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

authors: Henderson, William

subjects: chemistry

abstract: 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)].

text: ‘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)].

year: 2002

title: Interview with Pierre A. Lévy, French philosopher of collective intelligence

authors: Peters, Michael A.

abstract: Pierre A. Lévy is Professor in the Department of Communication, Uni- versity of Ottawa, Canada. He occupies the Canada Research Chair in Collective Intelligence where he is engaged in research on the design of a universal system for semantic addressing of digital documents. He completed his MA at the Sorbonne and his PhD at Ecole des Hautes Etudes en Sciences Sociales (EHESS), Paris. His Habilitation (PhD) was in sciences of information and communication at the Université de Grenoble. Professor Levy studies the concept of collective intelligence and knowl- edge-based societies. He is a world-leading thinker on ‘cyberculture’ and the author of many books, including L’intelligence collective (1994), Qu’est-ce que le virtuel? (1995), Cyber- culture (1997), World Philosophie (2000), Cyberdémocratie (2002), La sphère sémantique (2011), The Semantic Sphere (2011) (Photo: http://arts.uottawa.ca/communication/en/ people/levy-pierre).

text: Interview with Pierre A. Lévy, French philosopher of collective intelligence Pierre A. Lévy is Professor in the Department of Communication, Uni- versity of Ottawa, Canada. He occupies the Canada Research Chair in Collective Intelligence where he is engaged in research on the design of a universal system for semantic addressing of digital documents. He completed his MA at the Sorbonne and his PhD at Ecole des Hautes Etudes en Sciences Sociales (EHESS), Paris. His Habilitation (PhD) was in sciences of information and communication at the Université de Grenoble. Professor Levy studies the concept of collective intelligence and knowl- edge-based societies. He is a world-leading thinker on ‘cyberculture’ and the author of many books, including L’intelligence collective (1994), Qu’est-ce que le virtuel? (1995), Cyber- culture (1997), World Philosophie (2000), Cyberdémocratie (2002), La sphère sémantique (2011), The Semantic Sphere (2011) (Photo: http://arts.uottawa.ca/communication/en/ people/levy-pierre).

year: 2015

title: Ngāti Whakaue Māngai Nui

authors: Hiini, Anaha Te Wheoro

subjects: Ngāti Whakaue Māngai Nui

abstract: Ko Ngāti Whakaue tētehi iwi ahurei o te waka o Te Arawa.  Ko tētehi taha ōna kei ngā tahataha o te kōroto moana o Te Rotorua-nui-a-Kahumatamomoe, i Waingaehe ki Waimihia.  Ko tētehi atu taha ōna kei te ūnga o te waka rongomaiwhiti o Te Arawa, arā ki Maketū.  
Kua whai mana a Ngāti Whakaue i ngā rautau e tū whakahīhī ai rātau hei iwi mana nui i ō rātau pūkenga me ō rātau pūmanawa kia mau tonu tō rātau Whakauetanga, tō rātau ahurea me ā rātau tikanga.   Ko tētehi pūkenga pēnei i te āheinga ki te whakairo i te kupu rōreka, ki te tuitui i te kōrero i whakaputaina ai te kōrero ‘Te Arawa Māngai Nui’.  He mea whakapuaki te kōrero rā e iwi kē ki te whakanui i ngā pūkōrero o ngā paepae o Te Arawa, ka mutu, koirā hoki tētehi pūkenga i hau ai te rongo o Ngāti Whakaue.  
Nā, ko te pūkenga e kōrerohia nei, ko te reo o Ngāti Whakaue.  Ko tōna oranga tonutanga te kaupapa matua o tēnei tuhinga e rangahaua ana i te putanga o te kōrero a tētehi o ngā koroua matatau o te iwi i te tau 1992, arā a Hamuera Mitchell, nāna tonu nei i whakapuaki ‘Ka mate te reo o Ngāti Whakaue ā te tekau tau’.  

Nō reira, he whakatewhatewhahanga tēnei tuhinga o te reo o Ngāti Whakaue o tua, o mohoa noa nei hoki kia mōhiotia ai te oranga, te matenga haeretanga rānei o te reo o te iwi, o ngā hapū, o te hapori, o te kāinga o nāianei, kia tau hoki mehemea āe rānei kua whai hua ngā rautaki reo o mua a Ngāti Whakaue ki te whakarauora i tōna ake reo, ā, ka aha te iwi e anga whakamua ai.  Ka mātaitia te āhua o te reo o Ngāti Whakaue kia mōhiotia mehemea i tika tā Hamera Mitchell i kī ai i te tau 1992, karekau rānei, mehemea rānei he wero kē nāna kia kaua e tukuna e te iwi o Ngāti Whakaue tō rātau reo kia mate.

Ko te tikanga rangahau Pākehā, ko te tikanga rangahau Māori, me ngā tikanga ako reo ka kaha mātaitia i tēnei tuhinga kia tika ai te kohinga o ngā raraunga o tēnei momo rangahau, ngā tikanga matatika a te wānanga, ngā tukanga tātari me te whakahōrapatanga atu i ngā whakataunga o te rangahau.  

Hei āpiti atu, ka kōrerohia ngā kaupapa mātauranga a Ngāti Whakaue, tae noa atu ki ngā tini kaupapa whakarauora reo a te iwi kua whakahaerehia mai i te tau 2005 ki ēnei rangi tonu nei mō te oranga o te reo o Ngāti Whakaue te take e anga tōtika atu ai ki te wetenga o te rautaki reo o mua a Ngāti Whakaue i whakahaerehia ai i ngā tau 2013 ki te tau 2017 i kitea ai ōna pikinga, ōna hekenga, ōna ngoikoretanga me ōna hua.  

Heoi anō, hei whaiwhai noa ake i te rautaki o mua nei, ko ngā mātātuhi kua mahue iho rā, ko te korenga o ngā arotakenga, ko te korenga o ngā pūrongo, ko te korenga o ētehi taunakitanga ā-tuhi nei, ko te korenga o tētehi aha kē atu rānei kia kitea he hua, he pikinga, he hekenga, he aha rānei.  Ahakoa tērā raru, nā te kitenga me te rongotanga o te pikinga haeretanga o te āhua o te reo, nā ngā kōrero ā-waha me ngā kauhau a ētehi mō ngā hua i puta ai i te rautaki reo o mua a Ngāti Whakaue i mana ai te whakahaumanutanga o te reo o ngā paepae o te iwi.

Nā te mea ko te reo Māori te remurere o te kaituhi nei, kua tekau mā waru tau ia e whai ana i te kaupapa i a ia e whakaako ana, i a ia e wānanga ana, i a ia hoki e whakapau kaha ana ki te whakaora anō i te reo Māori, kua whakaritea e ia tētehi rautaki reo hou e toru tekau tau te roa hei kōkiri mā te iwi e ora rawa atu anō ai te reo o Ngāti Whakaue, e whai hua anō ai hoki te whakapuakitanga o te kōrero rā ‘Te Arawa Māngai Nui’, hei tohu whakanui i ngā pūkenga kōrero o te iwi.

E ai ki te kōrero, ‘he tīmohea kua pakari’.  Nā roto i te āta rangahaua o te kaupapa nei i mōhio ai e ora tonu nei te reo o Ngāti Whakaue, heoi, kāore e pērā rawa te kaha o te oranga i te wā i a kui mā, i a koro mā.  Ahakoa te kōrero mō te matenga haeretanga o te reo o Ngāti Whakaue, nā ngā kaupapa whakaora reo a te iwi i ngā tau i piki anō ai te oranga o te reo, ka mutu, mā te whakahaerenga tonutanga o ngā wānanga nei e ora tonu anō ai te reo.

text: Ngāti Whakaue Māngai Nui Ko Ngāti Whakaue tētehi iwi ahurei o te waka o Te Arawa.  Ko tētehi taha ōna kei ngā tahataha o te kōroto moana o Te Rotorua-nui-a-Kahumatamomoe, i Waingaehe ki Waimihia.  Ko tētehi atu taha ōna kei te ūnga o te waka rongomaiwhiti o Te Arawa, arā ki Maketū.  
Kua whai mana a Ngāti Whakaue i ngā rautau e tū whakahīhī ai rātau hei iwi mana nui i ō rātau pūkenga me ō rātau pūmanawa kia mau tonu tō rātau Whakauetanga, tō rātau ahurea me ā rātau tikanga.   Ko tētehi pūkenga pēnei i te āheinga ki te whakairo i te kupu rōreka, ki te tuitui i te kōrero i whakaputaina ai te kōrero ‘Te Arawa Māngai Nui’.  He mea whakapuaki te kōrero rā e iwi kē ki te whakanui i ngā pūkōrero o ngā paepae o Te Arawa, ka mutu, koirā hoki tētehi pūkenga i hau ai te rongo o Ngāti Whakaue.  
Nā, ko te pūkenga e kōrerohia nei, ko te reo o Ngāti Whakaue.  Ko tōna oranga tonutanga te kaupapa matua o tēnei tuhinga e rangahaua ana i te putanga o te kōrero a tētehi o ngā koroua matatau o te iwi i te tau 1992, arā a Hamuera Mitchell, nāna tonu nei i whakapuaki ‘Ka mate te reo o Ngāti Whakaue ā te tekau tau’.  

Nō reira, he whakatewhatewhahanga tēnei tuhinga o te reo o Ngāti Whakaue o tua, o mohoa noa nei hoki kia mōhiotia ai te oranga, te matenga haeretanga rānei o te reo o te iwi, o ngā hapū, o te hapori, o te kāinga o nāianei, kia tau hoki mehemea āe rānei kua whai hua ngā rautaki reo o mua a Ngāti Whakaue ki te whakarauora i tōna ake reo, ā, ka aha te iwi e anga whakamua ai.  Ka mātaitia te āhua o te reo o Ngāti Whakaue kia mōhiotia mehemea i tika tā Hamera Mitchell i kī ai i te tau 1992, karekau rānei, mehemea rānei he wero kē nāna kia kaua e tukuna e te iwi o Ngāti Whakaue tō rātau reo kia mate.

Ko te tikanga rangahau Pākehā, ko te tikanga rangahau Māori, me ngā tikanga ako reo ka kaha mātaitia i tēnei tuhinga kia tika ai te kohinga o ngā raraunga o tēnei momo rangahau, ngā tikanga matatika a te wānanga, ngā tukanga tātari me te whakahōrapatanga atu i ngā whakataunga o te rangahau.  

Hei āpiti atu, ka kōrerohia ngā kaupapa mātauranga a Ngāti Whakaue, tae noa atu ki ngā tini kaupapa whakarauora reo a te iwi kua whakahaerehia mai i te tau 2005 ki ēnei rangi tonu nei mō te oranga o te reo o Ngāti Whakaue te take e anga tōtika atu ai ki te wetenga o te rautaki reo o mua a Ngāti Whakaue i whakahaerehia ai i ngā tau 2013 ki te tau 2017 i kitea ai ōna pikinga, ōna hekenga, ōna ngoikoretanga me ōna hua.  

Heoi anō, hei whaiwhai noa ake i te rautaki o mua nei, ko ngā mātātuhi kua mahue iho rā, ko te korenga o ngā arotakenga, ko te korenga o ngā pūrongo, ko te korenga o ētehi taunakitanga ā-tuhi nei, ko te korenga o tētehi aha kē atu rānei kia kitea he hua, he pikinga, he hekenga, he aha rānei.  Ahakoa tērā raru, nā te kitenga me te rongotanga o te pikinga haeretanga o te āhua o te reo, nā ngā kōrero ā-waha me ngā kauhau a ētehi mō ngā hua i puta ai i te rautaki reo o mua a Ngāti Whakaue i mana ai te whakahaumanutanga o te reo o ngā paepae o te iwi.

Nā te mea ko te reo Māori te remurere o te kaituhi nei, kua tekau mā waru tau ia e whai ana i te kaupapa i a ia e whakaako ana, i a ia e wānanga ana, i a ia hoki e whakapau kaha ana ki te whakaora anō i te reo Māori, kua whakaritea e ia tētehi rautaki reo hou e toru tekau tau te roa hei kōkiri mā te iwi e ora rawa atu anō ai te reo o Ngāti Whakaue, e whai hua anō ai hoki te whakapuakitanga o te kōrero rā ‘Te Arawa Māngai Nui’, hei tohu whakanui i ngā pūkenga kōrero o te iwi.

E ai ki te kōrero, ‘he tīmohea kua pakari’.  Nā roto i te āta rangahaua o te kaupapa nei i mōhio ai e ora tonu nei te reo o Ngāti Whakaue, heoi, kāore e pērā rawa te kaha o te oranga i te wā i a kui mā, i a koro mā.  Ahakoa te kōrero mō te matenga haeretanga o te reo o Ngāti Whakaue, nā ngā kaupapa whakaora reo a te iwi i ngā tau i piki anō ai te oranga o te reo, ka mutu, mā te whakahaerenga tonutanga o ngā wānanga nei e ora tonu anō ai te reo.

year: 2020