91464-49-2Relevant academic research and scientific papers
Reaction chemistry of some new hybrid phosphine amide complexes of platinum(II) and palladium(II). Isolation and X-ray structure determination of an ortho-metalated platinum(II) complex derived from a chelated phosphine amide complex of platinum(II)
Hedden, David,Max Roundhill,Fultz, William C.,Rheingold, Arnold L.
, p. 336 - 343 (2008/10/08)
Refluxing the complex trans-PtCl2(o-Ph2PC6H4NHC(O)Ph) 2 in DMF/Et3N gives the cyclometalated complex cis-Pt(o-Ph2PC6H4NC(O)C6H 4)(o-Ph2PC6H4NHC(O)Ph). The complex crystallizes in a triclinic P1 space group with a = 12.038 (3) ?, b = 12.576 (5) ?, c = 16.220 (6) ?, α = 105.80 (3)°, β = 104.84 (3)°, and γ = 95.73 (3)°. The structure shows respective values of 2.063 (7) and 2.065 (8) ? for Pt-N(1) and Pt-C(3). The monodentate P-bonded PNH(CPhO) ligand shows a close "agostic" interaction of the type N-H?Pt. The hydrogen atom has been located at a distance of 2.318 (22) ? from Pt. The analogous palladium complex has been synthesized. The transfer of the ortho carbon hydrogen to the amido nitrogen has been confirmed by deuteration studies using o-Ph2PC6H4NHC(O)C6D5. The "agostic" hydrogen atom undergoes H/D exchange with benzene, acetonitrile, or chloroform. These cyclometalated complexes add HCl to give cis-MCl2(o-Ph2PC6H4NHC(O)Ph) 2 (M = Pd, Pt). With CF3CO2H the reaction is reversible, and N-alkylation occurs with Me2SO4 to give [Pd(o-Ph2PC6H4N(Me)C(O)C6H 4)(o-Ph2PC6H4NHC(O)Ph)]SO 4Me. These amido complexes are stable to water and acetic acid.
Synthesis of new hybrid phosphine amine and phosphine amide compounds. Preparation of a series of new phosphine amido chelate complexes of palladium(II) and platinum(II) and their reactions with bases and br?nsted acids
Hedden, David,Roundhill, D. Max
, p. 4152 - 4158 (2008/10/08)
The phosphine amine and phosphine amide compounds o-Ph2PC6H4NHCH2Ph (PNHBz), o-Ph2PC6H4CH2NHPh (PCNHPh), o-Ph2PC6H4NHC(O)Ph (PNH(CPhO)), and o-Ph2PC6H4C(O)NHPh (P(CO)NHPh) have been synthesized and characterized. The reaction of PNH(CPhO) or P(CO)NHPh with PtCl42- or PdCl42- gives trnas-PtCl2L2 or -PdCl2L2 (L = PNH(CPhO) or P(CO)NHPh)) where L is bonded monodentately through phosphorus. Treatment of these complexes with bases can be used to synthesize the N-bonded amido complexes cis- and trans-M(P(CO)NPh)2 (M = Pd, Pt) and cis-Pt(PN(CPhO))2. The amido complexes react with HCl to give MCl2(PNH(CPhO))2 and MCl2(P(CO)NHPh)2 (M = Pd, Pt). Structures are deduced by a combination of IR, 1H NMR, and 31P{1H} NMR techniques.
