82582-67-0

Basic information

• Product Name: [((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]⁽¹⁺⁾*BF₄^(1-)=[((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]BF₄
• Synonyms: [((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]⁽¹⁺⁾*BF₄^(1-)=[((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]BF₄
• CAS NO: 82582-67-0
• Molecular Weight: 921.782
• Mol File: 82582-67-0.mol
• Article Data: 4

Chemical Properties

• CAS DataBase Reference: [((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]⁽¹⁺⁾*BF₄^(1-)=[((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]BF₄(CAS DataBase Reference)
• NIST Chemistry Reference: [((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]⁽¹⁺⁾*BF₄^(1-)=[((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]BF₄(82582-67-0)
• EPA Substance Registry System: [((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]⁽¹⁺⁾*BF₄^(1-)=[((C₆H₅)3P)2IrH₂(CO(CH₃)2)2]BF₄(82582-67-0)

Safety Data

• Hazardous Substances Data: 82582-67-0(Hazardous Substances Data)

Upstream product

• 38834-40-1 [Ir(1,5-COD)(P(C₆H₅)3)2]BF₄ 
• 36075-06-6 2-(diethylamino)pyridine 
• 1333-74-0 hydrogen 
• 67-64-1 acetone 
• 67969-82-8 tetrafluoroboric acid diethyl ether 
• 53470-69-2 pentahydridobis(triphenylphosphine)iridium(III) 
• 603-35-0 triphenylphosphine 
• 5683-33-0 2-(Dimethylamino)pyridine 
• 380500-12-9 2-hexamethyleneiminopyridine 
• 54660-06-9 2-pyrrolidinopyridine 

Downstream Products

• 38834-40-1 [Ir(1,5-COD)(P(C₆H₅)3)2]BF₄ 
• 89691-00-9 dihydrido(η3(Cl,C,C)-2,6-dichlorostyrene)bis(triphenylphosphine)iridium(III) tetrafluoroborate 
• 741291-43-0 trans-[carbonylhydridobis(triphenylphosphine)(N,C-2-pyrrolidinopyridine-1'-yl)iridium(III)] fluoroborate 
• 866867-58-5 IrH(P(C₆H₅)3)2((CH₃)2CO)CHCHCOCH₃⁽¹⁺⁾*BF₄^(1-)=IrH(P(C₆H₅)3)2((CH₃)2CO)CHCHCOCH₃BF₄ 
• 835890-35-2 IrH(P(C₆H₅)3)2((CH₃)2CO)C₆H₅CCHCCH₃O⁽¹⁺⁾*BF₄^(1-)=IrH(P(C₆H₅)3)2((CH₃)2CO)C₆H₅CCHCOCH₃BF₄ 
• 866867-62-1 IrH(P(C₆H₅)3)2((CH₃)2CO)CH₃CCHCOOCH₂CH₃⁽¹⁺⁾*BF₄^(1-)=IrH(P(C₆H₅)3)2((CH₃)2CO)CH₃CCHCOOCH₂CH₃BF₄ 
• 866867-56-3 IrH(P(C₆H₅)3)2((CH₃)2CO)C₁₀H₉O⁽¹⁺⁾*BF₄^(1-)=IrH(P(C₆H₅)3)2((CH₃)2CO)C₁₀H₉OBF₄ 
• 96394-23-9 [((C₆H₅)3P)2IrH₃NC₉H₆CH₂]⁽¹⁺⁾*BF₄^(1-)=[((C₆H₅)3P)2IrH₃NC₉H₆CH₂]BF₄ 
• 167642-54-8 dihydrido(carbonyl)(η1-2-aminopyridine)bis(triphenylphosphine)iridium(III) tetrafluoroborate 
• 167642-65-1 dihydridohalo(η1-2-aminopyridine)bis(triphenylphosphine)iridium(III) 
• 161335-18-8 dihydridohalo(η1-2-aminopyridine)bis(triphenylphosphine)iridium(III) 
• 167642-66-2 dihydridohalo(η1-2-aminopyridine)bis(triphenylphosphine)iridium(III) 
• 167642-52-6 dihydridoacetonitrile(η1-2-aminopyridine)bis(triphenylphosphine)iridium(III) tetrafluoroborate 
• 79792-68-0 Ir(C₇H₇)H{(C₆H₅)3P}2⁽¹⁺⁾*BF₄^(1-) 

Relevant articles and documents

Double geminal C-H activation and reversible α-elimination in 2-aminopyridine iridium(III) complexes: The role of hydrides and solvent in flattening the free energy surface

[H2Ir(OCMe2)2L2]BF4 (1) (L = PPh3), a preferred catalyst for tritiation of pharmaceuticals, reacts with model substrate 2-(dimethylamino)pyridine (py-NMe2; py = 2-pyridyl) to give chelate carbene [H 2Ir(py-N(Me)CH=)L2]BF4 (2a) via cyclometalation, H2 loss, and reversible α-elimination. Agostic intermediate [H2Ir(py-N(Me)CH2-H)L2]BF 4 (4a), seen by NMR, is predicted (DFT(B3PW91) computations) to give C-H oxidative addition to form the alkyl intermediate [(H)(η2- H2)Ir(py-N(Me)CH2-)L2]BF4. Loss of H2 leads to the fully characterized alkyl [HIr(OCMe 2)(py-N(Me)CH2-)L2]BF4 (3a Me2CO), which loses acetone to give alkylidene hydride 2a by rapid reversible α-elimination. 2a rapidly reacts with excess H2 in d6-acetone to generate [H2Ir(OC(CD3) 2)2L2]BF4 (1-d12), 3a(CD3)2CO, and py-NMe2 in a 1:1:1 ratio, showing reversibility and accounting for the selective isotope exchange catalyzed by 1. Reaction of 1 with py-N(CH2)4 gives the fully characterized carbene 2c. A cis-L2 carbene intermediate, cis-2c, observed by NMR, reacts with CO via retro α-elimination to give the alkyl 3cCO, while the trans isomer, 2c, does not react; retro α-elimination thus requires the Ir-H bond to be orthogonal to the carbene plane. Consistent with experiment, computational studies show a particularly flat PE surface with activation of the agostic C-H bond giving a less stable H2 complex, then formation of a kinetic carbene complex with cis-L, only seen experimentally for py-N(CH2)4. Hydrides at key positions, together with gain or loss of solvent and H2, flatten the PE (AG) surfaces to allow fast catalysis.

Solvento complexes of tungsten, rhenium, osmium, and iridium and the X-ray crystal structure of [IrH2(Me2CO)2(PPh3) 2]BF4

[WH6(PMe2Ph)3], [ReH5(PMe2Ph)3], [ReH7(PPh3)2], [OsH4(PMe2Ph)3], and [IrH5(PPh3)2] react with HBF4 in MeCN (=S) to give [WH2S3(PMe2Ph)3]2+, [ReHS3(PMe2Ph)3]2+, [ReHS4(PPh3)2]2+, [OsS3(PMe2Ph)3]2+, and [IrH2S2(PPh3)2]+ as the BF4 salts. The reaction mechanism and evidence for the initial protonation of some of the d0 polyhydrides at an M-H bond is discussed. In all but the iridium case, MeOH and Me2CO failed to give analogous complexes and no alkane or alkene dehydrogenation reactions were ever observed with the acetonitrile complexes. In the iridium case a variety of solvento complexes can be obtained. Where S = Me2CO, these are active in alkene and alkane dehydrogenation, and in this case a single-crystal X-ray diffraction study was performed: monoclinic unit cell; a = 10.565 (2) ?; b = 25.315 (7) ?; c = 15.460 (4) ?; β = 95.74 (2)°; V = 4114 (4) ?3; space group P21/c; Z = 4; R = 5.6%. The trans influence of the hydride ligands on the O-bound acetone groups was pronounced: Ir-O = 2.228 (5) ? (av), ca. 10% longer than the expected 2.02 ?. This is consistent with the high reactivity of the acetone complex.