79027-47-7

Upstream product

• 94090-32-1 {Ir(CO)HCl(P(C₂H₅)3)2(PH₃)}⁽¹⁺⁾ 
• 113890-86-1 {Ir(CO)(P(C₂H₅)3)2(PH₃)2}⁽¹⁺⁾ 
• 10294-34-5 boron trichloride 
• 87431-89-8 trans-carbonyldichloro(dichlorophosphido)bis(triethylphospine)iridium(III) 
• 94090-26-3 carbonylchloro(dihydrogenarsenido)hydridobis(triethylphosphine)iridium(III) 

Relevant academic research and scientific papers

Reactions of Phosphine, Arsine, and Stibine with Carbonylbis(triethylphosphine)iridium(I) halides. Part 2. Reactions in Dichloromethane

In CD2Cl2, as in toluene, AsH3 and SbH3 react with trans- , by oxidative addition.With PH3, the product of the initial reaction at 180 K gives +, (3).In the presence of excess of PH3, (3) is converted into tH3)(P'cH2)>+, (4) (c and t imply cis and trans respectively to hydride).All these species were identified by 1H and 31P n.m.r. spectroscopy.The spectra show that P't is much more basic than P'c; P'tH3 in (4) can be deprotonated by NMe3, to give tH2)(P'cH2)>, (5), and P'cH2 in (4) can be protonated with excess of HCl to give tH3)(P'cH3)>2+, (6).Compound (5) reacts with B2H6 to give tH2BH3)(P'cH2BH3)>, (9); compound (4) reacts with a half-molar proportion of B2H6 to give (6) and (9).Reaction of6-MeC6H4CHMe2-p)>2>, (10), with (5) in a 1:1 molar ratio gives 6-MeC6H4CHMe2-p)>2>, (11); with a 2:1 molar ratio, the initial product appears to be tH2RuCl2(η6-MeC6H4CHMe2-p)>(P'cH2)>, but on standing at room temperature for several hours this gives tH2)(μ-P'cH2)RuCl(η6-MeC6H4CHMe2-p)>. tH3)(μ-P'cH2)RuCl2(η6-MeC6H4CHMe2-p)> was formed from (4) and (10), and this could be deprotonated with NMe3.Reactions of (5) with (nbd=bicyclohepta-2,5-diene) and with (cod=cyclo-octa-1,5-diene) are also described.

Reactions of Phosphine, arsine, and Stibine with Carbonylbis(triethylphosphine)iridium(I) Halides. Part 1. Reactions in Toluene; X-Ray Crystal Structures of and 6-MeC6H4CHMe2-p)> (X=Br, Z=P; X=Cl, Z=As)

trans- (X=Br or Cl) reacts with ZH3 (Z=P, As, or Sb) in toluene at 180 K to give .When Z=P or As, the product is monoisomeric, but with Z=Sb two isomers are formed.. (4) reacts with Cl2 to give ; with Se, is the product.Reaction with HCl at 200 K gives (1+), but as the solution is allowed to warm PH3 is displaced by Cl, and a similar reaction with H2Se leads to the formation of .Boron trifluoride does not interact with (4), but B2H6 reacts to give a BH3 adduct that is stable in solution at room temperature.Compound (4) reacts with 6-MeC6H4CHMe2-p)>2>, forming 6-MeC6H4CHMe2-p)>.Reactions of (5) are similar, except that treatment with Se leads to decomposition.The crystal structures of (5) and the complexes formed by both (4) and (5) with 6-MeC6H4CHMe2-p)>2> are reported.

Synthesis, Crystal Structure and some Reactions of trans-

Reaction between trans- (1) and PCl3 gives trans- (2), which has been characterised by partial elemental analysis, X-ray crystal-structure analysis, and mass and n.m.r. spectra.Reaction with HCl leads to slow cleavage of the Ir-P' bond at room temperature, but HCl-BCl3 (1:1) protonates the P'Cl2 group.A BH3 adduct is formed with B2H6 at low temperature, but with an excess of B2H6 at room temperature a mixture of adducts is produced containing both Ir-H and P'-H bonds.An equimolar adduct is formed by (2) with BCl3 but not with BF3.Reaction with O2, S8, or Se8 gives trans- (Y= O, S, or Se): the reaction with O2 is very slow, but trans- (3) is also formed from (2) and N2O4.The crystal structure of (3) was also determined and has been shown to form adducts with both BCl3 and AlCl3.Complex (2) reacts with H2Se to give first trans-, then trans-, and finally trans-, the last of which was isolated.Reaction with H2S is much slower, and gives only trans-.With water, the phosphinate complex trans- is formed, which crystallizes with H3O(1+)*Cl(1-).The Ir-P' bond is broken by methanol.There is no reaction with either 6-MeC6H4CHMe2-p))2> or (cod= cyclo-octa-1,5-diene).