832744-54-4

Upstream product

• 181228-49-9 Ir(H)(Cl)2(CS)(P(C₆H₅)3)2 
• 61926-61-2 [IrH(C[S]SMe)Cl(CO)(PPh₃)2] 
• 937-63-3 p-Tolyl chlorothionoformate 
• 59246-46-7 bis(triphenylphosphine)carbonyliridium(I) chloride 

Downstream Products

• 135929-06-5 {Fe(CO)3(Si(OMe)3)(μ-dppm)(CS)RhPPh3} 
• 181028-60-4 Ir(Cl)2(CS)2(P(C₆H₅)3)2⁽¹⁺⁾*Cl^(1-)=[Ir(Cl)2(CS)2(P(C₆H₅)3)2]Cl 
• 181028-55-7 Ir(Cl)(SCSC₆H₅)(CS)(P(C₆H₅)3)2⁽¹⁺⁾*PF₆^(1-)=[Ir(Cl)(SCSC₆H₅)(CS)(P(C₆H₅)3)2]PF₆ 
• 71817-50-0 σ-pentachlorophenyl(thiocarbonyl)bis(triphenylphosphine)iridium(I) 
• 71817-49-7 σ-pentafluorophenyl(thiocarbonyl)bis(triphenylphosphine)iridium(I) 
• 71438-36-3 chloroiodo(methyl)(thiocarbonyl)bis(triphenylphosphine)iridium(III) 
• 936944-23-9 IrI(CS)(PPh₃)2 
• 1009121-63-4 [Ir(P(C₆H₅)3)2(CS)(NCCH₃)]⁽¹⁺⁾*O₃SCF₃^(1-)=[Ir(P(C₆H₅)3)2(CS)(NCCH₃)](O₃SCF₃) 
• 1187785-36-9 [Ir(SC₅H₄)(CH₃CN)(P(C₆H₅)3)2]⁽¹⁺⁾*CF₃SO₃^(1-)=[Ir(SC₅H₄)(CH₃CN)(P(C₆H₅)3)2][CF₃SO₃] 
• 1204764-73-7 [IrH(triphenylphosphine)(thiocarbonyl)(κ3-B,S,S'-HB(2-mercapto-3-methylimidazol-1-yl)2)] 
• 71308-75-3 trans-azido(thiocarbonyl)bis(triphenylphosphine)iridium(I) 
• 1204764-74-8 [Ir(triphenylphosphine)(thiocarbonyl)(κ4-B(2-mercapto-3-methylimidazol-1-yl)3)]Cl 
• 181028-50-2 Ir(Cl)2(P(C₆H₅)3)2(CS)(C(S)OC₆H₄CH₃) 
• 181028-58-0 Ir(Cl)2(CS)2(P(C₆H₅)3)2⁽¹⁺⁾*I₃^(1-)=[Ir(Cl)2(CS)2(P(C₆H₅)3)2]I₃ 

Relevant academic research and scientific papers

A 2-iridathiophene from reaction between IrCl(CS)(PPh3) 2 and Hg(CH=CHPh)2

The thiocarbonyl analogue of Vaska's compound is produced in high yield by first treating IrCl(CO)(PPh3)2 with CS2 and methyl triflate to give [Ir(κ2-C[S]SMe)Cl(CO)(PPh 3)2]CF3SO3 (1), secondly, reacting 1 with NaBH4 to give IrHCl(C[S]SMe)(CO)(PPh3)2 (2), and finally heating 2 to induce elimination of both MeSH and CO to produce IrCl(CS)(PPh3)2 (3). When IrCl(CS)(PPh3) 2 is treated with Hg(CH=CHPh)2 the novel 2-iridathiophene, Ir[SC3H(Ph-3)(CH=CHPh-5)]HCl(PPh3)2 (4) is produced. The X-ray crystal structure of the iodo-derivative of 4, Ir[SC 3H(Ph-3)(CH=CHPh-5)]HI(PPh3)2 (5) confirms the unusual 2-metallathiophene structure. Treatment of IrCl(CS)(PPh 3)2 with Hg(CH=CPh2)2 produces both a coordinatively unsaturated 1-iridaindene, Ir[C8H 5(Ph-3)]Cl(PPh3)2 (6) and a chelated dithiocarboxylate complex, Ir(κ2-S2CCH=CPh 2)Cl(CH=CPh2)(PPh3)2 (7). X-ray crystal structure determinations for 6 and 7 are reported.

Convenient syntheses of [IrCl(CS)(PPh3)2] and a Bis(thiocarbonyl) complex of iridium

Treating [IrCl(CO)(PPh3)2] with ClC(=S)OR (R = C6H4Me-4) provides [IrCl2{C(=S)OR}-(CO)(PPh3)2], which reacts with NaBH4 to give [IrHCl{C(=S)OR}(CO)(PPh3)2]. The aryloxide group is cleaved by HCl to give [IrHCl2(CS)(PPh3)2], which is dehydrochlorinated by DBU to provide [IrCl(CS)(PPh3)2] (overall yield for Ir(CO) → Ir(CS) 75%). Treating [IrCl(CS)-(PPH3)2] with ClC(=S)SPh provides [IrCl2{C(=S)SPh}(CS)(PPH3)2] (in equilibrium with [IrCl-(η2-SCSPh)(CS)(PPH3)2]Cl) which reacts subsequently with I2 or ICl to provide [IrCl2(CS)2-(PPH3)2]X (X = I3, Cl). [Ir(CS2Ph)Cl2(CO)(PPH3)2], however, reacts with I2 to provide [IrClI2(CS)(PPH3)2]. Reaction of [IrHCl2(CS)(PPH3)2] with CNC6H3Me2-2,6 does not proceed via migratory insertion but, rather, leads to reduction of iridium and formation of the salt [Ir(CNC6H3Me2-2,6)2(CS)(PPH 3)2]Cl. ? Dedicated to Professor Max Herberhold on the occasion of his 60th birthday.