Crystal Structures and Packing of the Tricarbonylbis(phosphine)iron(0) Complexes trans-Fe(CO)₃L₂ (L = PPh₂Me, PPh₃). Interplay between Arene-Arene Interactions and Phosphine Conformations

Rainer Glaser; Paul E. Haney; Charles Leslie Barnes

doi:10.1021/ic9509894

Crystal Structures and Packing of the Tricarbonylbis(phosphine)iron(0) Complexes trans-Fe(CO)₃L₂ (L = PPh₂Me, PPh₃). Interplay between Arene-Arene Interactions and Phosphine Conformations

Rainer Glaser
, Paul E. Haney
, Charles Leslie Barnes

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Structural effects of the nature of the phosphines on trans -tricarbonylbis(phosphine)iron(0) complexes trans -Fe(CO) 3 L 2 (L = PPh 2Me, PPh 3) are explored. The X-ray crystal structure of trans -Fe(CO) 3 (PPh 2 Me) 2 , 1 , is reported. Complex 1 crystallizes in the monoclinic space group P 2 1 / c with cell parameters a = 15.551(6) Å, b = 9.7024(12) Å, c = 17.320(6) Å,β = 91.081(11), and Z = 4. Refinement resulted in R = 0.045 and R w = 0.054 for 3614 independent reflections with I > 2.0σ( I ). The structure of 1 is compared to trans -Fe(CO) 3 (PPh 3 ) 2 , 2, and its etherate 2 ·OEt 2 , 3 . Further comparisons are made to the isoelectronic complex trans -[Co(CO) 3 (PPh 3 ) 2 ] + , 4 , and the radical cation [Fe(CO) 3 (PPh 3 ) 2 ] &dot;+ , 2 &dot;+ . Phosphine replacement affects intrinsic structural properties of 1-3 only marginally. In particular, the average Fe-P bond lengths in 1 (2.206 Å), 2 (2.217 Å), and 3 (2.216 Å) all are essentially the same in light of the standard deviations. The structures of the free and complexed phosphines also are essentially identical. Complexes 1-3 show a common motif of distortion from the trigonal planar (pseudo) C 3 v bipyramid (P-Fe-P nonlinearity, Fe(CO) 3 C 2 v -distortion, and phosphine nonequivalence). Ab initio calculations for trans -Fe(CO) 3 (PH 3 ) 2 at the MP2/LANL1DZ level suggest that these distortions are due to packing. The phosphines are more or less staggered with respect to the carbonyls and the methyl groups are gauche . Co(I) versus Fe(0) replacement retains the trigonal bipyramidal structure while the oxidation of 2 to 2 &dot;+ yields the square pyramidal structure with longer trans Fe - P bonds (2.282 Å). Of special interest are the unexpected phosphine conformations in 1-3 and they are shown to be beneficial for the optimization of intermolecular arene-arene interactions. The crystal packing of 1 reveals displaced face-to-face and displaced T-shape arene-arene contacts that place the two phenyl rings in relative orientations that lead to stabilization in the respective benzene dimers. A rotated displaced T-shape arrangement plays a crucial role in 2 . The analyses emphasize the interplay between intermolecular arene-arene packing interactions and the phosphine conformations.

Original language	American English
Journal	Inorganic Chemistry
Volume	35
DOIs	https://doi.org/10.1021/ic9509894
State	Published - Mar 1 1996

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Chemistry

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@article{114af79a1d684ec3b5e28596dbb26e79,

title = "Crystal Structures and Packing of the Tricarbonylbis(phosphine)iron(0) Complexes trans-Fe(CO)₃L₂ (L = PPh₂Me, PPh₃). Interplay between Arene-Arene Interactions and Phosphine Conformations",

abstract = " Structural effects of the nature of the phosphines on trans -tricarbonylbis(phosphine)iron(0) complexes trans -Fe(CO) 3 L 2 (L = PPh 2Me, PPh 3) are explored. The X-ray crystal structure of trans -Fe(CO) 3 (PPh 2 Me) 2 , 1 , is reported. Complex 1 crystallizes in the monoclinic space group P 2 1 / c with cell parameters a = 15.551(6) \Å, b = 9.7024(12) \Å, c = 17.320(6) \Å,\β = 91.081(11), and Z = 4. Refinement resulted in R = 0.045 and R w = 0.054 for 3614 independent reflections with I > 2.0\σ( I ). The structure of 1 is compared to trans -Fe(CO) 3 (PPh 3 ) 2 , 2, and its etherate 2 \·OEt 2 , 3 . Further comparisons are made to the isoelectronic complex trans -[Co(CO) 3 (PPh 3 ) 2 ] + , 4 , and the radical cation [Fe(CO) 3 (PPh 3 ) 2 ] \&dot;+ , 2 \&dot;+ . Phosphine replacement affects intrinsic structural properties of 1-3 only marginally. In particular, the average Fe-P bond lengths in 1 (2.206 \Å), 2 (2.217 \Å), and 3 (2.216 \Å) all are essentially the same in light of the standard deviations. The structures of the free and complexed phosphines also are essentially identical. Complexes 1-3 show a common motif of distortion from the trigonal planar (pseudo) C 3 v bipyramid (P-Fe-P nonlinearity, Fe(CO) 3 C 2 v -distortion, and phosphine nonequivalence). Ab initio calculations for trans -Fe(CO) 3 (PH 3 ) 2 at the MP2/LANL1DZ level suggest that these distortions are due to packing. The phosphines are more or less staggered with respect to the carbonyls and the methyl groups are gauche . Co(I) versus Fe(0) replacement retains the trigonal bipyramidal structure while the oxidation of 2 to 2 \&dot;+ yields the square pyramidal structure with longer trans Fe - P bonds (2.282 \Å). Of special interest are the unexpected phosphine conformations in 1-3 and they are shown to be beneficial for the optimization of intermolecular arene-arene interactions. The crystal packing of 1 reveals displaced face-to-face and displaced T-shape arene-arene contacts that place the two phenyl rings in relative orientations that lead to stabilization in the respective benzene dimers. A rotated displaced T-shape arrangement plays a crucial role in 2 . The analyses emphasize the interplay between intermolecular arene-arene packing interactions and the phosphine conformations.",

author = "Rainer Glaser and Haney, \{Paul E.\} and Barnes, \{Charles Leslie\}",

year = "1996",

month = mar,

day = "1",

doi = "10.1021/ic9509894",

language = "American English",

volume = "35",

journal = "Inorganic Chemistry",

}

TY - JOUR

T1 - Crystal Structures and Packing of the Tricarbonylbis(phosphine)iron(0) Complexes trans-Fe(CO)₃L₂ (L = PPh₂Me, PPh₃). Interplay between Arene-Arene Interactions and Phosphine Conformations

AU - Glaser, Rainer

AU - Haney, Paul E.

AU - Barnes, Charles Leslie

PY - 1996/3/1

Y1 - 1996/3/1

N2 - Structural effects of the nature of the phosphines on trans -tricarbonylbis(phosphine)iron(0) complexes trans -Fe(CO) 3 L 2 (L = PPh 2Me, PPh 3) are explored. The X-ray crystal structure of trans -Fe(CO) 3 (PPh 2 Me) 2 , 1 , is reported. Complex 1 crystallizes in the monoclinic space group P 2 1 / c with cell parameters a = 15.551(6) Å, b = 9.7024(12) Å, c = 17.320(6) Å,β = 91.081(11), and Z = 4. Refinement resulted in R = 0.045 and R w = 0.054 for 3614 independent reflections with I > 2.0σ( I ). The structure of 1 is compared to trans -Fe(CO) 3 (PPh 3 ) 2 , 2, and its etherate 2 ·OEt 2 , 3 . Further comparisons are made to the isoelectronic complex trans -[Co(CO) 3 (PPh 3 ) 2 ] + , 4 , and the radical cation [Fe(CO) 3 (PPh 3 ) 2 ] &dot;+ , 2 &dot;+ . Phosphine replacement affects intrinsic structural properties of 1-3 only marginally. In particular, the average Fe-P bond lengths in 1 (2.206 Å), 2 (2.217 Å), and 3 (2.216 Å) all are essentially the same in light of the standard deviations. The structures of the free and complexed phosphines also are essentially identical. Complexes 1-3 show a common motif of distortion from the trigonal planar (pseudo) C 3 v bipyramid (P-Fe-P nonlinearity, Fe(CO) 3 C 2 v -distortion, and phosphine nonequivalence). Ab initio calculations for trans -Fe(CO) 3 (PH 3 ) 2 at the MP2/LANL1DZ level suggest that these distortions are due to packing. The phosphines are more or less staggered with respect to the carbonyls and the methyl groups are gauche . Co(I) versus Fe(0) replacement retains the trigonal bipyramidal structure while the oxidation of 2 to 2 &dot;+ yields the square pyramidal structure with longer trans Fe - P bonds (2.282 Å). Of special interest are the unexpected phosphine conformations in 1-3 and they are shown to be beneficial for the optimization of intermolecular arene-arene interactions. The crystal packing of 1 reveals displaced face-to-face and displaced T-shape arene-arene contacts that place the two phenyl rings in relative orientations that lead to stabilization in the respective benzene dimers. A rotated displaced T-shape arrangement plays a crucial role in 2 . The analyses emphasize the interplay between intermolecular arene-arene packing interactions and the phosphine conformations.

AB - Structural effects of the nature of the phosphines on trans -tricarbonylbis(phosphine)iron(0) complexes trans -Fe(CO) 3 L 2 (L = PPh 2Me, PPh 3) are explored. The X-ray crystal structure of trans -Fe(CO) 3 (PPh 2 Me) 2 , 1 , is reported. Complex 1 crystallizes in the monoclinic space group P 2 1 / c with cell parameters a = 15.551(6) Å, b = 9.7024(12) Å, c = 17.320(6) Å,β = 91.081(11), and Z = 4. Refinement resulted in R = 0.045 and R w = 0.054 for 3614 independent reflections with I > 2.0σ( I ). The structure of 1 is compared to trans -Fe(CO) 3 (PPh 3 ) 2 , 2, and its etherate 2 ·OEt 2 , 3 . Further comparisons are made to the isoelectronic complex trans -[Co(CO) 3 (PPh 3 ) 2 ] + , 4 , and the radical cation [Fe(CO) 3 (PPh 3 ) 2 ] &dot;+ , 2 &dot;+ . Phosphine replacement affects intrinsic structural properties of 1-3 only marginally. In particular, the average Fe-P bond lengths in 1 (2.206 Å), 2 (2.217 Å), and 3 (2.216 Å) all are essentially the same in light of the standard deviations. The structures of the free and complexed phosphines also are essentially identical. Complexes 1-3 show a common motif of distortion from the trigonal planar (pseudo) C 3 v bipyramid (P-Fe-P nonlinearity, Fe(CO) 3 C 2 v -distortion, and phosphine nonequivalence). Ab initio calculations for trans -Fe(CO) 3 (PH 3 ) 2 at the MP2/LANL1DZ level suggest that these distortions are due to packing. The phosphines are more or less staggered with respect to the carbonyls and the methyl groups are gauche . Co(I) versus Fe(0) replacement retains the trigonal bipyramidal structure while the oxidation of 2 to 2 &dot;+ yields the square pyramidal structure with longer trans Fe - P bonds (2.282 Å). Of special interest are the unexpected phosphine conformations in 1-3 and they are shown to be beneficial for the optimization of intermolecular arene-arene interactions. The crystal packing of 1 reveals displaced face-to-face and displaced T-shape arene-arene contacts that place the two phenyl rings in relative orientations that lead to stabilization in the respective benzene dimers. A rotated displaced T-shape arrangement plays a crucial role in 2 . The analyses emphasize the interplay between intermolecular arene-arene packing interactions and the phosphine conformations.

UR - https://scholarsmine.mst.edu/chem_facwork/2757

UR - http://doi.org/10.1021/ic9509894

U2 - 10.1021/ic9509894

DO - 10.1021/ic9509894

M3 - Article

VL - 35

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

Crystal Structures and Packing of the Tricarbonylbis(phosphine)iron(0) Complexes trans-Fe(CO)₃L₂ (L = PPh₂Me, PPh₃). Interplay between Arene-Arene Interactions and Phosphine Conformations

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