Reactivity of the TpRu(HN = CPh 2 )(PPh 3 ) -Azido complex and Insertion of Methylene into the Tp B -H Bond

Herein, we report on the reactivity of an Ru(II) azido complex allowing the facile synthesis of further interesting complexes. Starting from the parent chlorido complex (HN = CPh2)[Ru] -Cl { 1 , [Ru] = Tp(PPh3)Ru; Tp = HB(pz)3, pz = pyrazolyl)} the title complex (HN = CPh2)[Ru] -N3 ( 2 ) was obtained upon reaction with NaN3. The N (2)-bound 4,5-bis-(methoxycarbonyl)-1,2,3-triazolato com-plex (HN = CPh2)[Ru] -{N3C2(CO2Me)2} ( 3 ) was obtained from reaction of 2 with dimethyl acety-lene dicarboxylate (DMAD). Protonation of 3 with HCl afforded the N-coordinated triazolato com-plex {HN3C2(CO2Me)2 }[Ru] -Cl ( 4 ). Reaction of CS2 with 2 produced the thiocyanato complex (HN = CPh2)[Ru] -NCS ( 5 ). The Ru tetrazolato complex (HN = CPh2)[Ru] -N4C[C(CN) = C(CN)2] ( 6 ) was pre-pared from 2 and tetracyanoethylene (TCNE). The reaction of 2 with HX gave the 17-electron Ru(III) complexes (Cl)[Ru] -X ( 7a , X = Cl; 7b , X = Br) and the Ru(II) complexes containing the methyl tris(pyrazolyl)borate ligand MeTp(PPh3)(HN = CPh2)Ru -X ( 8a , X = Cl; 8b , X = Br), as a result of an un-usual methylene insertion into the B -H bond of the Tp ligand with the CH2Cl2 solvent as the assumed source for the methylene. The structures of 4, 5, 7a, 7b and 8b had been determined by X-ray diffraction analysis.(c) 2022 Elsevier B.V. All rights reserved.