Preparation, spectroscopic and structural characterization of η¹-N and η²-Se,Se′ complexes of a P₂N₄Se₂ring

Abstract

The reaction of lr5-Ph4P2N4Se2, 1, prepared by the treatment of Ph2PN2(SiMe3)3 with a mixture of SeCI4 and Se2CI2 in acetonitrile, with [PtC12(PEt3)12 gives the adducts [PtCl2(PEt3)],[qI-N-Ph4P2N4Se2] (2, n = 1; 3, n = 2 ) in which the P2N4Se2 ring is shown by an X-ray structural determination of 3 to contain a transannular Se-Se interaction; the oxidative addition of 1 or 2 to Pt(C2H4)(PPh3)2 produces the corresponding q2-Se,Se' complexes.

Reactions of Sodium Bis(N-aryliminophosphoranyl)alkanides with Halide-Bridged Platinum(II) and Palladium(II) Phosphine Dimers Affording Four-Membered M−N−P−C Metallacycles and Orthometalated Platinum(II) and Palladium(II) Complexes

“…As reported earlier for complex 2a , the platinacycles 2a−f show broadening of most 1 H, 31 P, and 13 C signals at 293 K, which has been attributed to a dynamic process involving slow N,N‘ exchange of the C,N-coordinated ligand at 293 K. For 2a−f broad resonances are found in 31 P NMR at 293 K for P B (29.8−45.0 ppm) and P C (−1.6 to 8.0 ppm), whereas the peak due to P A R 3 is hardly broadened and shows characteristic 1 J (Pt,P A ) coupling of 3713−3913 Hz for trans P−Pt−N complexes. , The 2 J (Pt,P B ) value, ranging from 413 to 427 Hz, is characteristic for these types of four-membered platinacycles . Similar two-bond Pt,P couplings have been reported for related C,X-coordinated Pt compounds, i.e.…”