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首页> 外文期刊>Current Science: A Fortnightly Journal of Research >Aqueous organometallic chemistry: synthesis and characterization of gamma, delta unsaturated alkynyl substituted Fischer carbene complexes of group 6 transition metals
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Aqueous organometallic chemistry: synthesis and characterization of gamma, delta unsaturated alkynyl substituted Fischer carbene complexes of group 6 transition metals

机译：水性有机金属化学：6族过渡金属的γ，δ不饱和炔基取代的费希尔卡宾配合物的合成与表征

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摘要

A number of gamma, delta unsaturated alkynyl substituted carbene complexes [(CO)(5)M=C(OCH3)CHR(CH2C CH)], 4-7 (4: M = Cr, R = CH2C CH; 5: M = Mo, R = CH2C=CH; 6: M = W, R = CH2C=CH and 7: M = W, R = CH(CH2)(2)CH3) have been synthesized from group 6 metal-carbene complexes [(CO)(5)M=C(OCH3)CH3], 1-3 (1: M = Cr, 2: M = Mo, 3: M = W) under biphasic reaction conditions. The alkoxy group has been readily replaced by amino groups in 6 as rotamers 8a-b and 9a-b (syn and anti isomers), (CO)(5)WC(NHR')-CH(CH2CCH)(2), [8a-b: R' = CH3; 9a-b: R' = CH2Ph]. Further, when a CH2Cl2 solution of 4-6 was stirred at room temperature in the presence of trimethylamine-N-oxide for 30 min, the ester derivative CO(OCH3)CH-(CH2CCH)(2) was formed. UV-Vis spectra have been recorded for both alkoxy and amino carbene complexes, 4-8, which showed the gradual hypsochromic shift of metal-to-ligand charge transfer bands from Cr to W. Compounds 4-9 have been isolated as yellow oils in moderate to good yields and they have been characterized by IR, H-1, C-13 NMR spectroscopic analysis.
机译：若干个由γ-δ不饱和炔基取代的卡宾络合物[（CO）（5）M = C（OCH3）CHR（CH2C CH）]，4-7（4：M = Cr，R = CH2C CH; 5：M = Mo，R = CH2C = CH; 6：M = W，R = CH2C = CH和7：M = W，R = CH（CH2）（2）CH3）是由第6组金属-卡宾配合物合成的[[CO ）（5）M = C（OCH3）CH3]，1-3（1：M = Cr，2：M = Mo，3：M = W）在双相反应条件下。烷氧基已很容易被6中的氨基取代，成为旋转异构体8a-b和9a-b（顺式和反式异构体），（CO）（5）WC（NHR'）-CH（CH2CCH）（2），[8a -b：R'＝ CH 3; 9a-b：R'＝ CH 2 Ph]。此外，当在室温下在三甲胺-N-氧化物的存在下将4-6的CH2Cl2溶液搅拌30分钟时，形成酯衍生物CO（OCH3）CH-（CH2CCH）（2）。烷氧基和氨基卡宾配合物4-8的UV-Vis光谱都记录下来，表明金属到配体的电荷转移带从Cr逐渐向W转移。化合物4-9在黄色油中被分离为黄色油。产量中等至良好，并且已通过IR，H-1，C-13 NMR光谱分析对其进行了表征。

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