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首页> 外文期刊>Chemistry: A European journal >On the reaction of Ph2PNHPPh2 with RNCS (R = Et, Ph, p-NO2C6H4): Preparation of the zwitterionic ligand EtNHC(S)Ph2P=NPPh2C(S)NEt (HSNS) and the zwitterionic metalate [(SNS)Rh(CO)]
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On the reaction of Ph2PNHPPh2 with RNCS (R = Et, Ph, p-NO2C6H4): Preparation of the zwitterionic ligand EtNHC(S)Ph2P=NPPh2C(S)NEt (HSNS) and the zwitterionic metalate [(SNS)Rh(CO)]

机译：关于Ph2PNHPPh2与RNCS（R = Et，Ph，p-NO2C6H4）的反应：两性离子配体EtNHC（S）Ph2P = NPPh2C（S）NEt（HSNS）和两性离子金属酸盐[[SNS）Rh（CO）的制备]

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摘要

The reaction of Ph2PNHPPh2 (PNP) with RNCS (Et, Ph, p-NO2-(C6H4)) gives addition products resulting from the attack of the P atoms of PNP on the electrophilic carbon atom of the isothiocyanate. When PNP is reacted with EtNCS in a 1:2 molar ratio, the zwitterionic molecule EtNHC(S)PPh2=NP+Ph2C(S)N-Et (HSNS) is obtained in high yield. HSNS can be protonated (H2SNS+) or deprotonated (SNS-), behaving in the latter form as an S,N,S-donor pincer ligand. The reaction of HSNS with [(acac)Rh(CO)(2)] (acac = acetylacetonate) affords the zwitterionic metalate [(SNS)Rh(CO)]. Other products can be obtained depending on the R group, the PNP/RNCS ratio (1:1 or 1:2), and the reaction temperature. The proposed product of the primary attack of PNP on RNCS, Ph2PN=PPh2C(S)NHR (A), cannot be isolated. Reaction of A with another RNCS molecule leads to 1:2 addition compounds of the general formula RNHC(S)PPh2=NP+ Ph2C(S)N-R (1), which can rearrange into the non-zwitterionic product RNHC(S)PPh2=NP(S)Ph-2 (2) by eliminating a molecule of RNC. Two molecules of A can react together, yielding 1:1 PNP/RNCS zwitterionic products of the formula RNHCH[PPh2=NP(S)Ph-2]PPh=NP+Ph2C(S)N-R (3). Compound 3 can then rearrange into RNHCH[PPh2=NP(S)Ph-2](2) (4) by losing a RNC molecule. When R=Et (a), compounds 1a, 2a (HSNS), and 4 a have been isolated and characterized. When R=Ph (b), compounds 2b and 4b can be prepared in high yield. When R=p-NO2C6H4 (c), only compound 3c is observed and isolated in high yield. The crystal structures of HSNS, [(SNS)Rh(CO)], and of the most representative products have been determined by X-ray diffraction methods.
机译：Ph2PNHPPh2（PNP）与RNCS（Et，Ph，p-NO2-（C6H4））的反应产生加成产物，这是由于PNP的P原子攻击异硫氰酸酯的亲电子碳原子而产生的。当PNP与EtNCS以1：2的摩尔比反应时，可以高收率获得两性离子分子EtNHC（S）PPh2 = NP + Ph2C（S）N-Et（HSNS）。 HSNS可以质子化（H2SNS +）或去质子化（SNS-），以后者的形式表现为S，N，S供体钳位配体。 HSNS与[（acac）Rh（CO）（2）]（acac =乙酰丙酮化物）的反应提供两性离子金属盐[（SNS）Rh（CO）]。取决于R基团，PNP / RNCS比率（1：1或1：2）和反应温度，可以获得其他产物。无法分离出PNP对RNCS的主要攻击的提议产物Ph2PN = PPh2C（S）NHR（A）。 A与另一个RNCS分子的反应导致通式RNHC（S）PPh2 = NP + Ph2C（S）NR（1）的1：2加成化合物可以重新排列成非两性离子产物RNHC（S）PPh2 = NP （S）Ph-2（2）通过消除一个RNC分子。 A的两个分子可以一起反应，生成分子式为RNHCH [PPh2 = NP（S）Ph-2] PPh = NP + Ph2C（S）N-R的1：1 PNP / RNCS两性离子产物（3）。然后，化合物3可通过丢失RNC分子重新排列为RNHCH [PPh2 = NP（S）Ph-2]（2）（4）。当R ＝ Et（a）时，化合物1a，2a（HSNS）和4a已经被分离和表征。当R ＝ Ph（b）时，可以高收率制备化合物2b和4b。当R ＝对-NO 2 C 6 H 4（c）时，仅观察到化合物3c并且以高收率分离。 HSNS，[（SNS）Rh（CO）]和最具代表性的产品的晶体结构已通过X射线衍射法确定。

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