Bimetallic Activation of White Phosphorus

Abstract

The formation of novel complexes [M(dppm)(Ph 2 PCH 2 PPh 2 PPPP)]OTf (M = Rh, Ir, dppm = bisdiphenylphoshinomethane, OTf = OSO 2 CF 3 ) bearing in their coordination sphere a new type of oligophosphorus ligands results from bimetallic activation and consequent transformation of white phosphorus. These complexes display electrophilic properties and can be activated either electrochemically or by interaction with nucleophilic reagents.

P4 Activation by Late-Transition Metal Complexes

“…Both complexes 284 and 285 are electrochemically active at cathodic potentials and undergo a two-electron reduction at the cathodic peak C 1 (two-electron process, see Figure 58). 189 Thus, complexes 284 and 285 can be activated electrochemically by irreversible transfer of two electrons or by interaction with nucleophiles by reaction with [Pt(C 2 H 4 )-(PPh 3 ) 2 ], as clearly identified by 1 H and 31 P{ 1 H} NMR experiments. 190 The tetrahedral triiridium cluster, [{Ir(PF 3 ) 3 } 3 (µ 3 -P)] (290), was obtained in poor yield as an orange crystalline material from the high pressure (80-200 atm) reaction of IrCl 3 and PF 3 .…”

“…Both complexes 284 and 285 are electrochemically active at cathodic potentials and undergo a two-electron reduction at the cathodic peak C 1 (two-electron process, see Figure ) …”

“…Cyclic voltammogram (CV; cathodic part) in DMF of complex 285 (1.0 × 10 −2 M) on glassy carbon (GC) electrode in the presence of 0.1 M (NBu 4 )BF 4 [CV curve was recorded at the first scan: (a) from 0.00 to −2.50 V and back to 0.00 V; (b) from 0.00 to −1.90 V and back to 0.00 V; vs Ag/AgNO 3 1.0 × 10 −2 M in CH 3 CN; 50 mV s −1 ]. Reproduced with permission from Figure in ref . Copyright 2008 Taylor and Francis Ltd.…”