Synthesis and crystal structure of [(Ph3P)2N][HRu3(CO)9(PhNCO)], a ruthenium cluster with a phenyl isocyanate ligand

Abstract

The ruthenium cluster [PPN][HRu,(CO),(PhNCO)] {[PPN] = (Ph3Pj2N} has been synthesised by intramolecular nucleophilic attack on CO and characterised by X-ray structure determination.

Homogeneous catalytic carbonylation of nitroaromatics. 5. Kinetics and mechanism of aniline and carbamate formation using ruthenium complex Ru(Ph2PCH2CH2PPh2)(CO)3

“…The NAr group, originally present in II, was converted to aniline. The formulation of IV Proton NMR spectral series for the reaction of Ila with a 10-fold excess of methanol in benzene-d6 under 2.5 atm of CO: (A) 5.1 h, (B) 15.5 h, (C) 29.7 h, (D) 37.5 h, (E) 74.0 h, (F) After heating at Compound II was found to react with other Bronsted acids. Anhydrous HC1 rapidly converts II into the dichloride, V, according to eq 4.…”

“…Figure3. Phosphorus-31 NMR series for the reaction of Ila with a 10-fold excess of methanol in benzene-d6 under 2.5 atm of CO: (A) 5.1 h, (B) 15.5 h, (C)29.7 h, (D) 37.5 h, (E)60.5 h, (F) 74.0 h. The doublet of doublets at 43.0 ppm is due to an unidentified species. The resonance for I appears as a singlet at 73.3 ppm.…”

Chain-transfer agents for living ROMP [Ring-Opening Metathesis Polymerization] reactions of norbornene

“…Catalysts of the type M(CH-í-Bu)(NAr)(0-í-Bu)2 (M = Mo1 or W2) have now been used to polymerize norbornene,3 5,6-disubstituted norbornadienes (stereoselectively),4 and 7,8-bis(trifluoromethyl)tricyclo[4.2.2.02'5]deca-3,7,9-triene5 by living ring-opening metathesis polymerization (ROMP). 6 Living ROMP requires that a propagating alkylidene complex react only with monomer, not with the substituted double bonds in the polymer chain. Up to now, the living polymer has been quenched with an aldehyde in order to remove the metal and cap the polymer in a Wittig-like reaction.…”

Ruthenium catalysed N,N′-diarylurea synthesis from N-aryl substituted formamides and aminoarenes

“…Oxidative addition of the formyl C-H bond to the active ruthenium centre (4) would afford a hydride carbamoyl ruthenium intermediate (5) ,6 followed by P-hydride elimination to give an isocyanate co-ordinated dihydride or hydrogen ruthenium intermediate (6). 7 Nucleophilic attack of amines (2) on the isocyanate moiety of (6) gives the corresponding…”