Supported organometallic complexes Part 31: diaminediphosphineruthenium(II) precursor complexes for parallel synthesis in interphases

The hemilabile, triethoxysilyl functionalized ether–phosphine ligand 4(To) was obtained by reaction of PhP(H)CH2CH2OCH3 (2) with 4-fluorobenzylamine in 1,1′-dimethoxyethane in the presence of potassium and subsequent treatment of the resulting coupling product 3 with (EtO)3Si(CH2)3NCO in dichloromethane. The modified ligand 4(To) was used in the synthesis of a matrix of T-silyl functionalized ruthenium(II) complexes Cl2Ru(P∼O)2(diamine) [6a(To)–6g(To)] by addition of a series of aliphatic and aromatic diamines a–g to the bis(chelated) precursor complex Cl2Ru(P∼O)2 [5(To)]. The corresponding monocationic ruthenium(II) complexes [ClRu(P∩O)(P∼O)(diamine)][BF4] [7a(To)–7g(To)] were available by chloride abstraction from 6a(To) to 6g(To) with AgBF4 or TlPF6 in dichloromethane. Only in the case of 6a(To) it was possible to partially abstract both chlorides to give the dicationic complex [Ru(P∩O)2(diamine)] [PF6]2 [8a(To)] in low yields. Complexes 6a(To)–6g(To) and 7a(To)–7g(To) can be regarded as valuable precursors for sol–gel processing to carry out parallel synthesis in interphases in the field of catalysis.