complexes and their Use as Catalysts for Ethylene Polymerization [C] . Natta Srisupap, Kritdikul Wised, Kotohiro Nomura 石油・石油化学討論会 . 2016

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5. Synthesis and reactivity of tungsten tris-(tri-tertbutyl) silyl imido complexes: Neutral and anionic derivatives, indirect evidence for the intermediacy of metal-alkane complexes in solution [D] . Schafer, Daniel Francis, II 1999

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6. Synthesis of Tungsten Imido Alkylidene Complexes thatContain an Electron-Withdrawing Imido Ligand [O] . JonathanC. Axtell, Richard R. Schrock, *, -1

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7. Bis(Imido) Tungsten Complexes: Efficient Precatalysts for the Homogeneous Dimerization of Ethylene [O] . Antonis M. Messinis, Andrei S. Batsanov, William R. H. Wright, 2018

机译：BIS（咪啶）钨配合物：高效丙烯均匀二聚化的预催化剂

Exploring the reactivity of tungsten bis(imido) dimethyl complexes with methyl aluminium reagents: Implications for ethylene dimerization

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