Unusual products from CO/ethene reactions catalysed by β-ketophosphine and related complexes of rhodium
作者:Ruth A. M. Robertson、David J. Cole-Hamilton、Andrew D. Poole、Marc J. Payne
DOI:10.1039/b007989h
日期:——
of tertiary phosphines with carbonyl groups β to the P atom, ethene and CO react in methanol to give products involving increased chain growth (octane-3,6-dione, methyl 4-oxohexanoate) compared with PEt3 complexes and unsaturated products (methyl propenoate, penten-3-one and 1-methoxypentan-3-one from addition of methanol to penten-3-one); mechanistic studies suggest that the ligand carbonyl group prevents
使用在 P 原子上具有 β 位羰基的叔膦的铑配合物,乙烯和 CO 在甲醇中反应,生成与 PEt3 配合物和不饱和产物相比增加链增长的产物(辛烷-3,6-二酮、4-氧代己酸甲酯)(将甲醇加入到 penten-3-one 中得到的丙烯酸甲酯、penten-3-one 和 1-methoxypentan-3-one);机理研究表明,配体羰基阻止了生长链中酮基的配位。
Complexes of rhodium and iridium with the β-ketophosphines PBu<sup>t</sup><sub>2</sub>-(CH<sub>2</sub>COR)(R = Ph or Bu<sup>t</sup>)
作者:H. David Empsall、Stephen Johnson、Bernard L. Shaw
DOI:10.1039/dt9800000302
日期:——
behave towards rhodium or iridium either as unidentate ligands (through phosphorus), as bidentate ligands through phosphorus and the keto-group, or as bidentate enolate ions. Treatment of [Rh2Cl2(CO)4] with Q or Q′ gives trans-[RhCl(CO)Q2] or trans-[RhCl(CO)Q′2] These react with sodium methoxide to give complexes of type [[graphic ommitted])R}PBut2(CH2COR)}](R = Ph or But) which with hydrogen chloride give
庞大的β-酮膦化合物PBu t 2(CH 2 COPh)(Q)和PBu t 2(CH 2 COBu t)(Q')已显示出作为铑或铱的身份不明的配体(通过磷),作为二齿配体通过磷和酮基,或作为双齿烯酸酯离子。的[Rh的治疗2氯2(CO)4 ]具有Q或Q'给出反式- [的RhCl(CO)问2 ]或反式- [的RhCl(CO)Q' 2 ]这些与甲醇钠反应,得到式的配合物[[略去图形])R} PBu t 2(CH 2COR)}](R =苯基或丁基吨),其与氯化氢给回反式- [的RhCl(CO)PBU吨2(CH 2 COR)} 2 ]。带有PBu t 2(CH 2 COPh)的盐RhCl 3 ·3H 2 O得到[[图形省略] Ph}-PBu t 2(CH 2 COPh);(4a),其中两个膦都是双齿的,并且酮基该小组的工作非常协调,没有因一氧化碳的大力处理而被取代。六配位的铑(III)与甲醇钠
Shevchenko, I. V.; Furmanova, M. V.; Kukhar', V. P., Journal of general chemistry of the USSR, 1989, vol. 59, # 10.1, p. 1977 - 1981
作者:Shevchenko, I. V.、Furmanova, M. V.、Kukhar', V. P.、Kolodyazhnyi, O. I.
Complexes of nickel(<scp>II</scp>), palladium(<scp>II</scp>), and platinum(<scp>II</scp>) with the β-ketophosphines PBu<sup>t</sup><sub>2</sub>(CH<sub>2</sub>COR)(R = Ph or Bu<sup>t</sup>)