REACTIONS OF TRIETHYLAMMONIUM SALTS OF THE (MU -CO)(MU -RS)FE2(CO)6- ANIONS WITH ALKYNYLMERCURY COMPOUNDS. UNEXPECTED PRODUCTS VIA HYDROGEN MIGRATION PROCESSES
REACTIONS OF TRIETHYLAMMONIUM SALTS OF THE (MU -CO)(MU -RS)FE2(CO)6- ANIONS WITH ALKYNYLMERCURY COMPOUNDS. UNEXPECTED PRODUCTS VIA HYDROGEN MIGRATION PROCESSES
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DOI：
10.1021/om00022a019
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发表时间：
1994-10
期刊：
影响因子：
2.8
通讯作者：
D. Seyferth;D. Ruschke;W. M. Davis;M. Cowie;A. D. Hunter
中科院分区：
文献类型：
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作者：
D. Seyferth;D. Ruschke;W. M. Davis;M. Cowie;A. D. Hunter
OCH 3，N（CH 3）2。乙烯基碳炔产物是由从炔丙基碳原子到原始炔属单元的β-碳原子的净1，2-氢移位产生的。此外，与二（3-甲氧基-1-丙炔基）汞反应得到了一个四铁簇合物[（n-CH_3 OCH_2-CHC）（M-RS）Fe_2（CO）_6]_（12）Hg，它是由两个蝶形六羰基二铁（每个二铁都有亚乙烯基和硫醇根的双桥连配体）通过蝶形铰链上的汞原子桥连而成的。对乙烯基碳炔络合物（n-CH 3 OCH-CHC）（n-i-BuS）Fe 2（CO）6以及二聚汞产物[（n-CH 3 OCH 2CH = C）（n-BuS）Fe 2（CO）6] 2 Hg进行X射线晶体结构测定。炔丙基取代的1-溴代炔的反应也依赖于乙炔的性质。3-甲氧基-1-溴丙炔形成w-？/ 1：？/ 2-乙炔化物络合物CNOM-//1：？/ 2-C= CCH 2 OCH 3）（2-i-BuS）Fe 2（CO）6以及双桥连乙烯基碳炔产物，而3-二甲氨基-1-溴丙炔仅得到乙烯基碳炔络合物。乙烯基碳炔络合物（m-CH 30 CH = CHC）（m-i-BuS）-Fe 2（CO）e转化为甲酰基取代的μ-·。2-\？\络合物（iw-？/ 1：？/ 2-CH= CHC-（0）H）（wi-BuS）Fe2（CO）6。
OCH3, N (CH3) 2. The vinylcarbyne products resulted from a net 1, 2-hydrogen shift from the propargylic carbon atom to the/3-carbon atom of the original acetylenic unit. In addition, the reaction with bis (3-methoxy-l-propynyl) mercury gave a tetrairon cluster,[(/Í-CH3OCH2-CHC)(M-RS) Fe2 (CO) 6l2Hg, composed of two butterfly diiron hexacarbonyl moieties (each of which possessed doubly bridging vinylidene and thiolate ligands) bridged by a mercury atom on the butterfly hinges. X-ray crystal structure determinations were carried out on the vinyl carbyne complex (/1-CH3OCH—CHC)(«-i-BuS) Fe2 (CO) 6 as well as the dimeric mercury product [(ti-CH30CH2CH= C)(Mi-BuS) Fe2 (C0) 6l2Hg. The reactions of propargylic substituted 1-bromoalkynes also were dependent on the nature of the acetylene. 3-Methoxy-l-bromopropyne formed the w-?/1:?/2-acetylide complex ÍM-//1:?/2-C= CCH2OCH3)(^-í-BuS) Fe2 (CO) 6, as well as the doubly bridging vinylcarbyne product, while 3-dimethylamino-l-bromopropyne gave only the vinylcarbyne complex. The vinylcarbyne complex (m-CH30CH= CHC)(m-í-BuS)-Fe2 (CO) e was converted to the formyl-substituted µ-·. 2-\?\complex (iw-?/1:?/2-CH= CHC-(0) H)(wi-BuS) Fe2 (C0) e upon treatment with aqueous hydrochloric acid or trifluoroacetic acid.