TY - JOUR
T1 - The structure of hydridocarbonyl(fumaronitrile)bis(triphenylphosphine)iridium, an olefin-metal hydride complex
AU - Muir, Kenneth W.
AU - Ibers, James A.
N1 - Funding Information:
We are grateful to Dr. W. H. Baddiey and miss M. Shirley Fraser for supplying us with crystals and to Dr. W. C. Hamilton for making results available to us prior to publication. This work was supported by the U.S. National Science Foundation and the U.S. National Institutes of Health.
PY - 1969/7
Y1 - 1969/7
N2 - The structure of the complex hydridocarbonyl(fumaronitrile)bis(triphenylphosphine)iridium, IrH(CO)(trans-NCCHCHCN)[P(C6H5)3]2, has been determined from a single crystal X-ray analysis. The complex crystallizes in a monoclinic cell of dimensions a = 21.289(14), b = 9.383(3), c = 21.650(10) Å, β= 123.87(2)°. The observed density is 1.53 g·cm-3, whereas the density calculated for four formula units per unit cell is 1.524 g·cm-3. On the basis of a successful structure analysis, the space group is C2/c. The structure has been refined by least-squares methods to a conventional R-factor of 0.056 for the 2274 independent reflections whose intensities were above background, when measured by counter techniques. The molecules are monomeric; the configuration around the iridium atom is trigonal bipyramidal, with the olefin and phosphine ligands in the equatorial plane, which also contains a twofold axis of crystallographic symmetry. The fumaronitrile ligand is nonplanar, the dihedral angle between the two planes which contain a carbon atom of a cyanide group and both olefinic carbon atoms is 136(2)°. The IrP and IrC distances are respectively 2.317(3) and 2.110(9) Å, while the CC distance is 1.431 (20) Å. Assuming an IrH bonded distance of 1.6 Å, the nonbonded contact between the hydridic hydrogen atom and an olefin carbon atom is 2.6 Å. It is of interest that the hydridic hydrogen atom is cis to the olefin since complexes related to the present one are believed to play a role in the catalyzed hydrogenation reactions of olefins.
AB - The structure of the complex hydridocarbonyl(fumaronitrile)bis(triphenylphosphine)iridium, IrH(CO)(trans-NCCHCHCN)[P(C6H5)3]2, has been determined from a single crystal X-ray analysis. The complex crystallizes in a monoclinic cell of dimensions a = 21.289(14), b = 9.383(3), c = 21.650(10) Å, β= 123.87(2)°. The observed density is 1.53 g·cm-3, whereas the density calculated for four formula units per unit cell is 1.524 g·cm-3. On the basis of a successful structure analysis, the space group is C2/c. The structure has been refined by least-squares methods to a conventional R-factor of 0.056 for the 2274 independent reflections whose intensities were above background, when measured by counter techniques. The molecules are monomeric; the configuration around the iridium atom is trigonal bipyramidal, with the olefin and phosphine ligands in the equatorial plane, which also contains a twofold axis of crystallographic symmetry. The fumaronitrile ligand is nonplanar, the dihedral angle between the two planes which contain a carbon atom of a cyanide group and both olefinic carbon atoms is 136(2)°. The IrP and IrC distances are respectively 2.317(3) and 2.110(9) Å, while the CC distance is 1.431 (20) Å. Assuming an IrH bonded distance of 1.6 Å, the nonbonded contact between the hydridic hydrogen atom and an olefin carbon atom is 2.6 Å. It is of interest that the hydridic hydrogen atom is cis to the olefin since complexes related to the present one are believed to play a role in the catalyzed hydrogenation reactions of olefins.
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U2 - 10.1016/S0022-328X(00)80246-6
DO - 10.1016/S0022-328X(00)80246-6
M3 - Article
AN - SCOPUS:49849119873
SN - 0022-328X
VL - 18
SP - 175
EP - 187
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -