Synthesis and Characterization of Triazenide and Triazene Complexes of Ruthenium and Osmium

Citations Over TimeTop 16% of 2006 papers

Abstract

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.

Related Papers

• → Synthesis of methylene-bis(1-oxy-3,3-dialkyl-1-triazene 2-oxides) and their analogs(2015)24 cited
• → A facile route to the new triazene dyes based on substituted pyrazolidin-3,5-dione derivatives(2011)16 cited
• → tBu2PF as a ligand in tri-osmium clusters(1995)12 cited
• → The Surface of Inorganic Oxides: An Unusual Reaction Medium for the High‐Yield and Selective Synthesis of Various Osmium Carbonyl Clusters(1999)5 cited
• → ChemInform Abstract: 1‐ARYL‐3,3‐DIALKYL‐TRIAZENE 7. MITT. REVERSIBLE ZWEI‐ELEKTRONEN‐OX. 4‐SUBSTITUIERTER 1‐PHENYL‐3,3‐DIMETHYL‐TRIAZENE(1972)