15390-38-2

Upstream product

• 162020-56-6 (1-benzyl-2-imidazolyl)diphenylphosphine 
• 849441-63-0 [Ir(bis(diphenylphosphino)ethane)2][Ir(cyclooctene)2Cl₂] 
• 29894-56-2 (η2-peroxo)bis(1,2-bis(diphenylphosphino)ethane)iridium(I) chloride 
• 31603-13-1 {Ir(S₂)(((C₆H₅)2PCH₂)2)2}⁽¹⁺⁾*Cl^(1-)={Ir(S₂)(((C₆H₅)2PCH₂)2)2}Cl 
• 40603-51-8 {Ir(Se₂)(((C₆H₅)2PCH₂)2)2}⁽¹⁺⁾*Cl^(1-)={Ir(Se₂)(((C₆H₅)2PCH₂)2)2}Cl 
• 607-01-2 ethyl-diphenyl-phosphane 
• 15308-58-4 [IrCO(dppe)2]Cl 
• 13517-35-6 tris(triphenylphosphine)platinum⁽⁰⁾ 

Downstream Products

• 2548-47-2 2,3-diphenyl-1,3-butadiene 
• 56391-52-7 (C₂H₄(P(C₆H₅)2)2)2IrS₂O⁽¹⁺⁾*Cl^(1-)=(C₂H₄(P(C₆H₅)2)2)2IrS₂OCl 
• 91685-25-5 IrCl(CO)(((C₆H₅)2PCH₂)2)2⁽²⁺⁾*2BF₄^(1-) = [IrCl(CO)(((C₆H₅)2PCH₂)2)2](BF₄)2 
• 40603-51-8 [Ir(1,2-bis(diphenylphosphino)ethane)2Se₂]Cl 
• 79292-53-8 IrHCl((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2⁽¹⁺⁾*BF₄^(1-)=(IrHCl((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2)BF₄ 
• 12124-29-7 IrH₂((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2⁽¹⁺⁾*Cl^(1-)=(IrH₂((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2)Cl 
• 100228-68-0 Ir(CH₃)((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2 
• 100228-74-8 Ir((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2⁽¹⁺⁾*C₅H₅^(1-)*C₄H₈O=(Ir((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2)C₅H₅*C₄H₈O 
• 82522-45-0 [Ir(Se₂)((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2]⁽¹⁺⁾*B(C₆H₅)4^(1-)=[Ir(Se₂)((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2]B(C₆H₅)4 
• 29871-99-6 (Ir(dpe)2)⁽¹⁺⁾ 
• 3878-44-2 Triphenylphosphine selenide 
• 82522-41-6 [(((C₆H₅)2PCH₂)2)2IrSe₂IrCl(CO)(P(C₂H₅)2C₆H₅)2]⁽¹⁺⁾*Cl^(1-)=[(((C₆H₅)2PCH₂)2)2IrSe₂IrCl(CO)(P(C₂H₅)2C₆H₅)2]Cl 
• 66350-34-3 IrH(CO)(((C₆H₅)2PCH₂)2)2⁽²⁺⁾*2BF₄^(1-) = [IrH(CO)(((C₆H₅)2PCH₂)2)2](BF₄)2 
• 40603-50-7 [Ir(1,2-bis(diphenylphosphino)ethane)2S₂]Cl 

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.

Photochromism in dioxygen, disulfur, and diselenium complexes of rhodium and iridium

[M(X2)(L-L)2]+ (M = Rh, Ir; X2 = chelating O2, S2, Se2; L-L = dppe, dmpe) complexes are photochromic at liquid-nitrogen temperature, both in the solid state and in dilute EPA glass solution. Use of 250-350-nm light produces a color that is stable in the dark at 77 K but that is bleached back to the original color by warming to 100-110 K or by irradiation with 400-600-nm light., The photocolor is due to intense absorption in the 350-630-nm region of the spectrum. Magnetic susceptibility measurements show that photocolored [Rh(S2)(dmpe)2]+ is diamagnetic at 10 K. SCF-Xα-SW calculations on a variety of models for the photocolored species indicate that M-X or X-X bond cleavage leads to paramagnetic ground states. Rotation of the X2 group about the M=X2 bond to a plane intermediate between the equatorial and axial MP2 planes accounts for the observed spectral changes and leaves the molecule diamagnetic. The rotation can take place in an excited state where M-X2 π bonding is weakened by occupation of an M-X2 π* orbital.

Oxidation of the carbonylbis(1,2-bis(dipbenylphosphino)ethane)iridium(I) cation. Preparation and characterization of a series of iridium(III) carbonyl dications

Oxidation of Ir(CO)(dppe)2+ with halogens affords cis-IrX(CO)(dppe)22+ (X = Cl, Br) while oxidation with HBF4 affords cis-IrH(CO)(dppe)22+. The species trans-IrX(CO)(dppe)22+ (X = Cl, Br) are prepared by the oxidation of Ir(CO)(dppe)2+ with nitrosonium ion in the presence of Cl- or Br-. The complex trans-IrH(CO)(dppe)22+ is most conveniently prepared by protonation of [Ir(dppe)2]BF4 with HBF4·Et2O to afford the intermediate IrH(dppe)22+, followed by CO addition. In contrast, both cis- and trans-IrCl(CO)(dppe)22+ species are formed by the electrochemical oxidation of Ir(CO)(dppe)2+ in chloride media. The trans isomer is reduced at a more negative potential and is thus thermodynamically the more stable. Reversible deprotonation of cis-[IrH(CO)(dppe)2][BF4]2 by chloride implies that the acidity of this compound is of the order of that of HCl, unusually strong for a third-row transition-metal hydrido complex.

Synthesis and reactivity of [Ir(η2-E2R) (Ph2PCH2CH2PPh2)2] 2+ (E = S, Se; R = H, CH3)

The stereochemistry and reactivity of [Ir(E2R)(dppe)2]2+ (dppe = Ph2P(CH2)2PPh2; E = S, Se; R = H, CH3) have been examined. In solution, [Ir(E2CH3)(dppe)2]2+ exists as a mixture of two diastereomers in the ratio of 20:1 (E = S) and 6:1 (E = Se). Protonation of [Ir(E2)(dppe)2]+ with strong acids gave [Ir(E2H)(dppe)2]2+ complexes, which are spectroscopically and stereochemically similar to the η2-E2CH3 derivatives. In contrast to [Ir(S2)(dppe)2]+, the [Ir(S2CH3)(dppe)2]2+ (1) complex can act as both a potent sulfur atom and CH3S+ transfer reagent. The nature of the S-transfer reaction depends on the substrate (X) used and the stability of the corresponding S-X and [X-SCH3]+ products. 1 reacts rapidly with PPh3 (2 equiv) to give [Ir(dppe)2]+, Ph3PS, and [Ph3PSCH3]+. With CH3NC (2 equiv) and 1, sulfur atom transfer occurs, and cis-[Ir(SCH3)(CH3NC)(dppe)2]2+ and CH3NCS are produced. Reaction of CN- with 1 gave cis-[Ir(SCH3)(SCN)(dppe)2]+. Oxidative addition of CH3SH and CH3SCl to [Ir(dppe)2]+ gave [Ir(SCH3)H(dppe)2]+ and [Ir(SCH3)Cl(dppe)2]+, respectively. 1H NMR species confirmed the utility of the high-field ortho phenyl, the S2CH3, and the SCH3 resonances in structure elucidation. Also described is the applicability of gel-permeation chromatography and field-desorption mass spectrometry for the purification and characterization of these ionic, high molecular weight complexes.

Disulfur and diselenium complexes of rhodium and iridium

Coordinatively unsaturated low-valent rhodium and iridium complexes cleave S8 and Se8 rings and form complexes with the fragments. With square-planar [M(L-L)2]Cl (M = Rh, Ir; L-L = (C6H5)2PCH2CH2P(C 6H5)2 (dppe), (CH3)2PC-H2CH2P(CH3) 2 (dmpe)) this reaction affords the monomeric electrolytes [M(Y2)(L-L)2]Cl (Y2 = S2, Se2). Oligomeric compounds are obtained from the reactions with IrX(CO)(EPh3)2 and RhX(EPh3)3 (X = Cl, Br; E = P, As); the products are [{Ir(Se2)X(CO)(PPh3)}3], [{Ir(Se2)Cl(CO)(AsPh3}3], [{IrS6Cl(CO)(PPh3)2}n], [{RhS3X(PPh3)4}], [{RhSe3Cl(PPh3)}4], and [{RhY2Cl(AsPh3)}n] (Y2 = S2, Se2). In the compounds [M(Y2)(L-L)2]Cl, disulfur and diselenium are side-on bonded to the metal at equatorial positions of a distorted octahedron. An X-ray structure determination of the diselenium complex [Ir(Se2)(dppe)2]Cl·H2O·0.5C 6H6 shows the cation to be very similar to its dioxygen and disulfur analogues. The Se-Se distance is 2.312 (3) A?, about the same as the bond length in Se8 and 0.16 A? longer than the Se-Se bond in the free Se2 molecule. [M(Y2)(L-L)2]+ complexes have ν(S-S) at 510-550 cm-1 and ν(Se-Se) at 300-310 cm-1. The lowest energy feature of their electronic absorption spectra is a weak (ε 40-100 M-1 cm-1) band assigned as an a2π⊥* → b1 intraligand transition. 193Ir(1/2+ → 3/2 +) Mo?ssbauer spectra of [Ir(Y2)(dppe)2]Cl give isomer shifts that decrease along the series Y2 = O2, S2, Se2, in parallel with decreasing Y2 electronegativity. The disulfur or diselenium group in [M(Y2)(L-L)2]+ is readily reduced: mercury and tertiary phosphines strip sulfur or selenium from the complex with formation of HgS or HgSe and R3PS or R3PSe; the rate is very sensitive to the electronic environment of the disulfur or diselenium group and to the basicity of the phosphine. Low-valent group 8 metal complexes undergo oxidative addition across the S-S or Se-Se bond, allowing synthesis of the heterometallic (μ-S)2 dimers [(dppe)2Ir(μ-S)2PtL2]X (L = PPh3, X = Cl; L = PEtPh2, X = PF6) and [(dmpe)2Rh(μ-S)2Pt(PPh3)2]Cl, as well as the asymmetric dimer [(dppe)2Ir(μ-Se)2IrCl(CO)(PEt2Ph) 2]Cl. Oxidative addition together with displacement of [M(L-L)2]+ by excess of the addend complex also occurs, giving homometallic (μ-S)2 or (μ-Se)2 dimers such as [{Ir(μ-Se)Cl(CO)(PEt2Ph)2}2]. Iodine adds across the S-S bond of [Ir(S2)(dppe)2]Cl to form the novel cis-octahedral complex [Ir(SI)2(dppe)2]Cl.