Ruthenium(II) ammine and hydrazine complexes with [N(Ph₂PQ)₂]^- (Q = S, Se) ligands

Reactions of coordinatively unsaturated Ru[N(Ph₂PQ)₂]₂(PPh₃) (Q = S (1), Se (2)) with pyridine (py), SO₂, and NH₃ afford the corresponding 18e adducts Ru[N(Ph₂PQ)₂]₂(PPh₃)(L) (Q = S, L = NH₃ (5); Q = Se, L = py (3), SO₂ (4), NH₃ (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in 2 is pseudo square pyramidal with PPh₃ occupying the apical position, while that in 6 is pseudooctahedral with PPh₃ and NH₃ mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) Å, respectively. The Ru-N bond length in 6 is 2.185(3) Å. Treatment of 1 or 2 with substituted hydrazines L or NH₂OH yields the respective adducts Ru[N(Ph₂PQ)₂]₂(PPh₃)(L) (Q = S, L = NH₂NH₂ (12), t-BuNHNH₂ (14), 1-aminopiperidine (C₅H₁₀NNH₂) (15); Q = Se, L = PhCONHNH₂ (7), PhNHNH₂ (8), NH₂OH (9), t-BuNHNH₂ (10), C₅H₁₀NNH₂ (11), NH₂NH₂ (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a pseudooctahedral arrangement with PPh₃ and hydrazine mutually cis. The Ru-N bond lengths in cis-14·CH₂Cl₂ and cis-15 are 2.152(3) and 2.101(3) Å, respectively. The Ru-N-N bond angles in cis-14·CH₂Cl₂ and cis-15 are 120.5(4) and 129.0(2)°, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow 5 and red trans-Ru[N(Ph2PS)2]2(NH₃)(H₂O) (16), which are characterized by mass spectrometry, ¹H NMR spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH₃ and H₂O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) Å, respectively. Oxidation reactions of the above ruthenium hydrazine complexes are also studied.