Water‐Induced Rearrangement of a Platinacyclic Carbene Produces a Platinacyclic Carbaphosphazene with an Intraannular PtC Bond in a PtNPNPC Ring

Synthesis and structure of orthopalladated complexes derived from prochiral iminophosphoranes and phosphorus ylides

“…The orthometallation of these two species, iminophosphoranes R 3 P@NR 0 [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] and phosphorus ylides R 3 P@C(R 0 )(R 00 ) [49][50][51][52][53][54][55][56][57], is produced, in the vast majority of cases, regioselectively at the Ph rings of the phosphine unit. Some recent contributions have shown, however, that it is possible to obtain orthopalladated complexes derived from CH activation at Ph rings belonging to the R 0 or R 00 substituents of the ylidic carbon and, more precisely, belonging to benzamide moieties [45].…”

“…While this type of reaction has been extensively studied with a large variety of substrates, metallations developed with iminophosphoranes are still scarcely represented [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45]. The iminophosphoranes are compounds of general structure R 3 P@NR 0 (R = alkyl, aryl; R 0 = alkyl, aryl, acyl, .…”

(η6-Arene)−Ruthenium(II) Complexes Containing Methanide and Methandiide Anions of Ph2P(═S)CH2P(═NR)Ph2: Unprecedented Insertion of Isocyanide into a Ruthenium−Carbene Bond

“…Thus, pincer-type structures A have been found in some complexes of group II (Ca, Ba) and IV (Ti, Zr, Hf) , metals, samarium, and molybdenum, while both homobimetallic (M = M′= Cr, Al, Sn, Pb 10 ) and heterobimetallic (M = Ge, M′ = Rh; M = Li, M′ = Rh) species of type B are presently known. In addition, the synthesis and reactivity of the platinum carbene C , containing only one four-membered metallacarbene ring, and the bis(germavinylidene) complex D , ,,, which comprises two germavinylidene moieties [:GeC{P(NSiMe 3 )Ph 2 } 2 ] bonded together in a head-to-head manner, has also been described.…”

Phosphorus-substituted carbene complexes: Chelates, pincers and spirocycles

“…10) in which N-Pt bonding was converted to C-Pt bonding; there was no incorporation of the electrophile into this product [42].…”

“…The N-methylated complex 11 reacted (Scheme 6) with stoichiometric quantities of H 2 O diluted in solvent (uncontrolled addition of water gave intractable products) to give an unusual platinacyclophosphazene, [(g 4 -cod)Pt{CH 2 P-(Ph 2 )NP(Ph 2 )N(Me)-jC,jN}][OTf] ([15][OTf]) wherein both N-Si bonds have been hydrolyzed and a remarkable N-P-C-P-N to C-P-N-P-N rearrangement has taken place [42]. The reaction was complete within 24 h. The rearranged platinacyclic carbaphosphazene 15 (Fig.…”