Synthesis and Characterization of Phosphinecarboxamide and Phosphinecarbothioamide, and Their Complexation with Palladium(II) Complex

• Published in: Molecules (Basel, Switzerland) Switzerland), 2022-08, Vol.27 (17), p.5564
• Main Authors: Itazaki, Masumi, Okabayashi, Kento, Matsutani, Takanari, Nochida, Tomoya, Moriuchi, Toshiyuki, Nakazawa, Hiroshi
• Format: Article
• Language: English
• Subjects: cis/trans isomerization; Geometry; hydrogen bond; Hydrogen bonds; hydrophosphination; Isocyanates; Ligands; Molecular structure; NMR; Nuclear magnetic resonance; Palladium; Palladium chloride; palladium(II) complex; phosphinecarbothioamide; phosphinecarboxamide; Room temperature; Single crystals; Solvents; X-ray diffraction
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27175564

Reactions of isocyanates/isothiocyanates with primary and secondary phosphines without solvent at room temperature afforded phosphinecarboxamide/phosphinecarbothioamide, respectively, in excellent yields. Furthermore, palladium complex Pd(COD)Cl2 was allowed to react with Ph2PC(O)NHPh (1a) to afford [Pd{Ph2PC(O)NHPh-κP}2Cl2] (3). On the other hand, the reaction of Pd(COD)Cl2 with 1 eq. of Ph2PC(S)NHPh (2a) afforded [PdCl2{Ph2PC(S)NHPh-κP,S}] (4). In the case of a 1:2 molar ratio, [PdCl{Ph2PC(S)NHPh-κP,S}{Ph2PC(S)NHPh-κP}]Cl (5) was formed. The newly obtained compounds were fully characterized using multielement NMR measurements and elemental analyses. In addition, the molecular structures of Ph2PC(O)NH(CH2)2Cl (1j), Ph2PC(S)NHPh(4-Cl) (2c), and 3–5 were determined using single-crystal X-ray diffraction.