Synthesis of S2−- and PF2O2-Bridged Dinuclear Ruthenium(IV) Complex Obtained from the Reaction of Disulfide-Bridged Ruthenium(III) Dimer Complex with Dioxygen and Water

Abstract

Reaction of [{Ru(CH3CN)3[P(OMe)3]2}2(μ-S2)](PF6)3 with a mixture of acetylene and O2 gave a novel ruthenium(IV) dimer complex [{Ru(IV)(PFO3)[P(OMe)3]2}2(μ-S)(μ-PF2O2)2]. The newly formed bridging and terminal ligands PF2O2− and PFO32− are produced from the reaction of PF6− with trace amounts of H2O in the solvent. Although acetylene is not incorporated in the final product, it is necessary to accelerate the reaction. Ruthenium(IV) complexes with S2− ligand are rare and only two examples are previously known. The crystal of [{Ru(PFO3)[P(OMe)3]2}2(μ-S)(μ-PF2O2)2] is monoclinic, space group P21/n, a = 11.061(5), b = 20.764(4), c = 17.074(3) Å, β = 95.74(2)°, V = 3901(1) Å3, and Z = 4. The bridging PF2O2− ligand coordinates to Ru atoms with the two oxygen atoms, while the terminal PFO32− ligand coordinates to a Ru atom with one of the oxygen atoms. The molecular structure is confirmed by 31P and 19F NMR spectroscopy.

[B(3,5‐C6H3Cl2)4]– as a Useful Anion for Organometallic Chemistry

“…As the desired cationic species that partner these anions are often rather reactive, any associated anion is also required to be robust to metal‐promoted reactivity. Thus, the anions[PF 6 ] – and [BF 4 ] – , although ubiquitous, are often not the choice for demanding applications due to hydrolysis by adventitious water or fluoride abstraction 2. Although the range of possible anions is large, only a handful are used routinely (Scheme ).…”

Coordination behaviour of (diaryl disulfide)-bridged dinuclear thiairidaindan cores: ligand substitution by isocyanides, CO, hydrazines and hydroxylamine, and related reactions

“…During our extensive studies on the reactivities of thiolatobridged dinuclear chloro complexes having η 5 -C 5 Me 5 ligands, 5 we have already found that treatment of these complexes with silver cations is effective in producing open coordination sites on the dinuclear centres. 20 Thus, we carried out the reactions of the thiairidaindan complexes with silver cations to generate 21 The presence of the PF 2 O 2 ligand is also suggested by the IR spectrum, which shows ν(PO) bands at 1142 and 1263 cm Ϫ1 , and a ν(PF) band at 841 cm Ϫ1 ; a ν(NC) band due to the isocyanide ligands also appears at 2143 cm Ϫ1 . The molecular structure determined by an X-ray study is depicted in Fig.…”

“…21, 22 The transformation of the PF 6 anion into metal-bound PF 2 O 2 is known to be mediated by transition metals, including iridium and silver. [21][22][23] The oxygen source in these reactions seems to be adventitious water rather than dioxygen. For…”

“…. 21 On the basis of a mass spectroscopic experiment using 18 O 2 , they have concluded that the oxygen atoms in the difluorophosphato ligand are derived from a trace amount of water in the solvent. On the other hand, AgPF 6 is hydrolyzed by trace amounts of water in dichloromethane, even in the absence of other transition metals.…”

Novel C–H activation and C–S formation reactions on disulfide and diselenide ligands in dinuclear ruthenium complexes

“…The contribution from (iii) was shown to be negligible through spectroscopy studies [41][42][43][44][45][46]. Since our first report of the disulfide-bridged Ru III dinuclear complex, [{Ru(P(OCH 3 ) 3 ) 2 Cl} 2 (l-S 2 )(l-Cl) 2 ] (1) [53], we have developed various C-H cleavage and C-S formation reactions of unsaturated organic molecules on the disulfide ligand [54][55][56][57][58][59][60][61][62][63]. The selenium analogue, [{Ru(P(OCH 3 ) 3 ) 2 Cl} 2 (l-Se 2 )(l-Cl) 2 ] (2), has also been synthesized and similar reactions were performed [64].…”