Nuclear Magnetic Resonance Study of Structural Dynamics in μ-Carbonyl-bis-μ-stannylene-diiron Hexacarbonyl Clusters

Gregory W. Grynkewich; Tobin J. Marks

doi:10.1021/ic50160a012

Nuclear Magnetic Resonance Study of Structural Dynamics in μ-Carbonyl-bis-μ-stannylene-diiron Hexacarbonyl Clusters

Gregory W. Grynkewich, Tobin J. Marks^*

^*Corresponding author for this work

MRC - Materials Research Center

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

27 Scopus citations

Abstract

The compound μ-(C₆H₅)(CH₃)Sn]₂Fe₂(CO)₇ was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R₂Sn]₂Fe₂(CO)₇ complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C₄H₉)₂Sn]₂Fe₂(CO)₇ occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by ¹³C NMR spectra. The complex [(C₆H₅)(CH₃)SnFe(CO)₄]₂ exists in two isomeric forms which interconvert in solution with ΔG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R₂Sn→Fe stannylene intermediates.

Original language	English (US)
Pages (from-to)	1307-1314
Number of pages	8
Journal	Inorganic chemistry
Volume	15
Issue number	6
DOIs	https://doi.org/10.1021/ic50160a012
State	Published - Jun 1 1976

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{245f446ded224a61b72e4f99e9b062fa,

title = "Nuclear Magnetic Resonance Study of Structural Dynamics in μ-Carbonyl-bis-μ-stannylene-diiron Hexacarbonyl Clusters",

abstract = "The compound μ-(C6H5)(CH3)Sn]2Fe2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with ΔG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.",

author = "Grynkewich, {Gregory W.} and Marks, {Tobin J.}",

year = "1976",

month = jun,

day = "1",

doi = "10.1021/ic50160a012",

language = "English (US)",

volume = "15",

pages = "1307--1314",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "6",

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T1 - Nuclear Magnetic Resonance Study of Structural Dynamics in μ-Carbonyl-bis-μ-stannylene-diiron Hexacarbonyl Clusters

AU - Grynkewich, Gregory W.

AU - Marks, Tobin J.

PY - 1976/6/1

Y1 - 1976/6/1

N2 - The compound μ-(C6H5)(CH3)Sn]2Fe2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with ΔG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.

AB - The compound μ-(C6H5)(CH3)Sn]2Fe2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with ΔG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.

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ER -

Nuclear Magnetic Resonance Study of Structural Dynamics in μ-Carbonyl-bis-μ-stannylene-diiron Hexacarbonyl Clusters

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