Aspects of group 14 element - transition metal cluster chemistry
type: CreativeWork
description: The synthesis of Sn[Fe₂(CO)₈]₂ from the SnCl₄/[Fe(CO)₄]²⁻ and SnCl₄/[Fe₂(CO)₈]²⁻ systems has been investigated. The reaction of SnCl₄ with the product mixture obtained by Na/amalgam reduction of Fe(CO)₅ provided the optimum yield (64% based on Sn). E[Co₂(CO)₇]₂ (E = Si, Ge), (CO)₄CoECo₃(CO)₉ (E = Si, Ge) and E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn) have been reacted with various transition metal carbonyl anions. The Si[Co₂(CO)₇]₂/[Co(CO)₄]⁻ synthesis of [SiCo₉(CO)₂₁]²⁻, has also yielded [CCo₈(CO)₁₈]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy) and [Cl₂SiCo₇(CO)₂₁]⁻ (characterised by X-ray crystallography as the [Et₄N]⁺ salt). A [CCo₁₀(CO)₂₄]ⁿ⁻ species has also been detected by FABS mass spectroscopy. (CO)₄CoGeCo₃(CO)₉ with [Mn(CO)₅]⁻ provided (CO)₅MnGeCo₃(CO)₉ in improved yields (72%). The reaction of the Si analogue gave (CO)₅MnSiCo₃(CO)₉, characterised by infrared spectroscopy and FASS mass spectroscopy. [Co₆(CO)₁₅]= acted as a source of [Co(CO)₄]⁻ and Co₄(CO)₁₂ in reactions with (CO)₄CoECo₃(CO)₉ (E = Si, Ge). [SiCo₉(CO)₂₁]²⁻ and Co₄(CO)₁₂ were isolated as the major products from the Si reaction, and [GeCo₅(CO)₁₆]⁻ from the Ge reaction. [GeCo₅(CO)₁₆]⁻ was also isolated as the major product from the reaction of Ge[Co₂(CO)₇]₂ with [CpNi(CO)]₂. In reactions of Si[Co₂(CO)₇]₂ with [Fe2(CO)₈]²⁻ and [Fe(CO)₃NO]⁻, no Si-containing clusters were detected amongst the products. The first reaction yielded [FeCo₃(CO)₁₂]⁻ (characterised by infrared spectroscopy and preliminary X-ray diffraction), Co₄(CO)₁₂ and Fe(CO)₅; and the latter reaction, [FeCo₃(CO)₁₂]⁻, Co₄(CO)₁₂ and the nitrido cluster, [NCo₆(CO)₁₅]⁻ ( characterised by infrared spectroscopy and X-ray crystallography). Combining E[Fe₂(CO)₈]₂ with [Co(CO)₄]⁻, [Fe₂(CO)₈]²⁻ or [Mn(CO)₅]⁻ also failed to produce clusters containing E atoms. No reaction was detected with [Co(CO)₄]⁻; the second reaction yielded [HFe₃(CO)₁₁]⁻ and [Fe₄(CO)₁₃]²⁻; and the third, Mn₂(CO)₁₀ and the carbido cluster [CFe₆(CO)₁₆]²⁻ (charact…
abstract: The synthesis of Sn[Fe₂(CO)₈]₂ from the SnCl₄/[Fe(CO)₄]²⁻ and SnCl₄/[Fe₂(CO)₈]²⁻ systems has been investigated. The reaction of SnCl₄ with the product mixture obtained by Na/amalgam reduction of Fe(CO)₅ provided the optimum yield (64% based on Sn). E[Co₂(CO)₇]₂ (E = Si, Ge), (CO)₄CoECo₃(CO)₉ (E = Si, Ge) and E[Fe₂(CO)₈]₂ (E = Si, Ge, Sn) have been reacted with various transition metal carbonyl anions. The Si[Co₂(CO)₇]₂/[Co(CO)₄]⁻ synthesis of [SiCo₉(CO)₂₁]²⁻, has also yielded [CCo₈(CO)₁₈]²⁻ (characterised by infrared spectroscopy and FABS mass spectroscopy) and [Cl₂SiCo₇(CO)₂₁]⁻ (characterised by X-ray crystallography as the [Et₄N]⁺ salt). A [CCo₁₀(CO)₂₄]ⁿ⁻ species has also been detected by FABS mass spectroscopy. (CO)₄CoGeCo₃(CO)₉ with [Mn(CO)₅]⁻ provided (CO)₅MnGeCo₃(CO)₉ in improved yields (72%). The reaction of the Si analogue gave (CO)₅MnSiCo₃(CO)₉, characterised by infrared spectroscopy and FASS mass spectroscopy. [Co₆(CO)₁₅]= acted as a source of [Co(CO)₄]⁻ and Co₄(CO)₁₂ in reactions with (CO)₄CoECo₃(CO)₉ (E = Si, Ge). [SiCo₉(CO)₂₁]²⁻ and Co₄(CO)₁₂ were isolated as the major products from the Si reaction, and [GeCo₅(CO)₁₆]⁻ from the Ge reaction. [GeCo₅(CO)₁₆]⁻ was also isolated as the major product from the reaction of Ge[Co₂(CO)₇]₂ with [CpNi(CO)]₂. In reactions of Si[Co₂(CO)₇]₂ with [Fe2(CO)₈]²⁻ and [Fe(CO)₃NO]⁻, no Si-containing clusters were detected amongst the products. The first reaction yielded [FeCo₃(CO)₁₂]⁻ (characterised by infrared spectroscopy and preliminary X-ray diffraction), Co₄(CO)₁₂ and Fe(CO)₅; and the latter reaction, [FeCo₃(CO)₁₂]⁻, Co₄(CO)₁₂ and the nitrido cluster, [NCo₆(CO)₁₅]⁻ ( characterised by infrared spectroscopy and X-ray crystallography). Combining E[Fe₂(CO)₈]₂ with [Co(CO)₄]⁻, [Fe₂(CO)₈]²⁻ or [Mn(CO)₅]⁻ also failed to produce clusters containing E atoms. No reaction was detected with [Co(CO)₄]⁻; the second reaction yielded [HFe₃(CO)₁₁]⁻ and [Fe₄(CO)₁₃]²⁻; and the third, Mn₂(CO)₁₀ and the carbido cluster [CFe₆(CO)₁₆]²⁻ (charact…
author: Barris, Glen Clifton
license: https://researchcommons.waikato.ac.nz/bitstreams/ccba6c26-7136-4744-af44-c2ac8be8d03c/download
date published: 1990
date modified: 2026-07-24T05:57:46Z
provider: University Waikato
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: The University of Waikato