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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Hydride transfer reactivity of tetrakis(trimethylphosphine)(hydrido)(nitrosyl)molybdenum(0)
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Hydride transfer reactivity of tetrakis(trimethylphosphine)(hydrido)(nitrosyl)molybdenum(0)

机译：四（三甲基膦）（氢）（亚硝酰基）钼的氢化物转移反应性（0）

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摘要

The tetrakis(trimethylphosphine)molybdenum nitrosyl hydrido complex trans-Mo(PMe_3)_4(H)(NO)(2)and the related deuteride complex trnas-Mo(PMe_3)_4(D)(NO)(2a)were prepared from trans-Mo(PMe_3)_4(Cl)(NO)(1).From ~2H T_(1 min)measurements and solid-state ~2H NMR the bond ionicities of 2a could be determined and were found to be 80.0% and 75.3%,respectively,indicating a very polar Mo-D bond.The enhanced hydridicity of 2 is reflected in its very high propensity to undergo hydride transfer reactions.2 was thus reacted with acetone,acetophenone,and benzophenone to afford the corresponding alkoxide complexes trans-Mo(NO)(PMe_3)_4(OCHR'R")(R' = R" = Me(3);R' = Me,R" = Ph(4);R' = R" = Ph(5)).The reaction of 2 with CO_2 led to the formation of the formato-O-complex Mo(NO)(OCHO)(PMe_3)_4(6).The reaction of 2 with HOSO_2CF_3 produced the anion coordinated complex Mo(NO)(PMe_3)_4(OSO_2CF_3)(7),and the reaction with [H(Et_2O)_2][BAr_4~F] with an excess of PMe_3 produced the pentakis(trimethylphosphine)coordinated compound [Mo(NO)(PMe_3)_5][BAr_4~F](8).Inline insertions into the Mo-H bond of 2 were also accomplished.PhCH=NPh(N-benzylideneaniline)and C_(10)H_7CH=NPh(N-1-naphthylideneaniline)afforded the amido compounds Mo(NO)(PMe_3)_4[NR'(CH_2R")](R' = R" = Ph(9),R' = Ph,R" = naphthyl(11)).9 could not be obtained in pure form,however,its structure was assigned by spectroscopic means.At room temperature 11 reacted further to lose one PMe_3 forming 12(Mo(NO)PMe_3),[N(Ph)CH,C_(10)H_6)])with agostic stabilization.In a subsequent step oxidative addition of the agostic naphthyl C-H bond to the molybdenum centre occurred.Then hydrogen migration took place giving the chelate amine complex Mo(NO)(PMe_3)_3[NH(Ph)(CH_2C_(10)H_6)](15).The insertion reaction of 2 with C_(10)H_7N=CHPh led to formation of the agostic compound Mo(NO)(PMe_3)_3[N(CH_2Ph)(C_(10)H_7)](10).Based on the knowledge of facile formation of agostic compounds the catalytic hydrogenation of C_(10)H_7N=CHPhand PhN=CHC_(10)H_7 with 2(5 mol%)was tested.The best conversion rates were obtained in the presence of an excess of PMe_3,which were 18.4% and 100% for C_(10)H_7N=CHPh and PhN=CHC_(10)H_7,respectively.
机译：由反式制备四（三甲基膦）钼亚硝酰基氢化物复合物反式Mo（PMe_3）_4（H）（NO）（2）和相关的氘化物复合物trnas-Mo（PMe_3）_4（D）（NO）（2a） -Mo（PMe_3）_4（Cl）（NO）（1）。通过〜2H T_（1分钟）测量和固态〜2H NMR，可以确定2a的键离子，分别为80.0％和75.3％分别表示非常极性的Mo-D键。2的加氢性增强是由于其极高的氢化物转移反应倾向。2因此使其与丙酮，苯乙酮和二苯甲酮反应生成相应的烷氧基复合物Mo-D （NO）（PMe_3）_4（OCHR′R″）（R′＝ R″ ＝ Me（3）; R′＝ Me，R″ ＝ Ph（4）; R′＝ R″ ＝ Ph（5））。 2与CO_2的反应导致形成甲-O-络合物Mo（NO）（OCHO）（PMe_3）_4（6）.2与HOSO_2CF_3的反应产生阴离子配位的Mo（NO）（PMe_3） _4（OSO_2CF_3）（7），与[H（Et_2O）_2] [BAr_4〜F]与过量的PMe_3反应，生成五（三甲基膦） e）配位化合物[Mo（NO）（PMe_3）_5] [BAr_4〜F]（8）。也成功插入2的Mo-H键中。PhCH= NPh（N-苄叉基苯胺）和C_（10） H_7CH = NPh（N-1-萘叉基苯胺）满足酰胺化合物Mo（NO）（PMe_3）_4 [NR'（CH_2R“）]（R'= R” = Ph（9），R'= Ph，R“ =萘基（11））。9不能以纯净形式获得，但是其结构是通过光谱学方法确定的。在室温下，11进一步反应失去一个PMe_3，形成12（Mo（NO）PMe_3），[N（Ph） CH，C_（10）H_6）]）并具有稳定的化学稳定性。在随后的步骤中，将有害的萘基CH键氧化加成至钼中心。然后发生氢迁移，得到螯合胺络合物Mo（NO）（PMe_3）_3 [NH（Ph）（CH_2C_（10）H_6）]（15）。2与C_（10）H_7N = CHPh的插入反应导致形成有害化合物Mo（NO）（PMe_3）_3 [N（CH_2Ph） （C_（10）H_7）]（10）。基于容易形成的有害化合物的知识，C_（10）H_7N = CHPhand PhN = CHC_（10）H_7 wi的催化加氢测试了2（5 mol％）的最佳转化率。在过量的PMe_3存在下，C_（10）H_7N = CHPh和PhN = CHC_（10）H_7的转化率分别为18.4％和100％ 。

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