Cleavage of CS and OH Bonds by Platinum(0) Complexes To Give Five‐Membered 1,2‐Oxaplatinacycles

Abstract

Spectacular platinum(0): 1,2‐Oxaplatinacycles 2 were formed unexpectedly from 2‐hydroxybenzyl sulfide derivatives 1 by bond cleavage mediated by platinum(0) (see scheme; nb=norbornene). The thermal reaction of 2 gave novel six‐membered 1,2,3‐oxaphosphaplatinacycles through ring expansion accompanied by the insertion of a phosphorus atom into the PtO bond and the 1,2‐shift of a phenyl group.

Carbon–Hydrogen Bond Cleavage Reaction in Four-Coordinate (2,6-Dimethylbenzenethiolato)platinum(II) Complexes. Dramatic Acceleration by Thiolato Hydrogen Acceptor

“…This signal clearly indicates formation of the Pt–CH 2 bond, whose methylene protons couple to the cis and trans phosphorus ligands with coincidentally the same coupling constant. These NMR data unambiguously support the structure of 5c …”

Transition-metal mediated carbon–sulfur bond activation and transformations

“…[11][12][13] This transformation allows insight into the mechanistic aspects of two related heterogeneous catalytic HDS processes. 14 Thus, transition-metal mediated bond cleavage reactions have been well investigated and established for various C-S bonds. In this section, only a concise overview of C-S bond cleavage by stoichiometric amounts of transition metal compounds is presented although a variety of reports have been documented in this area.…”

“…32 (11 and 12) in 72% and 69% yields (eqn (5)), respectively. 14 Substituted thiophene such as 2-cyanothiophene reacted with [Pt(dippe)] 2 (cod)] 2 (13) at elevated temperature afforded Pt(dippe)(k 2 -C,S-C 4 H 3 S) (14) and the [Pt(dippe)] fragment via dissociation of cyclooctadiene (eqn ( 6)). 15 Two isomers, i.e., 14a (major) and 14b were generated.…”

“…71 In this area, organosulfur compounds have also been reported as electrophilic coupling partners. [72][73][74] Although the oxidative addition of organosulfur compounds to a low-valent transition metal species has been well documented, [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] the key to catalytic turnover with organosulfur compounds is activation of the very stable bond that is formed between the catalytically active metal and the soft sulfur atom. The selection of a nucleophilic organometallic reagent for the following transmetalation step is crucial for the reaction to smoothly proceed.…”