Preparation and properties of new methyl-(alkoxo)- and methyl-(thiolato)nickel and methyl(alkoxo)- and methyl(thiolato)-palladium complexes. Carbon monoxide and carbon disulfide insertion into the alkoxo-palladium bond
Preparation and properties of new methyl-(alkoxo)- and methyl-(thiolato)nickel and methyl(alkoxo)- and methyl(thiolato)-palladium complexes. Carbon monoxide and carbon disulfide insertion into the alkoxo-palladium bond
复制标题
新型甲基-(烷氧基)-和甲基-(硫醇)镍以及甲基(烷氧基)-和甲基(硫醇)-钯络合物的制备和性质。
DOI：
10.1021/om00100a016
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发表时间：
1988
期刊：
影响因子：
2.8
通讯作者：
A. Yamamoto
中科院分区：
文献类型：
--
作者：
Yong;K. Osakada;K. Sugita;Takakazu Yamamoto;A. Yamamoto
镍、钯； R= CH (CF3) 2、CH2CF3、CH (CF3) C «H6))。这些络合物已通过元素分析和NMR(1H,^)、19F和13C(xH))光谱进行了表征。由此获得的甲基(烷氧基)镍(II)和-钯(II)络合物在常压下与一氧化碳反应，以高收率得到羧酸酯。一氧化碳与 NiMe (SAr)(dpe)(Ar= C6H6, C6H4-p-CH3) 反应也能以良好的产率得到相应的硫代碳酸酯，而 PdMe (SPh)(dpe) 在类似条件下不与一氧化碳反应。 31P {1H| PdMe(OCH(CF3)2)(dpe)与等摩尔量的13CO在60℃下的反应混合物的NMR谱表明，通过将一氧化碳插入Pd-0键而形成PdMe(13COOCH(CF3)2)(dpe)。当反应温度升至约20℃时，该烷氧基羰基络合物发生还原消除，得到乙酸1,1,1,3,3,3-六氟-2-丙酯。该反应伴随着烷氧基羰基配体同时脱羰以再生PdMe (OCH-(CF3) 2)(dpe)。 PdMe (OCH (CF3) Ph)(dpe) 与二硫化碳反应生成可分离的钯配合物 PdMe (SCSOCH (CF3) Ph)(dpe)，其通过将 CS2 插入 Pd-0 键而形成，而 PdMe-(SPh)(dpe) 不与 CS2 发生反应。
Ni, Pd; R= CH (CF3) 2, CH2CF3, CH (CF3) C «H6)). These complexes have been characterized by elemental analysis and NMR (1H,^), 19F, and l3C {xH}) spec-troscopy. The methyl (alkoxo) nickel (II) and-palladium (II) complexes thus obtained react with carbon monoxide at normal pressure to give carboxylic esters in high yields. Reaction of carbon monoxide with NiMe (SAr)(dpe)(Ar= C6H6, C6H4-p-CH3) also gives the corresponding carbothioic esters in good yields, while PdMe (SPh)(dpe) is unreactive with carbon monoxide under similar conditions. The 31P {1H| and NMR spectra of the reaction mixture of PdMe (OCH (CF3) 2)(dpe) with an equimolar amount of 13CO at-60 C show the formation of PdMe (13COOCH (CF3) 2)(dpe) produced through insertion of the carbon monoxide into the Pd-0 bond. When the reaction temperature is raised to-20 C, this alkoxycarbonyl complex undergoes reductive elimination to give l, l, l, 3, 3, 3-hexafluoro-2-propyl acetate. The reaction is accompanied by simultaneous decarbonylation of the alkoxycarbonyl ligandto regenerate PdMe (OCH-(CF3) 2)(dpe). The reaction of PdMe (OCH (CF3) Ph)(dpe) with carbon disulfide gives an isolable palladium complex, PdMe (SCSOCH (CF3) Ph)(dpe), formed by insertion of CS2 into the Pd-0 bond, while PdMe-(SPh)(dpe) is unreactive with CS2.