2-Thia-1,3,5-triaza-7-phosphaadamantane-2,2-dioxide Revisited: Computational and Experimental Studies of a Neglected Phosphine

Abstract

The cage-phosphine 2-thia-1,3,5-triaza-7-phosphaadamantane-2,2-dioxide (PASO2) was reacted with various transition metal precursors to give the complexes cis-[Mo(CO)4(PASO2)2], [AuCl(PASO2)], cis-[PtCl2(PASO2)2], [Ru(η6-p-cym)Cl2(PASO2)], [Rh(η5-C5Me5)Cl2(PASO2)], and [Rh(η5-C5Me5)Cl(PASO2)2]+ as well as the cyclometalated palladium(II) complexes [PdCl{κC,N-C6H4C(Ph)NCH2CO2Et}(PASO2)] and [PdCl(κC,N-1,8-C10H6NMe2)(PASO2)]. The compounds were characterized by spectroscopic methods and several examples by single-crystal X-ray diffraction. The stereoelectronic properties of PASO2 were determined by computational methods and were compared with those of other phosphines, in particular 1,3,5-triaza-7-phosphaadamantane.

Interpreting Oxidative Addition of Ph–X (X = CH3, F, Cl, and Br) to Monoligated Pd(0) Catalysts Using Molecular Electrostatic Potential

“…MESP analysis has helped theoreticians and experimentalists in understanding the stereoelectronic profile of phosphine ligands, which led to the rational design of superior ligands. 55 Quantification of steric and electronic effects of NHC ligands toward metal coordination has also been carried out using topographical analysis of MESP in which a linear correlation between Tolman electronic parameter and electrostatic potential at carbene carbon ( V C ) was established. 56 Structure and reactivity of substituted arene–Cr(CO) 3 complexes are also well-explained using MESP topography analysis.…”

Homoleptic phosphino copper(i) complexes with in vitro and in vivo dual cytotoxic and anti-angiogenic activity

“…In the 1 H NMR spectrum of complex 3 ( Figure S6), the upper rim proton signals of coordinated PTA-SO2 showed disappearance of the coupling with the P atom, as previously reported by other authors in PTA-SO2 containing Au(I) and Pt(II) complexes. 31 .…”

“…S3, ESI †). 31 P NMR of complex 2 showed a broad singlet centered at À64.6 ppm (Fig. S2, ESI †), downfield shifted by 10.7 ppm compared to the corresponding signal in uncoordinated DAPTA.…”

“…S6, ESI †), the upper rim proton signals of coordinated PTA-SO 2 showed the disappearance of the coupling with the P atom, as previously reported by other authors in PTA-SO 2 containing Au(I) and Pt(II) complexes. 31 The ESI(+)-MS spectrum of complex 2 recorded in methanol or acetonitrile solutions did not show the signal corresponding to the [M] + molecular ion, but only the fragment ions due to [Cu(DAPTA) 2 ] + and [Cu(DAPTA)] + at m/z 521 (100%) and 292 (20%), respectively (Fig. S4, ESI †).…”

“…Elemental analyses were performed on a Carlo Erba 1106 Elemental Analyzer 1. H,31 P and13 C NMR spectra were recorded on a Bruker AMX-300 instrument (300.13 MHz for 1 H, 75.47 MHz for13 C and 121.41 MHz for 31 P), using SiMe 4 as internal reference ( 1 H and 13 C) and 85% aqueous H…”