title: Synthesis and characterisation of novel ferrocenyl compounds

authors: Alley, Steven R.

abstract: The ferrocenyl phosphonate mono-ester FcCH₂P(O)(OPh)OH 1 (Fc = ferrocenyl) was prepared from FcCH₂P(O)(OPh)₂. The related mono-ester FcCH₂P(O)(OEt)OH 2 was prepared by the reaction of FcCH₂NMe₃I with diethyl phosphite. The ferrocenyl phosphonic acids FcP(O)(OH)₂ 3, FcCH₂P(O)(OH)₂ 4, FcCH₂CH₂P(O)(OH)₂ 5, 1,1'-Fc' [P(O)(OH)₂]₂ 6 and 1,1'-Fc'[CH₂P(O)(OH)₂]₂ 7 were synthesised by hydrolysis of the corresponding phosphonate esters. X-ray crystal structure determinations were carried out for compounds 4 and 7. The ferrocenyl phenylphosphonate esters FcP(O)(OPh)₂ 8 and 1,1'-Fc'[P(O)(OPh)₂]₂ 9 were also synthesised and characterised. The ferrocenyl arsonic acid FcCH₂CH₂AѕP(O)(OH)₂ 10 was prepared by the reaction of FcCH₂CH₂Br with Na₃AѕO₃. The behaviour of 10 and the arsenic acids PhAѕ(O)(OH)₂, 2-NH₂-(C₆H₄)Aѕ(O)(OH)₂ and Me₂Aѕ(O)(OH) in negative ion ESMS was investigated in some depth. The carbon-arsenic bond in these compounds was found to cleave at moderate cone voltages.

The bis(triphenylphosphine)platinum complexes (Ph₃P)₂PtO₃PR (R = Fc 11,CH2Fc 12, CH₂CH₂Fc 13) and 1,1'-Fc'[PO₃Pt(PPh₃)₂]₂ 14 were prepared and characterised. Single crystal structural determination of these compounds showed the expected chelation of the ferrocenyl phosphonate ligand to the platinum centre.

The reduction of various ferrocenyl ethylphosphonate esters gave the known primary ferrocenyl phosphines FcCH₂PH₂ 15, FcPH₂ 16, and 1,1'-Fc'[PH₂]₂ 17 in high yield. In addition the novel ferrocenyl phosphines FcCH₂CH₂PH₂ 18, 1,1'-Fc'[CH₂PH₂]₂ 19, 1,2'-Fc'[CH₂PH₂]₂ 20 and the ferrocenyl arsine FcCH₂CH₂AѕH₂ 25 were prepared and characterised. The X-ray crystal structure determination was carried out for 25. This is one of the few structures known for primary arsine compounds. The crystal structure of 18 was found to be isomorphous with that of 25. The stability of phosphines 15-20 toward air oxidation was investigated using ³¹P nmr. The phosphines 18, 19 and 20 were found to be remarkably stable in air. The stability of 25 toward oxidation in air was investigated using elemental analysis. The arsine showed appreciable stability in air despite the sterically unencumbered nature of the arsine group.

Reaction of 19 and 20 with (Pip)Mo(CO)₄ (Pip = Piperidine) and (thf)Mo(CO)₅ resulted in the complexes, 1,2'-Fc'[CH₂PH₂]₂Mo(CO)₄ 21, 1,1'Fc'[CH₂PH₂]₂Mo(CO)₄ 22, 1,1'-Fc'[CH₂PH₂Mo(CO)₅]₂ 23, and 1,2'-Fc'[CH₂PH₂Mo(CO)₅]₂ 24 which were routinely characterised. A by-product of the synthesis of 22 was the larger oligomer [1,1'-Fc'[CH₂PH₂]₂Mo(CO)₄]₂ 22a which was identified by ESMS.

The chemical oxidation of 15 was undertaken using H₂O₂ and monitored by ³¹P nmr. Oxidation of the phosphine to phosphine oxide and phosphinic acid products was observed. Excess oxidant led to the oxidation of the ferrocene group and decomposition of the sample. The compounds FcCH₂P(O)H₂ 26 and FcCH₂P(O)(OH)H 27 were prepared and characterised by nmr and ESMS.

The ferrocenyl hydroxymethyl phosphines FcP(CH₂OH)₂ 28 and 1,1'-Fc'[P(CH₂OH)₂]₂ 29 were prepared by the reaction of 16 and 17 with formaldehyde. The crystal structure of 28 was determined and compared with that of the known compound ferrocenyl hydroxymethyl phosphine FcCH₂P(CH₂OH)₂.

The hydroxymethyl phosphine chalcogenides FcP(O)(CH₂OH)₂ 30, FcP(S)(CH₂OH)₂ 31 and FcP(Se)(CH₂OH)₂ 32 were prepared and fully characterised. The crystal structures of 30 and 31 were determined from single crystal X-ray data. The structure of 32 was found to be isomorphous with that of 31. Hydrogen bonding networks in the structures of 30 and 31 were compared to each other and to other analogous compounds. The hydroxymethyl phosphine chalcogenides 1,1'-Fc'[P(O)(CH₂OH)₂]₂ 33, 1,1'-Fc'[P(S)(CH₂OH)₂]₂ 34 and 1,1'-Fc'[P(Se)(CH₂OH)₂]₂ 35 were also prepared and characterised.

The platinum complex [FcP(CH₂OH)₂]₂PtCl₂ 36 was synthesised by the reaction of 28 and (COD)PtCl₂. Reaction of 29 with (COD)MCl₂ (M = Pt and Pd) gave the analogous metal complexes, 1,1'-Fc'[P(CH₂OH)₂]₂MCl₂ which were unable to be fully characterised. The platinum and palladium complexes of ferrocenyl hydroxymethylphosphines were found to form [M+Cl⁻]⁻ ions under ESMS conditions.

text: Synthesis and characterisation of novel ferrocenyl compounds The ferrocenyl phosphonate mono-ester FcCH₂P(O)(OPh)OH 1 (Fc = ferrocenyl) was prepared from FcCH₂P(O)(OPh)₂. The related mono-ester FcCH₂P(O)(OEt)OH 2 was prepared by the reaction of FcCH₂NMe₃I with diethyl phosphite. The ferrocenyl phosphonic acids FcP(O)(OH)₂ 3, FcCH₂P(O)(OH)₂ 4, FcCH₂CH₂P(O)(OH)₂ 5, 1,1'-Fc' [P(O)(OH)₂]₂ 6 and 1,1'-Fc'[CH₂P(O)(OH)₂]₂ 7 were synthesised by hydrolysis of the corresponding phosphonate esters. X-ray crystal structure determinations were carried out for compounds 4 and 7. The ferrocenyl phenylphosphonate esters FcP(O)(OPh)₂ 8 and 1,1'-Fc'[P(O)(OPh)₂]₂ 9 were also synthesised and characterised. The ferrocenyl arsonic acid FcCH₂CH₂AѕP(O)(OH)₂ 10 was prepared by the reaction of FcCH₂CH₂Br with Na₃AѕO₃. The behaviour of 10 and the arsenic acids PhAѕ(O)(OH)₂, 2-NH₂-(C₆H₄)Aѕ(O)(OH)₂ and Me₂Aѕ(O)(OH) in negative ion ESMS was investigated in some depth. The carbon-arsenic bond in these compounds was found to cleave at moderate cone voltages.

The bis(triphenylphosphine)platinum complexes (Ph₃P)₂PtO₃PR (R = Fc 11,CH2Fc 12, CH₂CH₂Fc 13) and 1,1'-Fc'[PO₃Pt(PPh₃)₂]₂ 14 were prepared and characterised. Single crystal structural determination of these compounds showed the expected chelation of the ferrocenyl phosphonate ligand to the platinum centre.

The reduction of various ferrocenyl ethylphosphonate esters gave the known primary ferrocenyl phosphines FcCH₂PH₂ 15, FcPH₂ 16, and 1,1'-Fc'[PH₂]₂ 17 in high yield. In addition the novel ferrocenyl phosphines FcCH₂CH₂PH₂ 18, 1,1'-Fc'[CH₂PH₂]₂ 19, 1,2'-Fc'[CH₂PH₂]₂ 20 and the ferrocenyl arsine FcCH₂CH₂AѕH₂ 25 were prepared and characterised. The X-ray crystal structure determination was carried out for 25. This is one of the few structures known for primary arsine compounds. The crystal structure of 18 was found to be isomorphous with that of 25. The stability of phosphines 15-20 toward air oxidation was investigated using ³¹P nmr. The phosphines 18, 19 and 20 were found to be remarkably stable in air. The stability of 25 toward oxidation in air was investigated using elemental analysis. The arsine showed appreciable stability in air despite the sterically unencumbered nature of the arsine group.

Reaction of 19 and 20 with (Pip)Mo(CO)₄ (Pip = Piperidine) and (thf)Mo(CO)₅ resulted in the complexes, 1,2'-Fc'[CH₂PH₂]₂Mo(CO)₄ 21, 1,1'Fc'[CH₂PH₂]₂Mo(CO)₄ 22, 1,1'-Fc'[CH₂PH₂Mo(CO)₅]₂ 23, and 1,2'-Fc'[CH₂PH₂Mo(CO)₅]₂ 24 which were routinely characterised. A by-product of the synthesis of 22 was the larger oligomer [1,1'-Fc'[CH₂PH₂]₂Mo(CO)₄]₂ 22a which was identified by ESMS.

The chemical oxidation of 15 was undertaken using H₂O₂ and monitored by ³¹P nmr. Oxidation of the phosphine to phosphine oxide and phosphinic acid products was observed. Excess oxidant led to the oxidation of the ferrocene group and decomposition of the sample. The compounds FcCH₂P(O)H₂ 26 and FcCH₂P(O)(OH)H 27 were prepared and characterised by nmr and ESMS.

The ferrocenyl hydroxymethyl phosphines FcP(CH₂OH)₂ 28 and 1,1'-Fc'[P(CH₂OH)₂]₂ 29 were prepared by the reaction of 16 and 17 with formaldehyde. The crystal structure of 28 was determined and compared with that of the known compound ferrocenyl hydroxymethyl phosphine FcCH₂P(CH₂OH)₂.

The hydroxymethyl phosphine chalcogenides FcP(O)(CH₂OH)₂ 30, FcP(S)(CH₂OH)₂ 31 and FcP(Se)(CH₂OH)₂ 32 were prepared and fully characterised. The crystal structures of 30 and 31 were determined from single crystal X-ray data. The structure of 32 was found to be isomorphous with that of 31. Hydrogen bonding networks in the structures of 30 and 31 were compared to each other and to other analogous compounds. The hydroxymethyl phosphine chalcogenides 1,1'-Fc'[P(O)(CH₂OH)₂]₂ 33, 1,1'-Fc'[P(S)(CH₂OH)₂]₂ 34 and 1,1'-Fc'[P(Se)(CH₂OH)₂]₂ 35 were also prepared and characterised.

The platinum complex [FcP(CH₂OH)₂]₂PtCl₂ 36 was synthesised by the reaction of 28 and (COD)PtCl₂. Reaction of 29 with (COD)MCl₂ (M = Pt and Pd) gave the analogous metal complexes, 1,1'-Fc'[P(CH₂OH)₂]₂MCl₂ which were unable to be fully characterised. The platinum and palladium complexes of ferrocenyl hydroxymethylphosphines were found to form [M+Cl⁻]⁻ ions under ESMS conditions.

year: 2001

title: Taste predicates and retraction data: An improved framework

authors: Wyatt, Jeremy

abstract: Predicates of personal taste (PPT), which include words like ‘tasty,’ ‘fun,’ and ‘cool,’ have been at the centre of a set of lively, interdisciplinary debates spanning the past 20 years. Over this period, philosophers and linguists have developed five major accounts of what PPT mean and the sort of truth (if any) for which assertions involving PPT are apt. In this talk, I will explore one of the main empirical diagnostics that should be used in evaluating the ‘big five’ analyses of PPT, which involves considerations about retraction. After setting out the ‘big five’ analyses, I'll review the most influential account of why retraction data matter in the PPT debates, which comes from John MacFarlane. I take MacFarlane’s account to suffer from two significant problems, and after identifying them, I’ll develop an improved framework for thinking about retraction data and PPT. I'll then draw on this improved framework in reframing the significance of our current empirical data.

text: Taste predicates and retraction data: An improved framework Predicates of personal taste (PPT), which include words like ‘tasty,’ ‘fun,’ and ‘cool,’ have been at the centre of a set of lively, interdisciplinary debates spanning the past 20 years. Over this period, philosophers and linguists have developed five major accounts of what PPT mean and the sort of truth (if any) for which assertions involving PPT are apt. In this talk, I will explore one of the main empirical diagnostics that should be used in evaluating the ‘big five’ analyses of PPT, which involves considerations about retraction. After setting out the ‘big five’ analyses, I'll review the most influential account of why retraction data matter in the PPT debates, which comes from John MacFarlane. I take MacFarlane’s account to suffer from two significant problems, and after identifying them, I’ll develop an improved framework for thinking about retraction data and PPT. I'll then draw on this improved framework in reframing the significance of our current empirical data.

year: 2022

title: The Wairua of Self: A Path of Love, Simplicity, and Connectedness

authors: Frishman, Lezlie

subjects: love

abstract: Love is an action of freedom until something else steps in – often fear – that insists we create a box of survival. Whether self-imposed, forced, or chosen, it is interesting to notice how we limit ourselves with love. This thesis examines love; love in its purest intent and creation as the simplest way to live. An analysis of personal experiences, illuminated by psychological, mythological, philosophical, and spiritual literature, suggests that living from a place of love can be accomplished through a dedicated journeying back to the Self. The Māori myth of Tāne-Mahuta and Hine-Tītama shows the significance of releasing shame, as well as how a tragic situation might offer a catalytic possibility that shifts a core belief about one’s self. The complications of love that are self-created through loss and grief can easily mask the barely underlying truth of love in its nakedness. Reconnecting with this underlying truth, aroha in its purest sense, is essential for healing and allows for increased connection with the Divine. Doing so is often a difficult task, as hypocrisies fueled by fear and perpetuated by blame are bountiful. When love is used as an instrument and convenience in order to defend a closely held idea, person, or way of life, one often moves further from their true Self, thus surrendering their deepest power and knowing of love. The silent assault of expectations, power, will, and control can turn love into a complication. The complications of being utterly human only serve to further obscure love. Within families, how one initially learns love is often complicated by interrupted attachment, causing rebellion and the need to look for love elsewhere. The components of Tikkun Olam, aroha, mikveh, and wairua of spirit, are intertwined and interconnected, such that the delineation between cultures and spiritual beliefs cannot be divided as oppositional forces. The denominator lives in the magnitude of love for all that has been created; beginning with the Self. In setting the foundation of self-love and allowing it to settle into the fractures and rifts of porousness, love may then be extended without attachment. When freely proffered without agenda, love will seep into every curve of the universe; thus, changing the world. Through the practice of mindfulness and loving-kindness, perception can change. It is this change in perception which can return love to its origin of simplicity. This thesis is a story of love.

text: The Wairua of Self: A Path of Love, Simplicity, and Connectedness Love is an action of freedom until something else steps in – often fear – that insists we create a box of survival. Whether self-imposed, forced, or chosen, it is interesting to notice how we limit ourselves with love. This thesis examines love; love in its purest intent and creation as the simplest way to live. An analysis of personal experiences, illuminated by psychological, mythological, philosophical, and spiritual literature, suggests that living from a place of love can be accomplished through a dedicated journeying back to the Self. The Māori myth of Tāne-Mahuta and Hine-Tītama shows the significance of releasing shame, as well as how a tragic situation might offer a catalytic possibility that shifts a core belief about one’s self. The complications of love that are self-created through loss and grief can easily mask the barely underlying truth of love in its nakedness. Reconnecting with this underlying truth, aroha in its purest sense, is essential for healing and allows for increased connection with the Divine. Doing so is often a difficult task, as hypocrisies fueled by fear and perpetuated by blame are bountiful. When love is used as an instrument and convenience in order to defend a closely held idea, person, or way of life, one often moves further from their true Self, thus surrendering their deepest power and knowing of love. The silent assault of expectations, power, will, and control can turn love into a complication. The complications of being utterly human only serve to further obscure love. Within families, how one initially learns love is often complicated by interrupted attachment, causing rebellion and the need to look for love elsewhere. The components of Tikkun Olam, aroha, mikveh, and wairua of spirit, are intertwined and interconnected, such that the delineation between cultures and spiritual beliefs cannot be divided as oppositional forces. The denominator lives in the magnitude of love for all that has been created; beginning with the Self. In setting the foundation of self-love and allowing it to settle into the fractures and rifts of porousness, love may then be extended without attachment. When freely proffered without agenda, love will seep into every curve of the universe; thus, changing the world. Through the practice of mindfulness and loving-kindness, perception can change. It is this change in perception which can return love to its origin of simplicity. This thesis is a story of love.

year: 2011