Preparation and reactions of some organic derivatives of manganese carbonyl compounds
type: CreativeWork
description: New orthomanganated aryl ketones of type 1 (Figure 1) have been prepared, including some in which the donor ketone carbonyl group is incorporated into a fused ring. Analogous derivatives of benzoates and heteroaromatic carboxylic acid esters are also described, together with several orthorheniated compounds. Single crystal X-ray structure determinations of η²-5-(1,4-benzopyronyl)tetracarbonylmanganese (13) and η²-(4-acetyl-2,5-dimethylthien-3 yl) tetracarbonylrhenium (32) are reported. Reactions of orthomanganated aryl ketones with SO₂ and with the electronically and structurally related cumulenes, N-sulfinylaniline (PhN=S=O), N-sulfinylbenzenesulfonamide (PhS(O)₂N=S=O) and the disulfonylsulfodiimide [PhS(O)₂N]₂S have been investigated. SO₂ inserts efficiently into the Mn-Cₐᵣᵧₗ bond of a range of orthomanganated ketones, to give the corresponding S-sulfinato complex e.g. (43) (Figure 1). The X-ray crystal structure of (43) was determined and it is the first reported example of a six-membered metallocycle incorporating an O, Mn and S atom. In contrast, reaction of PhN=S=O with a number of orthomanganated acetophenones led to the corresponding orthomanganated imines e.g. (38) (Figure 1). The structure of η²-3-chloro-2-[1-(N-phenylimino)ethyl]-phenyl-tetracarbonylmanganese (44) was determined by single crystal X-ray diffraction. PhS(O)₂NSO and [PhS(O)₂N]₂S did not react with orthomanganated p-methoxyacetophenone (39) under similar conditions. The palladium- and thermally-promoted coupling reactions of orthomanganated aryl ketones and esters with alkenes have been explored in detail. In the presence of Pd(II), η²-(o-acetylaryl)tetracarbonylmanganese compounds undergo coupling reactions with methyl acrylate, methyl vinyl ketone, acrylonitrile, acrolein, vinyl acetate and allyl alcohol. The coupling reactions normally proceed in excellent yield and produce three main products, arylalkene, arylalkane and indene, the ratios of which vary with reaction conditions and substra…
abstract: New orthomanganated aryl ketones of type 1 (Figure 1) have been prepared, including some in which the donor ketone carbonyl group is incorporated into a fused ring. Analogous derivatives of benzoates and heteroaromatic carboxylic acid esters are also described, together with several orthorheniated compounds. Single crystal X-ray structure determinations of η²-5-(1,4-benzopyronyl)tetracarbonylmanganese (13) and η²-(4-acetyl-2,5-dimethylthien-3 yl) tetracarbonylrhenium (32) are reported. Reactions of orthomanganated aryl ketones with SO₂ and with the electronically and structurally related cumulenes, N-sulfinylaniline (PhN=S=O), N-sulfinylbenzenesulfonamide (PhS(O)₂N=S=O) and the disulfonylsulfodiimide [PhS(O)₂N]₂S have been investigated. SO₂ inserts efficiently into the Mn-Cₐᵣᵧₗ bond of a range of orthomanganated ketones, to give the corresponding S-sulfinato complex e.g. (43) (Figure 1). The X-ray crystal structure of (43) was determined and it is the first reported example of a six-membered metallocycle incorporating an O, Mn and S atom. In contrast, reaction of PhN=S=O with a number of orthomanganated acetophenones led to the corresponding orthomanganated imines e.g. (38) (Figure 1). The structure of η²-3-chloro-2-[1-(N-phenylimino)ethyl]-phenyl-tetracarbonylmanganese (44) was determined by single crystal X-ray diffraction. PhS(O)₂NSO and [PhS(O)₂N]₂S did not react with orthomanganated p-methoxyacetophenone (39) under similar conditions. The palladium- and thermally-promoted coupling reactions of orthomanganated aryl ketones and esters with alkenes have been explored in detail. In the presence of Pd(II), η²-(o-acetylaryl)tetracarbonylmanganese compounds undergo coupling reactions with methyl acrylate, methyl vinyl ketone, acrylonitrile, acrolein, vinyl acetate and allyl alcohol. The coupling reactions normally proceed in excellent yield and produce three main products, arylalkene, arylalkane and indene, the ratios of which vary with reaction conditions and substra…
author: Cooney, Janine M.
license: https://researchcommons.waikato.ac.nz/bitstreams/58cf1f9d-7add-41d1-9d53-3a92003a1e94/download
date published: 1994
date modified: 2026-07-24T05:57:21Z
provider: University Waikato
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: The University of Waikato