Platinum(II) complexes containing ferrocene-derived phosphonate ligands; synthesis, structural characterisation and antitumour activity

Platinum ferrocenyl–phosphonate complexes, containing four-membered Pt---O---P(O)---O rings, have been synthesised by the reactions of cis-[PtCl₂(PPh₃)₂] with the ferrocene-derived phosphonic acids Fc(CH₂)nP(O)(OH)₂(n=0–2) [Fc=(η⁵-C₅H₄)Fe(η⁵-C₅H₅)] and 1,1′-Fc′[P(O)(OH)₂]₂ [Fc′=Fe(η⁵-C₅H₄)₂] in the presence of Ag₂O. The complexes have been characterised by NMR spectroscopy, together with crystal structure determinations on [Fc(CH₂)nPO₃Pt(PPh₃)₂] (n=1, 2) and [1,1′-Fc′{PO₃Pt(PPh₃)₂}₂]. The complexes [Fc(CH₂)nPO₃Pt(PPh₃)₂] (n=1, 2) show moderate activity against P388 leukaemia cells, whereas the parent phosphonic acids are inactive

Ferrocenyl hydroxymethylphosphines (η⁵-C₅H₅)Fe[η⁵⁻C₅H₄P(CH₂OH)₂] and 1,1′-[Fe{η⁵-C₅H₄P(CH₂OH)₂}₂] and their chalcogenide derivatives

The ferrocenyl hydroxymethylphosphines FcP(CH₂OH)₂ [Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄)] and 1,1′-Fc′[P(CH₂OH)₂]₂ [Fc′=Fe(η⁵⁻C₅H₄)₂] were prepared by reactions of the corresponding primary phosphines FcPH₂ and 1,1′-Fc′(PH₂)₂ with excess aqueous formaldehyde. The crystal structure of FcP(CH₂OH)₂ was determined and compared with the known ferrocenyl hydroxymethylphosphine FcCH₂P(CH₂OH)₂. The chalcogenide derivatives FcP(E)(CH₂OH)₂ and 1,1′-Fc′[P(E)(CH₂OH)₂]₂ (E=O, S, Se) were prepared and fully characterised. Crystal structure determinations on FcP(O)(CH₂OH)₂ and FcP(S)(CH₂OH)₂ were performed, and the hydrogen-bonding patterns are compared with related compounds. The sulfide shows no hydrogen-bonding involving the phosphine sulfide group, in contrast to other reported ferrocenyl hydroxymethylphosphine sulfides. The platinum complex cis-[PtCl₂{FcP(CH₂OH)₂}₂] was prepared by reaction of 2 mol equivalents of FcP(CH₂OH)₂ with [PtCl₂(1,5-cyclo-octadiene)], and was characterised by 31P-NMR spectroscopy and negative ion electrospray mass spectrometry, which gave a strong [M+Cl]⁻ ion

‘User-friendly’ primary phosphines and an arsine: synthesis and characterization of new air-stable ligands incorporating the ferrocenyl group

Reaction of FcCH₂CH₂P(O)(OH)₂ or FcCH₂P(O)(OH)(OEt) [Fc=Fe(η⁵-C₅H₄)(η⁵-C₅H₅)] with excess CH₂N₂ followed by reduction with Me₃SiCl–LiAlH₄ gives the air-stable primary phosphines FcCH₂CH₂PH₂ and the previously reported analogue FcCH₂PH₂ in high yields. Reduction of 1,1′-Fc′[CH₂P(O)(OEt)₂] [Fc′=Fe(η⁵-C₅H₄)₂] and 1,2-Fc″[CH₂P(O)(OEt)₂] [Fc″=Fe(η⁵-C₅H₅)(η⁵-C₅H₃)] similarly gives the new primary phosphines 1,1′-Fc′(CH₂PH₂)₂ and 1,2-Fc″(CH₂PH₂)₂, respectively. The arsine FcCH₂CH₂AsH₂, which is also air-stable, has been prepared by reduction of the arsonic acid FcCH₂CH₂As(O)(OH)₂ using Zn/HCl. An X-ray structure has been carried out on the arsine, which is only the second structure determination of a free primary arsine. The molybdenum carbonyl complex [1,2-Fc″(CH₂PH₂)₂Mo(CO)₄] was prepared by reaction of the phosphine with [Mo(CO)₄(pip)₂] (pip=piperidine), and characterized by a preliminary X-ray structure determination. However, the same reaction of 1,1′-Fc′(CH₂PH₂)₂with [Mo(CO)₄(pip)₂] gave [1,1′-Fc′(CH₂PH₂)₂Mo(CO)₄] and the dimer [1,1′-Fc′(CH₂PH₂)₂Mo(CO)₄]₂, characterized by electrospray mass spectrometry. 1,1′-Fc′[CH₂PH₂Mo(CO)₅]₂ and 1,2-Fc″[CH₂PH₂Mo(CO)₅]₂ were likewise prepared from the phosphines and excess [Mo(CO)₅(THF)]

New ferrocene-derived hydroxymethylphosphines: FcP(CH₂OH)₂ [Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄)] and the dppf analogue 1,1′-Fc′[P(CH₂OH)₂]₂ [Fc′=Fe(η⁵-C₅H₄)₂]

Reactions of the ferrocene-phosphines FcPH₂ and 1,1′-Fc′(PH₂)₂ with excess formaldehyde gives the new hydroxymethylphosphines FcP(CH₂OH)₂ 1 and 1,1′-Fc′[P(CH₂OH)₂]₂ 2, respectively. Phosphine 1 is an air-stable crystalline solid, whereas 2 is isolated as an oil. Reaction of 1 with H₂O₂, S₈ or Se gives the chalcogenide derivatives FcP(E)(CH₂OH)₂ (E=O, S or Se), whilst reaction of 2 with S8 gives 1,1′-Fc′[P(S)(CH₂OH)₂]₂, which were fully characterised. Phosphine 1 was also characterised by an X-ray crystal structure determination

Synthesis and characterisation of ferrocenyl-phosphonic and -arsonic

The ferrocene-derived acids FcCH₂CH₂E(O)(OH)₂ [4, E=P; 10, E=As; Fc=Fe(η₅-C₅H₅)(η⁵-C₅H₄)] have been synthesized by the reaction of FcCH₂CH₂Br with either P(OEt)₃ followed by hydrolysis, or with sodium arsenite followed by acidification. Reaction of FcCH₂OH with (EtO)₂P(O)Na gave FcP(O)(OEt)(OH), which was converted to FcCH₂P(O)(OH)₂ (3) by silyl ester hydrolysis using Me₃SiBr–Et₃N followed by aqueous work-up. Similarly, the known phosphonic acid FcP(O)(OH)₂and the new derivatives 1,1′-Fc′[P(O)(OH)₂]₂ [Fc′=Fe(η⁵-C₅H₄)₂] and 1,1′-Fc′[CH₂P(O)(OH)₂]₂(7) have been synthesized via their corresponding esters. X-ray crystal structure determinations have been carried out on 3 and 7, and the hydrogen-bonding networks discussed. Electrospray mass spectrometry has been employed in the characterization of the various acids. Phosphonic acids give the expected [M–H]− ions and their fragmentation at elevated cone voltages has been found to be dependent on the acid. FcP(O)(OH)₂ fragments to [C₅H₄PO₂H]−, but in contrast Fc(CH₂)nP(O)(OH)₂ (n=1, 2) give Fe{η⁵-C₅H₄(CH₂)nP(O)O₂]− ions, which are proposed to have an intramolecular interaction between the Fe atom and the phosphonate group. In contrast, arsonic acid (10), together with PhAs(O)(OH)₂for comparison, undergo facile alkylation (in methanol or ethanol solvent), and at elevated cone voltages (e.g. >60 V) undergo carbon–arsenic bond cleavage giving [CpFeAs(O)(OR)O]− (R=H, Me, Et) and ultimately [AsO₂]− ions

Manufacture of cream cheese involving the use of dry skim milk

Caption title.Digitized 2006 AES MoU

The relation of dry skim milk to several of the physical and chemical properties of cream cheese

Publication authorized June 28, 1934."The data presented in this bulletin were taken from a paper submitted by the junior author in partial fulfillment of the requirements for the degree of Master of Arts in the Graduate School of the University of Missouri, 1933"--P. [3].Includes bibliographical references (page 40)