Crystallographic and Theoretical Analyses of the Structures of Rhenium Formyl and Acyl Complexes of the Formula (n8-CSH5)Re(NO)(PR3)(COR')

Gerardo S. Bodner; Alan T. Patton; Danny E. Smith; Savas Georglou; Wilson Tam; Wai Kwok Wong; Charles E. Strouse; J. A. Gladysz

doi:10.1021/om00152a021

Crystallographic and Theoretical Analyses of the Structures of Rhenium Formyl and Acyl Complexes of the Formula (n⁸-C_SH₅)Re(NO)(PR₃)(COR')

Gerardo S. Bodner
, Alan T. Patton
, Danny E. Smith
, Savas Georglou
, Wilson Tam
, Wai Kwok Wong
, Charles E. Strouse
, J. A. Gladysz^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

23 Citations (Scopus)

Abstract

X-ray crystal structures of formyl complex (η⁵-C5H₅)Re(NO)(PPh₃)(CHO) (1) and acyl complex (SR,-RS)-(η⁵-C₅H₅)Re(NO)(PPh₃)(COCH(CH₃)CH₂C₆HJ•(THF)_0.5 (2•(THF)_0.5) are reported. Crystal data: 1, monoclinic, P2₁/c, a = 8.065 (3) Å, b = 15.156 (3) Å, c = 16.896 (4) Å, β = 95.44 (2)°, Z = 4; 2.(THF)_0.5, triclinic, P, a = 17.844 (4) Å, b = 11.101 (2) Å, c = 9.704 (2) Å, α = 64.62 (2)°, β = 75.55 (2)°, γ = 73.20 (2)°, Z = 2. Extended Hückel MO calculations on model compounds (η⁵-C₅H₅)Re(NO)(PH₃)(COR) predict that the ON-Re-C_α-O torsion angle (θ) should be near 0° or 180°, so that overlap of the rhenium fragment HOMO with the C==0 Π* orbital will be maximized. Accordingly, Re-C_α conformations with θ near 180° are found in 1 and 2•(THF)_0.5. This places the C==O oxygen anti to the NO ligand. The geometries of the formyl and acyl ligands are contrasted and compared to those of other formyl and acyl complexes.

Original language	English
Pages (from-to)	1954-1961
Number of pages	8
Journal	Organometallics
Volume	6
Issue number	9
DOIs	https://doi.org/10.1021/om00152a021
Publication status	Published - 1 Sept 1987

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@article{e46f15bccbbb4e839e5dde38ad546730,

title = "Crystallographic and Theoretical Analyses of the Structures of Rhenium Formyl and Acyl Complexes of the Formula (n8-CSH5)Re(NO)(PR3)(COR')",

abstract = "X-ray crystal structures of formyl complex (η5-C5H5)Re(NO)(PPh3)(CHO) (1) and acyl complex (SR,-RS)-(η5-C5H5)Re(NO)(PPh3)(COCH(CH3)CH2C6HJ•(THF)0.5 (2•(THF)0.5) are reported. Crystal data: 1, monoclinic, P21/c, a = 8.065 (3) {\AA}, b = 15.156 (3) {\AA}, c = 16.896 (4) {\AA}, β = 95.44 (2)°, Z = 4; 2.(THF)0.5, triclinic, P, a = 17.844 (4) {\AA}, b = 11.101 (2) {\AA}, c = 9.704 (2) {\AA}, α = 64.62 (2)°, β = 75.55 (2)°, γ = 73.20 (2)°, Z = 2. Extended H{\"u}ckel MO calculations on model compounds (η5-C5H5)Re(NO)(PH3)(COR) predict that the ON-Re-Cα-O torsion angle (θ) should be near 0° or 180°, so that overlap of the rhenium fragment HOMO with the C==0 Π* orbital will be maximized. Accordingly, Re-Cα conformations with θ near 180° are found in 1 and 2•(THF)0.5. This places the C==O oxygen anti to the NO ligand. The geometries of the formyl and acyl ligands are contrasted and compared to those of other formyl and acyl complexes.",

author = "Bodner, \{Gerardo S.\} and Patton, \{Alan T.\} and Smith, \{Danny E.\} and Savas Georglou and Wilson Tam and Wong, \{Wai Kwok\} and Strouse, \{Charles E.\} and Gladysz, \{J. A.\}",

note = "Publisher copyright: {\textcopyright} 1987 American Chemical Society",

year = "1987",

month = sep,

day = "1",

doi = "10.1021/om00152a021",

language = "English",

volume = "6",

pages = "1954--1961",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - Crystallographic and Theoretical Analyses of the Structures of Rhenium Formyl and Acyl Complexes of the Formula (n8-CSH5)Re(NO)(PR3)(COR')

AU - Bodner, Gerardo S.

AU - Patton, Alan T.

AU - Smith, Danny E.

AU - Georglou, Savas

AU - Tam, Wilson

AU - Wong, Wai Kwok

AU - Strouse, Charles E.

AU - Gladysz, J. A.

PY - 1987/9/1

Y1 - 1987/9/1

N2 - X-ray crystal structures of formyl complex (η5-C5H5)Re(NO)(PPh3)(CHO) (1) and acyl complex (SR,-RS)-(η5-C5H5)Re(NO)(PPh3)(COCH(CH3)CH2C6HJ•(THF)0.5 (2•(THF)0.5) are reported. Crystal data: 1, monoclinic, P21/c, a = 8.065 (3) Å, b = 15.156 (3) Å, c = 16.896 (4) Å, β = 95.44 (2)°, Z = 4; 2.(THF)0.5, triclinic, P, a = 17.844 (4) Å, b = 11.101 (2) Å, c = 9.704 (2) Å, α = 64.62 (2)°, β = 75.55 (2)°, γ = 73.20 (2)°, Z = 2. Extended Hückel MO calculations on model compounds (η5-C5H5)Re(NO)(PH3)(COR) predict that the ON-Re-Cα-O torsion angle (θ) should be near 0° or 180°, so that overlap of the rhenium fragment HOMO with the C==0 Π* orbital will be maximized. Accordingly, Re-Cα conformations with θ near 180° are found in 1 and 2•(THF)0.5. This places the C==O oxygen anti to the NO ligand. The geometries of the formyl and acyl ligands are contrasted and compared to those of other formyl and acyl complexes.

AB - X-ray crystal structures of formyl complex (η5-C5H5)Re(NO)(PPh3)(CHO) (1) and acyl complex (SR,-RS)-(η5-C5H5)Re(NO)(PPh3)(COCH(CH3)CH2C6HJ•(THF)0.5 (2•(THF)0.5) are reported. Crystal data: 1, monoclinic, P21/c, a = 8.065 (3) Å, b = 15.156 (3) Å, c = 16.896 (4) Å, β = 95.44 (2)°, Z = 4; 2.(THF)0.5, triclinic, P, a = 17.844 (4) Å, b = 11.101 (2) Å, c = 9.704 (2) Å, α = 64.62 (2)°, β = 75.55 (2)°, γ = 73.20 (2)°, Z = 2. Extended Hückel MO calculations on model compounds (η5-C5H5)Re(NO)(PH3)(COR) predict that the ON-Re-Cα-O torsion angle (θ) should be near 0° or 180°, so that overlap of the rhenium fragment HOMO with the C==0 Π* orbital will be maximized. Accordingly, Re-Cα conformations with θ near 180° are found in 1 and 2•(THF)0.5. This places the C==O oxygen anti to the NO ligand. The geometries of the formyl and acyl ligands are contrasted and compared to those of other formyl and acyl complexes.

UR - https://www.scopus.com/pages/publications/0348180226

U2 - 10.1021/om00152a021

DO - 10.1021/om00152a021

M3 - Journal article

AN - SCOPUS:0348180226

SN - 0276-7333

VL - 6

SP - 1954

EP - 1961

JO - Organometallics

JF - Organometallics

IS - 9

ER -

Crystallographic and Theoretical Analyses of the Structures of Rhenium Formyl and Acyl Complexes of the Formula (n⁸-C_SH₅)Re(NO)(PR₃)(COR')

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