Synthesis and characterisation of isomeric cycloaurated complexes derived from the iminophosphorane Ph3PNC(O)Ph

Abstract

Using different organomercury substrates, two isomeric cycloaurated complexes derived from the stabilised iminophosphorane Ph 3 P=NC(O)Ph were prepared. Reaction of Ph 3 P=NC(O)Ph with PhCH 2 Mn(CO) 5 gave the manganated precursor (CO) 4 Mn(2-C 6 H 4 C(O)N=PPh 3), metallated on the C(O)Ph substituent, which yielded the organomercury complex ClHg(2-C 6 H 4 C(O)N=PPh 3) by reaction with HgCl 2 in methanol. Transmetallation of the mercurated derivative with Me 4 N[AuCl 4 ] gave the cycloaurated iminophosphorane AuCl 2 (2-C 6 H 4 C(O)N=PPh 3) with an exo PPh 3 substituent. The endo-isomer AuCl 2 (2-C 6 H 4 Ph 2 P=NC(O)Ph) [aurated on a PPh 3 ring] was obtained by an independent reaction sequence, involving reaction of the diarylmercury precursor Hg(2-C 6 H 4 P(=NC(O)Ph)Ph 2) 2 1 [prepared from the known compound Hg(2-C 6 H 4 PPh 2) 2 and PhC(O)N 3 ] with Me 4 N[AuCl 4 ]. Both of the isomeric iminophosphorane derivatives were structurally characterised, together with the precursors (2-HgClC 6 H 4)C(O)N=PPh 3 and (CO) 4 Mn(2-C 6 H 4 C(O)N=PPh 3). The utility of 31 P NMR spectroscopy in monitoring reaction chemistry in this system is described.

An orthomanganation route to 2-substituted derivatives of N-methyl-1,8-naphthalimide

“…This is as expected from related compounds that have been structurally characterised [23,24]. This ready synthesis of the mercury derivative of naphthalimide provides a substrate for the many different syntheses that are established based on aryl-mercury compounds [25], giving many potential 2-substituted naphthalimide compounds.…”

In Vitro and in Vivo Evaluation of Water-Soluble Iminophosphorane Ruthenium(II) Compounds. A Potential Chemotherapeutic Agent for Triple Negative Breast Cancer

“…We followed the strategy for the preparation of Hg(Ph 3 P=N-CO-2-C 6 H 4 )Cl. 53 The C–H activation at the N-CO-Ph fragments takes place at a manganese center, and by transmetalation of the resulting cyclometalated iminophosphorane manganese compounds to HgCl 2 , the organomercury derivatives with PPh 3 [Hg(Ph 3 P=N-CO-2-C 6 H 4 )Cl] 53 or water-soluble phosphine PTA [Hg(PTA=N-CO-2-C 6 H 4 )Cl] ( 7 ) are obtained in high yields. Transmetalation reactions of [Hg(Ph 3 P=N-CO-2-C 6 H 4 )Cl] 53 and 7 with [(η 6 - p -cymene)Ru(μ-Cl)Cl] 2 afford new cyclometalated compounds [(η 6 - p -cymene)Ru(IM-k-C,N)Cl] (IM = Ph 3 P=N-CO-2-C 6 H 4 8 ; PTA=N-CO-2-C 6 H 4 9 ) in high yields (Scheme 2 ).…”

“…Solvents were purified by use of a PureSolv purification unit from Innovative Technology, Inc. Compounds [PhCH 2 Mn(CO) 5 ], 79 [(η 6 - p -cymene)Ru(μ-Cl)Cl] 2, 52 [Hg(2-C 6 H 4 C(O)N=PPh 3 )Cl], 53 and IM ligands Ph 3 P=N-CO-2-N-C 5 H 4 , 51 Ph 3 P=N-8-C 9 H 6 N, 49 [Cp-P(Ph 2 )=N–CH 2 -2-NC 5 H 4 }Fe(Cp)], 48 and Ph 3 P=N-CO-2-C 6 H 4 51 were prepared by reported methods. The purity of the compounds, based on elemental analysis, is ≥99.5%.…”

Cyclometalated gold(III) iminophosphoranes which incorporate carbohydrate groups

“…Azides are notorious for their explosive nature, but as the percentage of nitrogen in the azide decreases they become less explosive. The Smith rule [11] is an indication of whether an [30]. The phosphine was reacted with an azide to produce an intermediate mercurated iminophosphorane, which could be transmetalated with Au(III).…”

“…Monitoring of the reaction by 31 P NMR and ESI-MS showed that the intermediate mercurated iminophosphorane, 5a, had fully formed after 1.5 h. Removal of the solvent gave 5a which was used directly, after characterisation by 31 P NMR and ESI-MS. The ion [AuCl 4 ] À has been used to produce gold(III) iminophosphoranes [6,17,30]. To 5a was added [NMe 4 ][AuCl 4 ] and dry acetonitrile and the mixture stirred for several days in the dark.…”