Design, synthesis, and chemistry of sterically nondemanding primary bisphosphines.
Design, synthesis, and chemistry of sterically nondemanding primary bisphosphines.
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空间要求不高的伯双膦的设计、合成和化学。
DOI：
10.1021/ja047238y
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
Katti,KatteshV
中科院分区：
文献类型：
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作者：
Pillarsetty,Nagavarakishore;Raghuraman,Kannan;Barnes,CharlesL;Katti,KatteshV
设计并合成了在PIII中心上带有最小化学单元H的螯合双膦（（PH_2CH_2）_2CHCH_2NHPh（4）和（PH_2CH_2）_2CHCONHPh（5））。研究表明，没有庞大的化学取代基是必要的，以提供热/氧化稳定性的− PH 2基团4和5的描述。在5（或4）中的PIII中心周围的H原子符合有限/无空间影响，但膦表现出高亲核性以与W（0）和Re（I）强烈配位。研究了一种对空气稳定的伯双膦（5）的合成和X射线结构表征，以及它与W（CO）6和Re（CO）5 Br的过渡金属化学反应，分别得到了配合物（η2-（PH 2CH 2）2CHCONHPh）W（CO）4（6）和（η2-（PH 2CH 2）2CHCONHPh）Re（CO）3Br（7）。
Design and synthesis of chelating bisphosphines functionalized with the smallest chemical unit “H” on the PIIIcenters ((PH2CH2)2CHCH2NHPh (4) and (PH2CH2)2CHCONHPh (5)) are described. Studies demonstrating that no bulky chemical substituents are necessary to offer thermal/oxidative stability to the −PH2groups in4and5are described. The H atoms around the PIIIcenters in5(or4) concur limited/no steric influence, but yet the phosphines manifest high nucleophilicity to coordinate strongly with W(0) and Re(I). The studies include synthesis and X-ray structural characterization of an air-stable primary bisphosphine (5) and its transition-metal chemistry with W(CO)6and Re(CO)5Br to produce the complexes (η2-(PH2CH2)2CHCONHPh)W(CO)4(6) and (η2-(PH2CH2)2CHCONHPh)Re(CO)3Br (7), respectively.