Crystal Structure of trans-Fe(CO)₃(PPh₃)₂, Tricarbonylbis(Triphenylphosphine)Iron(0), and Ab Initio Study of the Bonding in Trans-Fe(CO)₃(PH₃)₂

Rainer Glaser; Younghee Yoo; Grace Shiahuy Chen; Charles Leslie Barnes

doi:10.1021/om00019a014

Crystal Structure of trans-Fe(CO)₃(PPh₃)₂, Tricarbonylbis(Triphenylphosphine)Iron(0), and Ab Initio Study of the Bonding in Trans-Fe(CO)₃(PH₃)₂

Rainer Glaser
, Younghee Yoo
, Grace Shiahuy Chen
, Charles Leslie Barnes

Chemistry

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

Abstract

The selective one-step preparation of trans -Fe(CO) ₃ (PPh ₃ ) ₂ , 1, in the absence of Fe(CO) _{4 ^-} (PPh ₃ ) has made it possible to obtain 1 pure and in crystalline form. trans -Fe(CO) ₃ (PPh ₃ ) ₂ crystallizes in the orthorhombic space group Pbca with cell parameters a = 18.216(5) Å, b = 17.0380(10) Å, c = 21.804(3) Å, and Z = 8; R = 0.042 and R _w = 0.056 for 3891 independent reflections with I > 2.0 Ïƒ ( I ). The crystal structure of 1 is compared to Ru(CO) ₃ (PPh ₃ ) ₂ , Os(CO) ₃ (PPh ₃ ) ₂ ) Fe(CO) ₂ (CS)(PPh ₃ ) ₂ , and a selection of complexes of the types trans -Fe(CO) ₃ (PR ₃ ) ₂ (R = Ph, NMe ₂ , OMe) and trans -Fe(CO) ₄ PR ₃ (R = Ph, NMe ₂ , CMe ₃ , SiMe ₃ ). Effects of equatorial CO substitution in 1 by the diazonium ion and nitrile ligands are discussed. Ab initio calculations that employ effective core potential basis sets at the Hartree-Fock level and which include perturbational corrections for electron correlation at the MP2 level are reported for trans -Fe(CO) ₃ (PH ₃ ) ₂ . Good agreement between theory and experiment can only be obtained at correlated levels of theory in conjunction with double-ζ quality basis sets on iron and all ligands. Population analyses are employed to examine the effects of electron correlation and to delineate the iron-ligand bonding. Electron correlation serves overall to reduce the molecular quadrupole moment. Comparison between the crystal structure of 1 and the theoretical structure of the model system allow differentiation between intrinsic structural preferences and packing effects. In particular, the comparison points out that the Fe-P bond length differences and the nonlinearity of the P-Fe-P backbone are not intrinsic bonding features but are caused by the packing.

Original language	American English
Journal	Organometallics
Volume	13
DOIs	https://doi.org/10.1021/om00019a014
State	Published - Jul 1 1994

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Chemistry

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@article{3d38da9458c14f199f803ee678a10d90,

title = "Crystal Structure of trans-Fe(CO)₃(PPh₃)₂, Tricarbonylbis(Triphenylphosphine)Iron(0), and Ab Initio Study of the Bonding in Trans-Fe(CO)₃(PH₃)₂",

abstract = " The selective one-step preparation of trans -Fe(CO) 3 (PPh 3 ) 2 , 1, in the absence of Fe(CO) 4 - (PPh 3 ) has made it possible to obtain 1 pure and in crystalline form. trans -Fe(CO) 3 (PPh 3 ) 2 crystallizes in the orthorhombic space group Pbca with cell parameters a = 18.216(5) {\AA}, b = 17.0380(10) {\AA}, c = 21.804(3) {\AA}, and Z = 8; R = 0.042 and R w = 0.056 for 3891 independent reflections with I > 2.0 {\"I}ƒ ( I ). The crystal structure of 1 is compared to Ru(CO) 3 (PPh 3 ) 2 , Os(CO) 3 (PPh 3 ) 2 ) Fe(CO) 2 (CS)(PPh 3 ) 2 , and a selection of complexes of the types trans -Fe(CO) 3 (PR 3 ) 2 (R = Ph, NMe 2 , OMe) and trans -Fe(CO) 4 PR 3 (R = Ph, NMe 2 , CMe 3 , SiMe 3 ). Effects of equatorial CO substitution in 1 by the diazonium ion and nitrile ligands are discussed. Ab initio calculations that employ effective core potential basis sets at the Hartree-Fock level and which include perturbational corrections for electron correlation at the MP2 level are reported for trans -Fe(CO) 3 (PH 3 ) 2 . Good agreement between theory and experiment can only be obtained at correlated levels of theory in conjunction with double-ζ quality basis sets on iron and all ligands. Population analyses are employed to examine the effects of electron correlation and to delineate the iron-ligand bonding. Electron correlation serves overall to reduce the molecular quadrupole moment. Comparison between the crystal structure of 1 and the theoretical structure of the model system allow differentiation between intrinsic structural preferences and packing effects. In particular, the comparison points out that the Fe-P bond length differences and the nonlinearity of the P-Fe-P backbone are not intrinsic bonding features but are caused by the packing.",

author = "Rainer Glaser and Younghee Yoo and Chen, \{Grace Shiahuy\} and Barnes, \{Charles Leslie\}",

year = "1994",

month = jul,

day = "1",

doi = "10.1021/om00019a014",

language = "American English",

volume = "13",

journal = "Organometallics",

issn = "1520-6041",

}

TY - JOUR

T1 - Crystal Structure of trans-Fe(CO)₃(PPh₃)₂, Tricarbonylbis(Triphenylphosphine)Iron(0), and Ab Initio Study of the Bonding in Trans-Fe(CO)₃(PH₃)₂

AU - Glaser, Rainer

AU - Yoo, Younghee

AU - Chen, Grace Shiahuy

AU - Barnes, Charles Leslie

PY - 1994/7/1

Y1 - 1994/7/1

N2 - The selective one-step preparation of trans -Fe(CO) 3 (PPh 3 ) 2 , 1, in the absence of Fe(CO) 4 - (PPh 3 ) has made it possible to obtain 1 pure and in crystalline form. trans -Fe(CO) 3 (PPh 3 ) 2 crystallizes in the orthorhombic space group Pbca with cell parameters a = 18.216(5) Å, b = 17.0380(10) Å, c = 21.804(3) Å, and Z = 8; R = 0.042 and R w = 0.056 for 3891 independent reflections with I > 2.0 Ïƒ ( I ). The crystal structure of 1 is compared to Ru(CO) 3 (PPh 3 ) 2 , Os(CO) 3 (PPh 3 ) 2 ) Fe(CO) 2 (CS)(PPh 3 ) 2 , and a selection of complexes of the types trans -Fe(CO) 3 (PR 3 ) 2 (R = Ph, NMe 2 , OMe) and trans -Fe(CO) 4 PR 3 (R = Ph, NMe 2 , CMe 3 , SiMe 3 ). Effects of equatorial CO substitution in 1 by the diazonium ion and nitrile ligands are discussed. Ab initio calculations that employ effective core potential basis sets at the Hartree-Fock level and which include perturbational corrections for electron correlation at the MP2 level are reported for trans -Fe(CO) 3 (PH 3 ) 2 . Good agreement between theory and experiment can only be obtained at correlated levels of theory in conjunction with double-ζ quality basis sets on iron and all ligands. Population analyses are employed to examine the effects of electron correlation and to delineate the iron-ligand bonding. Electron correlation serves overall to reduce the molecular quadrupole moment. Comparison between the crystal structure of 1 and the theoretical structure of the model system allow differentiation between intrinsic structural preferences and packing effects. In particular, the comparison points out that the Fe-P bond length differences and the nonlinearity of the P-Fe-P backbone are not intrinsic bonding features but are caused by the packing.

AB - The selective one-step preparation of trans -Fe(CO) 3 (PPh 3 ) 2 , 1, in the absence of Fe(CO) 4 - (PPh 3 ) has made it possible to obtain 1 pure and in crystalline form. trans -Fe(CO) 3 (PPh 3 ) 2 crystallizes in the orthorhombic space group Pbca with cell parameters a = 18.216(5) Å, b = 17.0380(10) Å, c = 21.804(3) Å, and Z = 8; R = 0.042 and R w = 0.056 for 3891 independent reflections with I > 2.0 Ïƒ ( I ). The crystal structure of 1 is compared to Ru(CO) 3 (PPh 3 ) 2 , Os(CO) 3 (PPh 3 ) 2 ) Fe(CO) 2 (CS)(PPh 3 ) 2 , and a selection of complexes of the types trans -Fe(CO) 3 (PR 3 ) 2 (R = Ph, NMe 2 , OMe) and trans -Fe(CO) 4 PR 3 (R = Ph, NMe 2 , CMe 3 , SiMe 3 ). Effects of equatorial CO substitution in 1 by the diazonium ion and nitrile ligands are discussed. Ab initio calculations that employ effective core potential basis sets at the Hartree-Fock level and which include perturbational corrections for electron correlation at the MP2 level are reported for trans -Fe(CO) 3 (PH 3 ) 2 . Good agreement between theory and experiment can only be obtained at correlated levels of theory in conjunction with double-ζ quality basis sets on iron and all ligands. Population analyses are employed to examine the effects of electron correlation and to delineate the iron-ligand bonding. Electron correlation serves overall to reduce the molecular quadrupole moment. Comparison between the crystal structure of 1 and the theoretical structure of the model system allow differentiation between intrinsic structural preferences and packing effects. In particular, the comparison points out that the Fe-P bond length differences and the nonlinearity of the P-Fe-P backbone are not intrinsic bonding features but are caused by the packing.

UR - https://scholarsmine.mst.edu/chem_facwork/2755

UR - http://doi.org/10.1021/om00019a014

U2 - 10.1021/om00019a014

DO - 10.1021/om00019a014

M3 - Article

SN - 1520-6041

VL - 13

JO - Organometallics

JF - Organometallics

ER -

Crystal Structure of trans-Fe(CO)₃(PPh₃)₂, Tricarbonylbis(Triphenylphosphine)Iron(0), and Ab Initio Study of the Bonding in Trans-Fe(CO)₃(PH₃)₂

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