Structure of an iridium complex of 1,1'-bisdiphenylphosphinoferrocene

Bedford, Robin B.; Chaloner, Penny A.; Hitchcock, Peter B.

doi:10.1107/s0108270193002288

Cited by 5 publications

(2 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The coordination planes of the ligands, containing the P(1), Ir, and P(2) atoms and the P(3), Ir, and P(4) atoms, form a dihedral angle of 85°, but only two of the P−Ir−P angles are essentially tetrahedral (Table ). The bite angles of the diphosphines (P(1)−Ir−P(2) = 104.8° and P(3)−Ir−P(4) = 99.8°) deviate significantly from ideal values, and one of them is very similar to that found in [Ir(C 8 H 12 )(dppf)] + (99.2°) . The Ir−P bond distances are in the range 2.242(3)−2.270(3) Å with an average value of 2.255 Å.…”

Section: Resultsmentioning

confidence: 68%

“…The bite angles of the diphosphines (P(1)-Ir-P(2) ) 104.8°and P(3)-Ir-P(4) ) 99.8°) deviate significantly from ideal values, and one of them is very similar to that found in [ (99.2°). 19 The Ir-P bond distances are in the range 2.242(3)-2.270(3) Å with an average value of 2.255 Å. The cyclopentadienyl rings are staggered (synclinal or gauche), forming angles of 37.9°(Cp1 and Cp2) 20 and 23.0°(Cp3 and Cp4), and slightly tilted away from the Fe center with dihedral angles of 3.6°(Cp1 and Cp2) and 3.4°(Cp3 and Cp4).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)₅][Ir(dppf)₂]·THF and [Ir(dppf)₂]

et al. 1999

View full text Add to dashboard Cite

The iridium(I) complex stabilized by the organometallic ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf), [Ir(dppf)(2)](+), 1, undergoes a cyclometalation reaction in solution to give the iridium(III) hydride [IrH(dppf(-H))(dppf)](+), 2, which has been isolated and characterized by spectroscopic methods. The compound is the final product of the intramolecular oxidative addition of the ortho C-H bond of a phenyl substituent of the diphosphine and is formed through an intermediate hydride, which has also been spectroscopically characterized. 1 can be electrochemically reduced to the Ir(0) and Ir(-I) species, [Ir(dppf)(2]), 3, and [Ir(dppf)(2)](-), 4, respectively, in two reversible single-electron processes. These low-valent metal complexes have been obtained by chemical reduction of 1 with sodium naphthalenide in tetrahydrofuran solution and their crystal and molecular structures determined by single-crystal X-ray analyses. 3 crystallizes in the triclinic system, space group P&onemacr;, with a = 13.019(4) Å, b = 13.765(6) Å, c = 15.549(5) Å, alpha = 93.74(3) degrees, beta = 90.35(3) degrees, gamma = 92.07(3) degrees, V = 2779(2) Å(3), and Z = 2. Anionic complex 4 crystallizes as sodium-solvated salt [Na(THF)(5)][Ir(dppf)(2)].THF, 4b, in which the sodium cation is surrounded by five molecules of THF in a slightly distorted trigonal-bipyramidal environment. 4b crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.325(3) Å, b = 23.976(5) Å, c = 26.774(7) Å, beta = 98.77(2) degrees, V = 8454(4) Å(3), and Z = 4. The coordination geometry around the metal in neutral d(9) complex 3 is intermediate between the highly distorted square-planar geometry, found earlier in cationic d(8) species 1, and the almost regular tetrahedral arrangement of the two diphosphines in the anionic d(10) complex 4. Reduction of Ir(I) to Ir(0) and Ir(-I) causes a stepwise decrease of the Ir-P bond length of 0.04 Å (average) and 0.05 Å, respectively, with a concomitant increase of the bite angle of the diphosphine which ranges from 94.3 degrees (average) in [Ir(dppf)(2)](+) to 102.3 degrees in [Ir(dppf)(2)](-).

show abstract

Section: Resultsmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)₅][Ir(dppf)₂]·THF and [Ir(dppf)₂]

et al. 1999

View full text Add to dashboard Cite

show abstract

Chiral Diphosphine ddppm‐Iridium Complexes: Effective Asymmetric Imine Hydrogenations at Ambient Pressures

2006

View full text Add to dashboard Cite

Complexes of the type [Ir(ddppm)(COD)]X were prepared and tested in the asymmetric hydrogenation of a range of imine substrates. Contrary to known iridium catalysts, the ddppm complexes formed efficient catalysts under an atmospheric hydrogen pressure, whereas at higher pressures the catalytic activity of the system was drastically reduced. Depending upon the reaction conditions, N-arylimines, Ar'N ¼ CMeAr, were hydrogenated to the corresponding secondary amines in high yields and enantioselectivities (80 -94% ee with molecular hydrogen at atmospheric pressure and were found to inhibit catalytic activity.

show abstract

4. Iridium 1993

Housecroft¹

1996

Coordination Chemistry Reviews

View full text Add to dashboard Cite

Structure of an iridium complex of 1,1'-bisdiphenylphosphinoferrocene

Cited by 5 publications

References 9 publications

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)₅][Ir(dppf)₂]·THF and [Ir(dppf)₂]

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)₅][Ir(dppf)₂]·THF and [Ir(dppf)₂]

Chiral Diphosphine ddppm‐Iridium Complexes: Effective Asymmetric Imine Hydrogenations at Ambient Pressures

4. Iridium 1993

Contact Info

Product

Resources

About

Structure of an iridium complex of 1,1'-bisdiphenylphosphinoferrocene

Cited by 5 publications

References 9 publications

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)5][Ir(dppf)2]·THF and [Ir(dppf)2]

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)5][Ir(dppf)2]·THF and [Ir(dppf)2]

Chiral Diphosphine ddppm‐Iridium Complexes: Effective Asymmetric Imine Hydrogenations at Ambient Pressures

4. Iridium 1993

Contact Info

Product

Resources

About

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)₅][Ir(dppf)₂]·THF and [Ir(dppf)₂]

Iridium(III, 0, and −I) Complexes Stabilized by 1,1‘-Bis(diphenylphosphino)ferrocene (dppf): Synthesis and Characterization. Crystal Structures of [Na(THF)₅][Ir(dppf)₂]·THF and [Ir(dppf)₂]