132939-91-4

Upstream product

• 2071-20-7 bis-diphenylphosphinomethane 

Downstream Products

• 132959-03-6 IrOs(H)2(CO)3((C₆H₄)C₆H₅PCH₂P(C₆H₅)2)((C₆H₅)2PCH₂P(C₆H₅)2) 
• 323185-87-1 [IrRu(CO)3(μ-H)(bis(diphenylphosphino)methane)2] 

Relevant academic research and scientific papers

Reactions of phosphine ligands with iridium complexes leading to C(sp 3)-H bond activation

Treatment of [Ir2(μ-Cl)2(coe)4 (coe = cyclooctene) with the short-bite bifunctional N,P-donor ligand 1-benzyl-2-imidazolyldiphenylphosphine (Ph2PBnIm) resulted in the oxidative addition of the C(sp3)-H bond from the benzyl group to the metal to give [IrHCl-{Ph2P(CHPh)Im}(Ph2PBnIm)] (1), fully characterized by an X-ray study. The related ligand 2-pyridyldiphenylphosphine (Ph2PPy) reacted with [Ir2(μ-Cl)2(coe) 4] to give the mononuclear iridium(I) complex [IrCl(Ph 2PPy)2] (2), which showed P,N-chelating and P-coordinated ligands. Addition of Ph2BnIm to 2 produced the replacement of the P-coordinated Ph2PPy ligand along with the benzyl C-H bond addition to indium to give [IrHCl{Ph2P(CHPh)Im}-(Ph2PPy)]. This result indicates that mononuclear complexes of the type [IrCl(Ph 2PBnIm)-(L)] (L = P,N-chelating ligand) are the active species undergoing the C-H bond activation reaction. A related C-H bond activation process of the methylene group of dppm occurs in the reaction of [Ir 2(μ-Cl)2(coe)4] with dppm in toluene to give the hydrido complex with one deprotonated dppm ligand [IrHCl(Ph 2PCHPPh2)(dppm)] (4). On the other hand, the hydride migrates to the methanide carbon in 4 on dissolving the complex in CD 2Cl2 to establish an equilibrium with [IrCl(dppm) 2] without H/D exchange. Protonating agents such as HBF 4·Et2O and water reacted with complex 4 easily to give [IrHCl(dppm)2]X (X = BF4, OH). The mononuclear complex 2 was found to be highly reactive. Reactions of 2 with O2, H2, and dichloromethane gave the complexes [IrCl(O 2)(Ph2PPy)2], [IrCl(H)2(Ph 2PPy)2], and [IrCl2(CH2Cl)-(Ph 2PPy)2], respectively.

Diphosphine-bridged, heterobimetallic complexes containing iridium and osmium. Reversible ortho metalation of a bridging bis(diphenylphosphino)methane group at the Iridium Center promoted by the Adjacent Osmium Center

The compound (PPN)[HOs(CO)4] reacts readily with [IrCl(η2-dppm)2] (PPN+ = (Ph3P)2N+, dppm = Ph2PCH2PPh2) at ambient temperature, yielding the heterobinuclear complex [IrOs(H)2(CO)3(μ2-η 3-(o-C6H4)PhPCH2PPh 2)(dppm)] (1), in which one phenyl group is ortho-metalated at the Ir center. Treatment of 1 with the electrophile sources HBF4-Et2O or [AuPPh3]BF4 reverses the ortho metalation to give the hydrido-bridged species, [IrOs(CO)3(μ-H)(μ-X)(dppm)2][BF4] (X = H (2), AuPPh3 (3)). Deprotonation of 2 with use of NaH regenerates compound 1. The AuPPh3 group in 3 is readily replaced by an iodo group in the reaction with I2 to give [IrOs(CO)3(μ-H)(μ-I)(dppm)2] [BF4] (4). Under a CO atmosphere, compound 2 yields [IrOs(CO)5(dppm)2] [BF4] (5), and reaction of 5 with Me3NO·2H2O results in loss of one carbonyl group from the Ir center to yield [IrOs(CO)4(dppm)2] [BF4] (6). The structure of 5 has been determined by X-ray techniques. This compound crystallizes, together with 1.5 equiv of CH2Cl2, in the monoclinic space group P21/c, with cell parameters a = 12.063 (2) A?, b = 22.725 (3) A?, c = 22.050 (3) A?, β = 101.66 (1)°, V = 5920 A?3, and Z = 4. The structure has refined to R = 0.043 and Rw = 0.063 on the basis of 5515 unique observations with 444 parameters varied. Compound 5 has a trans-bridging arrangement of diphosphine ligands and has two carbonyls bound to Ir and three on Os. The carbonyl and phosphine arrangement on Os suggests a trigonal bipyramidal (TBP) arrangement characteristic of Os(0), which then forms a dative Os → Ir bond to the Ir(+I) center, giving it a TBP geometry also. The Os-Ir separation of 2.9652 (4) A? is at the long end of the range expected for a normal single bond.