Mononuclear(η6-arene)ruthenium(II) and (η5-pentamethllcyclopentadienyl)rhodium(III) and binuclear ruthenium(II)-platimum(II) and ruthenium(II)-rhodium(I) complexes containing 2-(diphenylphosphino)pyridine

IrPd, IrHg, IrCu, and IrTl Binuclear Complexes Bridged by the Short-Bite Ligand 2-(Diphenylphosphino)pyridine. Catalytic Effect in the Hydroformylation of Styrene Due to the Monodentate P-Bonded 2-(Diphenylphosphino)pyridine Ligands oftrans-[Ir(CO)(Ph2PPy)2Cl]

“…Compounds 11 and 12 are soluble in chlorinated solvents, acetone, methanol, and, to a minor extent, benzene to give air-sensitive solutions. The 31 P{ 1 H} NMR spectra of 11 and 12 in CDCl 3 solution show singlets at δ 27.44 and δ 23.20 ppm, respectively, and support a structure with head-to-head bridging Ph 2 PPy ligands . As expected, in the 1 H NMR spectra in CDCl 3 solution, the 6-hydrogen of the pyridine ring is shifted to higher frequency (δ 9.39 and 9.15 ppm, respectively) with respect to 1 …”

“…The Ir−Hg bond length is comparable with the value of 2.618 Å found for the complexes [Cl 2 Hg(μ-Cl) 2 HgIr(CO)Cl(dpm)(μ-dpm)AuCl] (dpm =diphenylphosphinomethane) and [Ir(COD)(EpTT) 2 HgCl] 2 (EpTT = C 2 H 5 N 3 - p -CH 3 C 6 H 4 ) and longer than the value reported for the complex [IrCl 2 (CO)(PPh 3 ) 2 (HgX)] (X = Cl, Br) (Ir−Hg(Cl) = 2.570(1) Å, Ir−Hg(Br) = 2.578(2) Å). The metal−metal bond distance is shorter than the nonbonded P···N separations (P(1)···N(1) = 2.721 Å and P(2)···N(2) = 2.703 Å); the latter is in the range found for other Ph 2 PPy-bridged complexes 12b. Bond distances and angles for the coordinated Ph 2 PPy are nearly alike, as are the P−M−M−N torsion angles P(1)−Ir−Hg−N(1) = 32.2(4)° and P(2)−Ir−Hg−N(2) = −28.9(4)°.…”

“…The IR spectrum as a Nujol mull shows ν(CO) at 2016 cm -1 , indicating the occurrence of an oxidative-addition process at the iridium(I) center. In the 1 H NMR spectrum in CDCl 3 solution, the resonances of the 6-hydrogen atoms of the pyridine rings are shifted to higher frequency, as is usually observed when the pyridine nitrogen atom is coordinated . The 31 P{ 1 H} NMR spectrum in CDCl 3 solution shows a single resonance at δ −12.80 ppm, indicating a head-to-head configuration of the Ph 2 PPy bridging ligands.…”

“…In accordance, the IR spectrum of a Nujol mull shows ν(CO) at 1952 cm -1 and the 31 P{ 1 H} NMR spectrum in CDCl 3 solution shows a singlet at δ 24.46 ppm. Significantly, the 1 H NMR spectrum, in CDCl 3 solution, shows a distinct resonance at δ 8.77 ppm for the 6-hydrogen of the pyridine ring, as usual when the Ph 2 PPy acts as a monodentate P-bonded ligand . This resonance is further shifted to higher frequency when the Ph 2 PPy acts as a bifunctional ligand.…”

(p-cymene)Ruthenium(II)(diphenylphosphino)alkyne Complexes: Preparation of (μ-Cl)(μ-PPh2C⋮CR)-Bridged Ru/Pt Heterobimetallic Complexes

“…The chemistry of half-sandwich η 6 -arene-ruthenium complexes has been widely developed in the past decade, in part due to their catalytic potential, but also due to their usefulness in the synthesis of other Ru(0) and Ru(II) complexes. − In particular, (arene)ruthenium(II) complexes of the type [(η 6 -arene)RuCl 2 (PR 3 )] containing aryl or alkyl phosphine as ancillary ligands have been extensively studied, owing to their role as effective precursors for a variety of catalytic and stoichiometric organic transformations. ,− Special interest is also currently devoted to complexes stabilized by heterobifunctional phospines bearing a hard (N, O) donor atom, since these ligands show interesting hemilabile properties. − In contrast, the chemistry of analogous (arene)ruthenium(II) complexes containing unsaturated phosphines is relatively unexplored. Recently, Nelson and co-workers have reported (arene)Ru(II) derivatives with vinyl and allyl phosphines and 3,4-dimethyl-1-phenylphosphole, showing interesting reactivity with some of them. , Thus, they found that complexes (η 6 -arene)RuCl 2 (DPVP)] (DPVP = diphenylvinylphosphine) undergo a novel KO t Bu-promoted hydroalkylation to produce tethered phosphinopropylarene-ruthenium(II) compounds .…”