title: Platinum(II) complexes of chelating and monodentate thiourea monoanions incorporating chiral, fluorescent or chromophoric groups

authors: Henderson, William

subjects: Crystal structures

abstract: The reaction of cis-[PtCl2(PPh3)2] with trisubstituted thioureas [R1R2NC(=S)NHR3] in refluxing methanol with triethylamine base, followed by addition of NaBPh4 gives the salts [Pt{SC(=NR1R2)NR3}(PPh3)2]BPh4 in high yield; a range of thiourea substituents, including chiral, fluorescent and chromophoric groups can be incorporated. The azo dye-derived complex [Pt{SC(=N(CH2CH2)2O)NC6H4N=NC6H4NMe2}(PPh3)2]BPh4 has been characterised by a single-crystal X-ray diffraction study. The formation of a fluorescein-derivatised platinum-thiourea complex is also described. Reaction of cis-[PtCl2(PPh3)2] with PhNHC(S)NHPh or EtNHC(S)NHEt, triethylamine and NaBPh4 gives, respectively, [Pt{SC(=NHPh)NPh}(PPh3)2]+ and the known cation [Pt{SC(=NHEt)NEt}(PPh3)2]+, isolated as tetraphenylborate salts. Reaction of cis-[PtCl2(PPh3)2] with an excess of Na[MeNHC(S)NCN] in methanol gives the bis(thiourea monoanion) complex trans-[Pt{SC(=N---CN)NHMe}2(PPh3)2], characterised by NMR spectroscopy and an X-ray crystal structure determination. When cis-[PtCl2(PPh3)2] is reacted with 1 equiv. of Na[MeNHC(S)N---CN] in methanol, with added NaBPh4, a mixture of isomers of the [Pt{SC(=NHCN)NMe}(PPh3)2]+ cation is obtained.

text: Platinum(II) complexes of chelating and monodentate thiourea monoanions incorporating chiral, fluorescent or chromophoric groups The reaction of cis-[PtCl2(PPh3)2] with trisubstituted thioureas [R1R2NC(=S)NHR3] in refluxing methanol with triethylamine base, followed by addition of NaBPh4 gives the salts [Pt{SC(=NR1R2)NR3}(PPh3)2]BPh4 in high yield; a range of thiourea substituents, including chiral, fluorescent and chromophoric groups can be incorporated. The azo dye-derived complex [Pt{SC(=N(CH2CH2)2O)NC6H4N=NC6H4NMe2}(PPh3)2]BPh4 has been characterised by a single-crystal X-ray diffraction study. The formation of a fluorescein-derivatised platinum-thiourea complex is also described. Reaction of cis-[PtCl2(PPh3)2] with PhNHC(S)NHPh or EtNHC(S)NHEt, triethylamine and NaBPh4 gives, respectively, [Pt{SC(=NHPh)NPh}(PPh3)2]+ and the known cation [Pt{SC(=NHEt)NEt}(PPh3)2]+, isolated as tetraphenylborate salts. Reaction of cis-[PtCl2(PPh3)2] with an excess of Na[MeNHC(S)NCN] in methanol gives the bis(thiourea monoanion) complex trans-[Pt{SC(=N---CN)NHMe}2(PPh3)2], characterised by NMR spectroscopy and an X-ray crystal structure determination. When cis-[PtCl2(PPh3)2] is reacted with 1 equiv. of Na[MeNHC(S)N---CN] in methanol, with added NaBPh4, a mixture of isomers of the [Pt{SC(=NHCN)NMe}(PPh3)2]+ cation is obtained.

year: 2001-08-01

title: Future intentions, plans, and the problem of Buridan's Ass

authors: Ulatowski, Joseph W.

abstract: Suppose that:
1. an agent, S, is able to choose only one option, x or y;
2. S prefers neither x nor y in comparison to the other; and
3. S prefers having at least one of x or y to having none.1
Call this “the problem of Buridan’s Ass.” A theory of practical reasoning is supposed to tell us what to do. Which option, x or y, should S choose? Which theory of practical reasoning tells S to choose that option? While we are capable of overcoming the above situation, it seems that our choosing to act did not rely upon a theory of practical reasoning.
In response to the puzzle above, I show how Davidson’s theory faces a pair of difficulties, which are the result of his overly weak conception of the role of intentions and plans in practical reasoning. On one hand, Davidson’s theory seems unable to accommodate the possibility of a future intention in the face of equally desirable future options, and, on the other hand, his theory cannot ensure that rational intentions are agglomerative. Upon further inspection, however, it appears that Davidson’s theory is not an overly weak conception since he does seem to rule out the role of plans in practical reasoning. But even including plans in practical reasoning, as Bratman’s theory of intention does, fails to solve the seemingly insoluble problem of equipollent preference.

text: Future intentions, plans, and the problem of Buridan's Ass Suppose that:
1. an agent, S, is able to choose only one option, x or y;
2. S prefers neither x nor y in comparison to the other; and
3. S prefers having at least one of x or y to having none.1
Call this “the problem of Buridan’s Ass.” A theory of practical reasoning is supposed to tell us what to do. Which option, x or y, should S choose? Which theory of practical reasoning tells S to choose that option? While we are capable of overcoming the above situation, it seems that our choosing to act did not rely upon a theory of practical reasoning.
In response to the puzzle above, I show how Davidson’s theory faces a pair of difficulties, which are the result of his overly weak conception of the role of intentions and plans in practical reasoning. On one hand, Davidson’s theory seems unable to accommodate the possibility of a future intention in the face of equally desirable future options, and, on the other hand, his theory cannot ensure that rational intentions are agglomerative. Upon further inspection, however, it appears that Davidson’s theory is not an overly weak conception since he does seem to rule out the role of plans in practical reasoning. But even including plans in practical reasoning, as Bratman’s theory of intention does, fails to solve the seemingly insoluble problem of equipollent preference.

year: 2021

title: Taupiri rau kotahi - Taupiri rau manomano

authors: Sam-Turner, Hiko Akuhata Te Ngoungou Raniera

subjects: Taupiri marae

abstract: Kua roa nei te paepae o Taupiri marae e noho mokemoke ana, i te nuinga o te waa kaaore he tangata hei kawe i ngaa tikanga, aa, kua waiho maa te tokoiti e moohio ana me peewhea te whakahaere tika i ngaa tikanga o te marae. I te nuinga o te waa e waimarie ana maatou mehemea ka tae atu ngaa taangata e rua ki te manaaki i te mauri o te paepae moo te roanga ake o te kaupapa, ahakoa tangihanga mai, huritau mai, aha atu raanei.
I ngaa tau kua kaha kitea ahau te toimaha o teeraa o ngaa haepapa ka taka ki runga i te tokoiti. Naa teenaa, ka hua ake te uho o teenei o ngaa kaupapa rangahau, he waihanga i teetehi rautaki whaikoorero e piki ake ai ngaa nama o te hunga kawe i teenei aahuatanga. Ko taa te tuhingaroa nei he waiho i eetehi moohiotanga hei aawhina, hei whakapakari, hei whakamaamaa i ngaa aahuatanga ka tau ki runga i ngaa taangata whaikoorero. Kua waihotia e au eetehi kura hei aarahi, hei aawhina i ngaa whaanau o te marae, heoti, te hunga e piikoko ana ki te kawe i ngaa taonga o too taatou ahurea.
Ko te tino take kua ahu peenei taku rangahau kia moohio pai ngaa whakatupuranga ki eenei maatauranga, heoti, kia moohio pai ngaa whakatupuranga me peewhea te whakahaere i eenei aahuatanga. I runga anoo i te tuupono ka tae mai ki te waa me manaaki te reanga rangatahi i te paepae, ka taka raanei te haepapa whakahaere paepae ki a maatou te hunga rangatahi, ko te wawata ia ka aawhina teenei tuhingaroa i a taatou. Kaaore e kore hei ngaa tau e heke mai nei ka kii pohapoha te paepae o Taupiri marae i te hunga e moohio ana ki te whakatakoto i aana kupu, ki te whaikoorero. Koia te take i hua mai te ingoa o teenei o ngaa tuhingaroa, maa te whaangai i te rau kotahi ko te whaainga ia aa toona waa ka hora katoa eeraa maatauranga ki ngaa rau manomano.
“Hei aha te pae nekeneke, waiho mai raa ki ahau he pae kounga, he pae motuhake”

text: Taupiri rau kotahi - Taupiri rau manomano Kua roa nei te paepae o Taupiri marae e noho mokemoke ana, i te nuinga o te waa kaaore he tangata hei kawe i ngaa tikanga, aa, kua waiho maa te tokoiti e moohio ana me peewhea te whakahaere tika i ngaa tikanga o te marae. I te nuinga o te waa e waimarie ana maatou mehemea ka tae atu ngaa taangata e rua ki te manaaki i te mauri o te paepae moo te roanga ake o te kaupapa, ahakoa tangihanga mai, huritau mai, aha atu raanei.
I ngaa tau kua kaha kitea ahau te toimaha o teeraa o ngaa haepapa ka taka ki runga i te tokoiti. Naa teenaa, ka hua ake te uho o teenei o ngaa kaupapa rangahau, he waihanga i teetehi rautaki whaikoorero e piki ake ai ngaa nama o te hunga kawe i teenei aahuatanga. Ko taa te tuhingaroa nei he waiho i eetehi moohiotanga hei aawhina, hei whakapakari, hei whakamaamaa i ngaa aahuatanga ka tau ki runga i ngaa taangata whaikoorero. Kua waihotia e au eetehi kura hei aarahi, hei aawhina i ngaa whaanau o te marae, heoti, te hunga e piikoko ana ki te kawe i ngaa taonga o too taatou ahurea.
Ko te tino take kua ahu peenei taku rangahau kia moohio pai ngaa whakatupuranga ki eenei maatauranga, heoti, kia moohio pai ngaa whakatupuranga me peewhea te whakahaere i eenei aahuatanga. I runga anoo i te tuupono ka tae mai ki te waa me manaaki te reanga rangatahi i te paepae, ka taka raanei te haepapa whakahaere paepae ki a maatou te hunga rangatahi, ko te wawata ia ka aawhina teenei tuhingaroa i a taatou. Kaaore e kore hei ngaa tau e heke mai nei ka kii pohapoha te paepae o Taupiri marae i te hunga e moohio ana ki te whakatakoto i aana kupu, ki te whaikoorero. Koia te take i hua mai te ingoa o teenei o ngaa tuhingaroa, maa te whaangai i te rau kotahi ko te whaainga ia aa toona waa ka hora katoa eeraa maatauranga ki ngaa rau manomano.
“Hei aha te pae nekeneke, waiho mai raa ki ahau he pae kounga, he pae motuhake”

year: 2022